Materials and manufacturing methods

Abstract

The array comprises a support substrate, surface structures protruding from a surface of the support substrate formed or coated with a first material, and a second material deposited on at least some of the surface structures such that the second material is in contact with the first material, wherein the first material, the second material, or the first and second materials are conductive or semiconductive, and the first and second materials at least partially form a composite.

Description

[Technical Field]

[0001] This invention relates to materials and methods for producing materials. In particular, this invention relates to arrays suitable for use as catalysts and methods for forming arrays. This invention further relates to catalysts and methods for forming catalysts. In particular, the catalyst is part of the array structure. [Background technology]

[0002] Catalysts are used to increase reaction rates or to reduce the energy required to initiate or propel a reaction. They are particularly commercially useful in large-scale, general-purpose reactions such as hydrogenation, dehydrogenation, reforming, and oxidation reactions.

[0003] Precious metals such as platinum (Pt) and palladium (Pd) have traditionally been used as high-performance catalysts. However, due to their high price and scarcity, considerable effort has been made to develop substitutes or alternatives. In recent years, the focus has been on improving catalytic performance by combining catalysts with other less valuable materials (see, for example, W. Yu, et al. Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts, Chem. Rev. 2012, 112, 5780-5817).

[0004] International Publication No. 2018106128 (Manufacturing Systems Limited) shows that the catalytic activity of platinum can be enhanced by changing the planar electrode to one with a surface structure to which platinum is applied. [Overview of the Initiative] [Means for solving the problem]

[0005] In the first embodiment: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first material; The second material is deposited on at least some of the surface structures such that the second material is in contact with the first material. An array including the following is provided: Here, the first material, the second material, or the first material and the second material are conductive or semiconductive; Here, the first material and the second material form a composite at least partially.

[0006] In some embodiments, the composite is the product of an electrolytic reaction between a first material and a second material.

[0007] In some embodiments, the electrolytic reaction product is prepared by applying a sufficiently dense current to the array to induce a reaction between the first material and the second material.

[0008] In some embodiments, the composite exhibits a modified electronic structure compared to the first and second materials.

[0009] In some embodiments, the modified electronic structure is indicated by observing the change in linear sweep voltammetry between an array containing the first and second materials and an array further containing the composite.

[0010] In some embodiments, the change in linear sweep voltammetry includes an oxidation or reduction shift to a more positive or negative voltage.

[0011] In some embodiments, the modified electronic structure is shown by observing the changes in energy-dispersive X-ray spectroscopy between an array containing the first and second materials and an array further containing the composite.

[0012] In the second embodiment: A support substrate having a surface structure that protrudes from the surface of the support substrate; and Composite material formed on at least a portion of the surface structure An array including the following is provided: Here: The composite material is the product of the electrolytic reaction of the first material and the second material; The first material, the second material, or the first material and the second material are conductive or semiconducting.

[0013] In some embodiments, the electrolytic reaction product is prepared by applying a sufficiently dense current to the array to induce a reaction between the first material and the second material.

[0014] In the third embodiment: Support substrate; and Surface structures that protrude from the surface of the support substrate; Surface substructures in each of the surface structures A catalyst array is provided which includes the following: The surface substructure contains composite materials; Here, the composite material is formed from at least a first material and a second material during the pretreatment of the catalyst array; and Here, the composite material exhibits a modified electronic structure compared to a mixture of the first and second materials before pretreatment.

[0015] In some embodiments, the composite is prepared by pre-treating the array by applying a bias to the first and second materials.

[0016] In some embodiments, the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0017] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0018] In some embodiments, the modified electronic structure is indicated by observing the changes in the array in energy-dispersive X-ray spectroscopy before and after the application of a bias.

[0019] In the fourth embodiment: A support substrate having a surface structure that protrudes from the surface of the support substrate; and Composite material formed on at least a portion of the surface structure A catalyst array including the following is provided: Here: The composite material is the product of the electrolytic reaction of the first material and the second material; and The surface structure is: Pyramidal structures having a height of less than 100 microns to approximately 10 microns, and a base dimension of approximately 10 microns to approximately 100 microns; and / or A circular or elongated dome-shaped structure with a height of approximately 1000 nm to 1 nm and a diameter of approximately 1000 nm to 1 nm. It has.

[0020] In some embodiments, the electrolytic reaction product is prepared by applying a sufficiently dense current to the array to induce a reaction between the first material and the second material.

[0021] The following are embodiments of the first, second, third, or fourth aspects.

[0022] In some embodiments, the first material is a material that forms a surface structure, or a material on a surface structure.

[0023] In some embodiments, the second material is applied to the first material.

[0024] In some embodiments, the composite material is an intermetallic compound, a polymer-metal composite, an organic-inorganic composite, an alloy, or a polymetallic compound. For example, an alloy can be a metal-element alloy (e.g., carbon, sulfur, or silicon combined with a metal) or a metal-metal alloy.

[0025] In some embodiments, the composite material is an intermetallic compound, where the intermetallic compound is an alloy.

[0026] In the fifth embodiment: Support substrate; A surface structure that protrudes from the surface of the support substrate and is integral with the support substrate; and Surface structure including a composite material formed from at least a first material and a second material A catalyst array comprising the above is provided, and Here, the composite material exhibits a modified electronic structure compared to a mixture of the first and second materials.

[0027] In some embodiments, the first material is the same as the material constituting the substrate, or the first material is a different material from the substrate.

[0028] In some embodiments, the composite is prepared by pre-treating the array by applying a bias to the first and second materials.

[0029] In some embodiments, the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0030] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0031] In some embodiments, the modified electronic structure is indicated by the change in the array in energy-dispersive X-ray spectroscopy before and after the application of a bias.

[0032] In some embodiments, the second material is applied to the first material.

[0033] In some embodiments, the composite material is an intermetallic compound, a polymer-metal composite, an organic-inorganic composite, an alloy, or a polymetallic compound. For example, the alloy can be a metal-element alloy (e.g., carbon, sulfur, or silicon combined with a metal) or a metal-metal alloy.

[0034] In some embodiments, the composite material is an intermetallic compound, where the intermetallic compound is an alloy.

[0035] In the sixth embodiment: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first material; The second material is deposited on at least some of the surface structures such that the second material is in contact with the first material. An array including the above is provided, and Here, the first material, the second material, or the first material and the second material are conductive or semiconductive; Here, there is a change in the orbital overlap of the electronic structures of the first material, the second material, or the first material and the second material.

[0036] In some embodiments, changes in the orbital overlap of the electronic structure are demonstrated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0037] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0038] In some embodiments, changes in the orbital overlap of the electronic structure are demonstrated by observing the changes in energy-dispersive X-ray spectroscopy of the array before and after the application of a bias.

[0039] In the seventh embodiment: Support substrate; A surface structure that protrudes from the surface of the support substrate and is integral with the support substrate; and A surface structure having catalytic properties and comprising a composite material formed from at least a first material and a second material. A catalyst array is provided which includes the following: Here, the composite material exhibits a modified electronic structure compared to a mixture of the first and second materials; and Here, the surface structure is 100 / cm 2 It exists on the surface of the support.

[0040] In some embodiments, the first material is the same as the material constituting the substrate, or the first material is a different material from the substrate.

[0041] In some embodiments, the composite is prepared by pre-treating the array by applying a bias to the first and second materials.

[0042] In some embodiments, the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0043] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0044] In some embodiments, the modified electronic structure is indicated by observing the changes in the array in energy-dispersive X-ray spectroscopy before and after the application of a bias.

[0045] In the eighth embodiment: Support substrate; and Surface structures that protrude from the surface of the support substrate; Surface substructures in each of the surface structures A catalyst array comprising the above is provided, and The surface substructure includes a composite material having catalytic properties; Here, The composite material is formed from at least a first material and a second material during the pretreatment of the catalyst array; The composite material exhibits a modified electronic structure compared to the mixture of the first and second materials before pretreatment; and The surface structure is 100 / cm 2 It exists on the surface of the support.

[0046] In some embodiments, the first material is the same as the material constituting the substrate, or the first material is a different material from the substrate.

[0047] In some embodiments, the composite is prepared by pre-treating the array by applying a bias to the first and second materials.

[0048] In some embodiments, the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0049] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0050] In some embodiments, the modified electronic structure is indicated by observing the changes in the array in energy-dispersive X-ray spectroscopy before and after the application of a bias.

[0051] In the ninth embodiment, a method for forming an array is provided, which is The procedure includes the step of applying an electric current between a first electrode and a second electrode in a conductive solution, The first electrode is: Support substrate; Surface structures protruding from the surface of a support substrate formed or coated with a first material; and A second material deposited on at least some of the surface structures in contact with the first material. This includes, and here: The first material, the second material, or the first and second materials are conductive or semiconductive; The applied current density is sufficient to form a composite at least at the interface between the first material and the second material.

[0052] In some embodiments, the first material is a material that forms a surface structure, or a material on a surface structure.

[0053] In some embodiments, the composite is the product of an electrolytic reaction between a first material and a second material.

[0054] In some embodiments, the composite material is an intermetallic compound, a polymer-metal composite, an organic-inorganic composite, an alloy, or a polymetallic compound. For example, the alloy can be a metal-element alloy (e.g., carbon, sulfur, or silicon combined with a metal) or a metal-metal alloy.

[0055] In some embodiments, the composite material is an intermetallic compound, where the intermetallic compound is an alloy.

[0056] In a tenth embodiment, a method for forming a complex is provided, which is: A structure comprising edges and / or vertices, and the step of conducting an electric current between a first material and a second material at the edges and / or vertices, wherein the first material and the second material are in contact, wherein the first and / or second materials are conductive or semiconducting, and wherein the current density at the edges and / or vertices is sufficient to form a composite at the interface between the first material and the second material.

[0057] In some embodiments, the composite is the product of an electrolytic reaction between a first material and a second material.

[0058] In some embodiments, the composite material is an intermetallic compound, a polymer-metal composite, an organic-inorganic composite, an alloy, or a polymetallic compound. For example, the alloy can be a metal-element alloy (e.g., carbon, sulfur, or silicon combined with a metal) or a metal-metal alloy.

[0059] In some embodiments, the composite material is an intermetallic compound, where the intermetallic compound is an alloy.

[0060] In the eleventh embodiment, a method for pre-treating a catalyst array is provided, which is The procedure includes the step of applying a current between the first electrode and the second electrode in a conductive solution sufficient to form a composite from the first material and the second material in the first electrode, the second electrode, or both the first electrode and the second electrode, Here, the catalyst array includes a first electrode, a second electrode, or both the first electrode and the second electrode.

[0061] In some embodiments, the composite is the product of an electrolytic reaction between a first material and a second material.

[0062] In some embodiments, the composite material is an intermetallic compound, a polymer-metal composite, an organic-inorganic composite, an alloy, or a polymetallic compound. For example, the alloy can be a metal-element alloy (e.g., carbon, sulfur, or silicon combined with a metal) or a metal-metal alloy.

[0063] In some embodiments, the composite material is an intermetallic compound, where the intermetallic compound is an alloy.

[0064] In some embodiments, the first electrode and / or the second electrode are: Support substrate; Surface structures protruding from the surface of a support substrate formed or coated with a first material; and A second material deposited on at least some of the surface structures in contact with the first material. Includes, Here, the first material, the second material, or the first material and the second material are conductive or semiconductive.

[0065] In a twelfth embodiment, a method for forming an alloy array is provided, the method is The procedure includes the step of applying an electric current between a first electrode and a second electrode in a conductive solution, The first electrode is: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first alloy component; Second alloying component deposited on the surface structure Includes, Here, the applied current density is sufficient to at least partially form an alloy of the first alloy component and the second alloy component on the surface structure; Here, the alloy array is formed on the first electrode.

[0066] For example, an alloy can be a metal-element alloy (e.g., carbon, sulfur, or silicon combined with a metal) or a metal-metal alloy.

[0067] In the 13th embodiment, a method for forming an array is provided, which is The procedure includes the step of applying an electric current between a first electrode and a second electrode in a conductive solution, The first electrode is: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first material; The second material is deposited on the surface structure such that it is in contact with the first material. Includes, Here, the first material, the second material, or the first material and the second material are conductive or semiconductive; Here, the applied current density is sufficient to distort the energy of the outer shell electrons of the first and second materials when the current is no longer applied.

[0068] In some embodiments, the energy strain of outer shell electrons is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of current.

[0069] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage.

[0070] In some embodiments, the energy distortion of outer shell electrons is demonstrated by observing the change in the array in energy-dispersive X-ray spectroscopy before and after the application of a current.

[0071] In a fourteenth embodiment, a method is provided for pre-treating a catalyst array, comprising the steps of providing a catalyst array, contacting an electrolyte solution with the catalyst array, and applying a bias to the array with a voltage and current for a specific time to form a pre-treated array, wherein the material in the pre-treated array has a modified electronic structure compared to the material before the bias is applied. In this method, the array comprises: a support substrate; surface structures protruding from the surface of the support substrate formed or coated with a first material; and a second material deposited on at least some of the surface structures such that the second material is in contact with the first material.

[0072] In some embodiments, the modified electronic structure has a modified or altered orbital overlap compared to the material before the bias is applied.

[0073] In some embodiments, changes in the orbital overlap of the electronic structure are demonstrated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0074] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0075] In some embodiments, the modified electronic structure is indicated by changes in the energy dispersive X-ray spectroscopy of the array before and after applying a bias.

[0076] In some embodiments, the specific time is from about 0.5 hours to about 200 hours, or from about 1 hour to about 10 hours, or from about 3 hours to about 9 hours.

[0077] In some embodiments, the specific time is at least about 1 second, at least about 1 minute, at least about 5 minutes, at least about 10 minutes or at least about 0.5 hours. In some embodiments of the method of forming an array, the current is applied for from about 1 second to about 1 week, from about 1 second to about 24 hours, from about 1 minute to about 24 hours, from about 5 minutes to about 24 hours, from about 10 minutes to about 24 hours or from about 0.5 hours to about 24 hours. In some embodiments of the method of forming an array, the current is applied for from about 1 hour to about 12 hours.

[0078] In some embodiments, the voltage is from about -20 volts to about +20 volts, or from + / -20 volts to about + / -0.5 volts, or from about + / -10 volts to about + / -0.5. In some embodiments, the voltage is from about -20V to +20V. In some embodiments, it is from about -10V to +10V. In some embodiments, it is from about -5V to +5V. In some embodiments, it is from about -1V to +1V.

[0079] In some embodiments, the current density is 0 A / cm 2 super to about 10 A / cm 2 to about 1 A / cm 2 to about 5 A / cm 2 or about 2 A / cm 2 is.

[0080] In some embodiments, the current density is at least about 0.1 A / cm 2 at least about 0.2 A / cm 2 at least about 0.3 A / cm 2at least about 0.5 A / cm² 2 at least about 0.7 A / cm² 2 , at least about 1 A / cm 2 at least about 1.5 A / cm² 2 That is the case.

[0081] In some embodiments, the current density is approximately 500 A / cm². 2 Less than approximately 100 A / cm² 2 Less than approximately 50 A / cm² 2 Less than approximately 20 A / cm² 2 Less than approximately 15 A / cm² 2 Less than approximately 10 A / cm² 2 Less than approximately 8 A / cm² 2 Less than approximately 5 A / cm² 2 Less than approximately 4 A / cm² 2 Less than approximately 3 A / cm² 2 Less than or approximately 2 A / cm² 2 It is less than.

[0082] In some embodiments, the current density across the first and / or second electrodes is approximately 0.1 to approximately 500 A / cm². 2 ; approx. 0.1~approx. 50A / cm 2 , about 0.1~about 20A / cm 2 , about 0.2~about 20A / cm 2 , about 0.2~about 15A / cm 2 , about 0.5~about 500A / cm 2 , about 0.5~about 50A / cm 2 , about 0.5~about 20A / cm 2 , about 0.5~about 10A / cm 2 , about 0.5~about 8A / cm 2 , about 0.5~about 5A / cm 2 , about 0.5~about 4A / cm 2 , about 1~4A / cm 2 That is the case.

[0083] In some embodiments of this method, the electrolyte is an alkaline electrolyte. In various embodiments, the electrolyte may contain a metal oxide or a metal hydroxide. If the electrolyte contains a metal hydroxide, the metal hydroxide may be sodium hydroxide (NaOH) or potassium hydroxide (KOH). In some embodiments, NaOH or KOH is present in the electrolyte at about 0.5 M to about 10 M, about 2 M to about 8 M, or about 4 M to about 6 M.

[0084] In some embodiments of this method, the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias. In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0085] In some embodiments, the modified electronic structure is indicated by the change in the array in energy-dispersive X-ray spectroscopy before and after the application of a bias.

[0086] In some embodiments of this method, the second material exists in thicknesses of approximately 1 nm to 1 μm, approximately 1 nm to 500 nm, approximately 5 nm to 250 nm, approximately 5 nm to 100 nm, approximately 5 nm to 50 nm, approximately 5 nm to 30 nm, approximately 5 nm to 25 nm, approximately 5 nm to 15 nm, or approximately 5 nm to 10 nm. In some embodiments of this method, the array further comprises alternating layers of the first and second materials, where there are 200 or fewer layers of each material. In some embodiments, each layer of the array has a thickness of 1 to 10 nm.

[0087] In some embodiments, the array comprises layers of a first material and a second material, where these layers are Ni / Pt;Ni / Au;Ni / Co;Ni-supported Co / Pt;Ni-supported Pt / Co;Ni-supported Pt / Ni; and Ni-supported Pt / Ni / Pt / Ni / Pt / Ni / Pt.

[0088] Another 15th embodiment provides a method for forming a catalyst array, the method being The procedure includes the step of applying an electric current between a first electrode and a second electrode in a conductive solution, The first electrode is: Support substrate; and Surface structure that protrudes from the surface of the support substrate and includes a composite material having catalytic properties. Equipped with, and Here: The composite material is formed from a combination of a first material and a second material; The applied current density is sufficient to form a composite material at the interface; and The composite material exhibits a modified electronic structure compared to the combination containing the first and second materials before the application of current.

[0089] In some embodiments, the first material is the same as the material constituting the substrate, or the first material is a different material from the substrate.

[0090] In some embodiments, the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0091] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0092] In some embodiments, the modified electronic structure is indicated by observing the changes in the array in energy-dispersive X-ray spectroscopy before and after the application of a bias.

[0093] To avoid misunderstanding, the following embodiments are applicable to any of the above-described first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelfth, thirteenth, fourteenth, or fifteenth embodiments, or any of the following sixteenth, seventeenth, eighteenth, nineteenth, twenty-first, twenty-second, twenty-third, twenty-fourth, twenty-fifth, or twenty-sixth embodiments.

[0094] In some embodiments, the composite exhibits a modified electronic structure compared to the mixture of the first and second materials before the composite was formed.

[0095] In some embodiments, the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array.

[0096] In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage.

[0097] In some embodiments, the modified electronic structure is indicated by changes in energy-dispersive X-ray spectroscopy of the array.

[0098] In some embodiments, the array is a catalyst.

[0099] In some embodiments, the first material is a conductive material or a semiconductor material.

[0100] In some embodiments, the first material is selected from polymers, organic compounds, inorganic compounds, and metals.

[0101] In some embodiments, the first material is a metal.

[0102] In some embodiments, the second material is selected from polymers, organic compounds, inorganic compounds, and metals.

[0103] In some embodiments, the second material is an s-block element (groups 1 and 2 of the periodic table), a p-block element (groups 13, 14, 15, 16, or 17 of the periodic table), or a d-block metal (transition metal).

[0104] In some embodiments, the second material is selected from alkali metals (Group 1), alkaline earth metals, transition metals, and metalloids.

[0105] In some embodiments, the second material is selected from one or more of the following: C, S, Si, organometallic materials (such as purfilin), carbonaceous materials (e.g., graphene), and fullerenes (such as buckyballs or carbon nanotubes).

[0106] In some embodiments, the second material is deposited, incorporated, or embedded on the surface structure by reduction or oxidation.

[0107] In some embodiments, the second material is deposited, incorporated, or embedded by one or more physical deposition processes such as chemical vapor deposition (CVD), physical vapor deposition, thermal vapor deposition, or plasma CVD. Other methods include cathode arc deposition, electron beam PVD, vapor deposition, closed-space sublimation, pulsed laser deposition, or pulsed electrodeposition. The material can be coated by a series of non-vacuum methods, including sublimation, spray coating, dip coating, spin coating, coating, rotary gravure coating, wet impregnation, slurry, use of organometallic cluster precursors, reductive precipitation, electroless plating, reverse micelle synthesis, and dendrimer-supported synthesis.

[0108] In some embodiments, the conductive solution comprises a second material, which is electrochemically deposited on at least some of the surface structures when a current or bias voltage is applied. In some embodiments, the current or bias voltage is the current or bias voltage that forms the composite. In some embodiments, the current or bias voltage is applied prior to the current or bias voltage that forms the composite.

[0109] In some embodiments, the conductive solution comprises a second material, which, when an electric current is applied, is electrochemically deposited on the edges and / or vertices.

[0110] In some embodiments, the first or second material is a metal.

[0111] In some embodiments, at least one of the first material and the second material is a metal.

[0112] In some embodiments, the inorganic compound is sulfur, carbon (e.g., elemental carbon, graphene, fullerene, or carbon nanotube), or silicon.

[0113] In some embodiments, the first alloying component and the second alloying component are selected from a first material and a second material capable of forming an alloy.

[0114] In some embodiments, the surface structure is integrated with the support substrate.

[0115] In some embodiments, the surface structure is formed integrally with the support substrate.

[0116] In some embodiments, the surface structure is made of the same material as the support substrate.

[0117] In some embodiments, the surface structure is formed from a first material.

[0118] In some embodiments, the support substrate and surface structure are formed from a first material.

[0119] In some embodiments, the support substrate and surface structure are made of different materials.

[0120] In some embodiments, the support substrate includes a composite material, polymer, ceramic, metal, silica, or glass.

[0121] In some embodiments, the first or second material is a metal, and the composite is an alloy.

[0122] In some embodiments, the first material is a metal, and the composite is an alloy.

[0123] In some embodiments, both the first material and the second material are metals.

[0124] In some embodiments, the first material and the second material are both metals, and the composite is an alloy.

[0125] It will be obvious to those skilled in the art that the first and second metals must be different. However, this difference may be solely in their crystal structure. In some embodiments, the first material is a first metal having a first crystal structure, and the second material is the same metal as the first metal but with a different crystal structure.

[0126] In some embodiments, the first material is a first metal.

[0127] In some embodiments, the second material is a second metal.

[0128] In some embodiments, the first material is a first metal, and the second material is a second metal.

[0129] In some embodiments, the support substrate is formed from a first metal.

[0130] In some embodiments, the surface structure is formed from a first metal.

[0131] In some embodiments, the support substrate and surface structure are formed from a first metal.

[0132] In the 16th embodiment: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first metal; The second metal is deposited on at least some of the surface structures such that the second metal is in contact with the first metal. A catalyst array including the following is provided: Here, the first and second metals form an alloy at least partially.

[0133] In some embodiments, the composite is the product of an electrolytic reaction between a first material and a second material.

[0134] In some embodiments, the electrolytic reaction product is prepared by applying a sufficiently dense current to the array to induce a reaction between the first material and the second material.

[0135] In the 17th embodiment: A support substrate having a surface structure that protrudes from the surface of the support substrate; and A composite formed on at least a portion of the surface structure. An array including the following is provided: Here: The complex is the product of the electrolytic reaction between the first metal and the second metal.

[0136] In some embodiments, the electrolytic reaction product is prepared by applying a sufficiently dense current to the array to induce a reaction between the first material and the second material.

[0137] In the 18th embodiment: Support substrate; and Surface structures that protrude from the surface of the support substrate; Surface substructures in each of the surface structures A catalyst array is provided which includes the following: The surface substructure contains composite materials; Here, the composite material is formed from at least a first metal and a second metal during the pretreatment step of the catalyst array; and Here, the composite material exhibits a modified electronic structure compared to the mixture of the first and second metals before the pretreatment step.

[0138] In the 19th embodiment: Support substrate; A surface structure that protrudes from the surface of the support substrate and is integrated with the support substrate. A catalyst array comprising the following is provided: The surface structure includes a composite material formed from at least a first metal and a second metal; Here, the composite material exhibits a modified electronic structure compared to a mixture of the first and second metals.

[0139] In the 20th embodiment: A support substrate having a surface structure that protrudes from the surface of the support substrate; and Composite material formed on at least a portion of the surface structure A catalyst array including the following is provided: Here: The composite material is an electrolytic reaction product of a first metal and a second metal; and The surface structure is: Pyramidal structures having a height of less than 100 microns to approximately 10 microns, and a base dimension of approximately 10 microns to approximately 100 microns; and / or A circular or elongated dome-shaped structure with a height of approximately 1000 nm to 1 nm and a diameter of approximately 1000 nm to 1 nm. It has.

[0140] In some embodiments, the electrolytic reaction product is prepared by applying a sufficiently dense current to the array to induce a reaction between the first material and the second material.

[0141] In the 21st embodiment: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first metal; The second metal is deposited on at least some of the surface structures such that the second metal is in contact with the first metal. An array including the following is provided; and Here, there is a change in the orbital overlap of the electronic structures of the first metal, the second metal, or the first and second metals.

[0142] In the 22nd embodiment, Steps include applying an electric current between a first electrode and a second electrode in a conductive solution. A method for forming a catalyst array including is provided. The first electrode is: Support substrate; Surface structures protruding from the surface of a support substrate formed or coated with a first metal; and The second metal is deposited on the surface structure such that it is in contact with the first metal. Includes, Here, the applied current density is sufficient to form an alloy at least partially on the surface structure.

[0143] In the 23rd embodiment, Steps include applying a current between the first electrode and the second electrode in a conductive solution sufficient to form an intermetallic compound from the first metal and the second metal in the first electrode, the second electrode, or both the first electrode and the second electrode. A method for forming a catalyst array including is provided. The first electrode and / or the second electrode are: Support substrate; Surface structures protruding from the surface of a support substrate formed or coated with a first metal; and The second metal is deposited on at least some of the surface structures such that the second metal is in contact with the first metal. Includes, Here, the catalyst array is formed on the first electrode and / or the second electrode.

[0144] In the 24th embodiment, a method for forming an alloy is provided, The method includes a structure having a rim and / or apex, and the step of conducting an electric current between a first metal and a second metal at the rim and / or apex, wherein the first and second metals are in contact, and wherein the current density at the rim and / or apex is sufficient to form an alloy at the interface between the first material and the second material.

[0145] In the 25th embodiment, a method for pre-treating a catalyst array is provided, which is Steps include applying a current between the first electrode and the second electrode in a conductive solution sufficient to form an intermetallic compound from the first metal and the second metal in the first electrode, the second electrode, or both the first electrode and the second electrode. Includes, Here, the catalyst array includes a first electrode, a second electrode, or both the first electrode and the second electrode.

[0146] In some embodiments, the first electrode and / or the second electrode are: Support substrate; Surface structures protruding from the surface of a support substrate formed or coated with a first metal; and A second metal deposited on at least some of the surface structures in contact with the first metal. Includes.

[0147] In a 26th embodiment, a method is provided for pre-treating a catalyst array, comprising the steps of providing a catalyst array, contacting an electrolyte solution with the catalyst array, and applying a bias to the array with a voltage and current for a specific time to form a pre-treated array, wherein the metal in the pre-treated array has a modified electronic structure compared to the metal before the bias is applied. In this method, the array includes a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with a first metal, and a second metal deposited on at least some of the surface structures such that the second metal is in contact with the first metal.

[0148] In some embodiments, the modified electronic structure has altered orbital overlaps of the metal compared to the metal before the bias is applied.

[0149] In some embodiments, the specific time ranges from approximately 0.5 hours to approximately 200 hours, or from approximately 0.5 hours to approximately 20 hours, or from approximately 1 hour to approximately 10 hours, or from approximately 3 hours to approximately 9 hours.

[0150] In some embodiments, the voltage is approximately -20 volts to approximately +20 volts, or + / -20 volts to approximately + / -0.5 volts, or approximately + / -10 volts to approximately + / -0.5 volts. In some embodiments, the current density is 0 A / cm². 2 Super ~ about 10A / cm 2 , about 1A / cm 2 ~About 5A / cm 2 , or approximately 2 A / cm² 2 That is the case.

[0151] In some embodiments of this method, the electrolyte is an alkaline electrolyte. In various embodiments, the electrolyte may contain a metal oxide or a metal hydroxide. If the electrolyte contains a metal hydroxide, the metal hydroxide may be sodium hydroxide (NaOH) or potassium hydroxide (KOH). In some embodiments, NaOH or KOH is present in the electrolyte at about 0.5 M to about 10 M, about 2 M to about 8 M, or about 4 M to about 6 M.

[0152] In some embodiments of this method, the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias. In some embodiments, the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0153] In some embodiments, the modified electronic structure is indicated by the change in the array in energy-dispersive X-ray spectroscopy before and after the application of a bias.

[0154] In some embodiments of this method, the second metal is present in thicknesses of approximately 1 nm to 1 μm, approximately 1 nm to 500 nm, approximately 5 nm to 250 nm, approximately 5 nm to 100 nm, approximately 5 nm to 50 nm, approximately 5 nm to 30 nm, approximately 5 nm to 25 nm, approximately 5 nm to 15 nm, or approximately 5 nm to 10 nm.

[0155] In some embodiments of this method, the array further comprises alternating layers of a first metal and a second metal, where there are 200 or fewer layers of each metal. In some embodiments, each layer of the array has a thickness of 1 to 10 nm.

[0156] In some embodiments, the array comprises first and second metal layers, and these layers are Ni / Pt;Ni / Au;Ni / Co;Ni-supported Co / Pt;Ni-supported Pt / Co;Ni-supported Pt / Ni; and Ni-supported Pt / Ni / Pt / Ni / Pt / Ni / Pt.

[0157] In some embodiments, the composite, alloy, or intermetallic compound is formed at least partially at the edges and / or vertices of the surface structure.

[0158] In the embodiment, the composite, alloy, or intermetallic compound is formed at the edges and / or vertices of the surface structure.

[0159] In the embodiment, the composite, alloy, or intermetallic compound is preferably formed at the edges and / or vertices of the surface structure.

[0160] In some embodiments, the composite, alloy, or intermetallic compound is formed at the interface between the first material and the second material. In some embodiments, the composite is formed at the interface between the first material and the second material.

[0161] In some embodiments, the first metal is selected from transition metals or post-transition metals.

[0162] In some embodiments, the first metal is Ni, Ti, V, Cr, Fe, Co, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, R h、 Selected from Pd, Ag, Cd, In, Sb, Sn, Cs, Ba, La, Ce, Pr, Nd, W, Os, Ir, Au, Pb, Bi, Ra, U, Pt, and Au.

[0163] In some embodiments, the second metal is different from the first metal and is selected from transition metals or post-transition metals.

[0164] In some embodiments, the second metal differs from the first metal and is Ni, Ti, V, Cr, Fe, Co, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, R h、 Selected from Pd, Ag, Cd, In, Sb, Sn, Cs, Ba, La, Ce, Pr, Nd, W, Os, Ir, Au, Pb, Bi, Ra, U, Pt, and Au.

[0165] In some embodiments, the first metal is Ni. In some embodiments, the first metal is Ni 2θ(200).

[0166] In some embodiments, the first material is Ni and the second material is Pt, or the first material is Pt and the second material is Ni.

[0167] In some embodiments, the first metal is selected from Ni, Cu, Zn, Co, Al, and Ti, and the second metal is selected from Pt, Co, Au, Ni, Ag, Ti, Cr, Cu, Mg, Mn, Fe, and Zn.

[0168] In some embodiments, the first metal is Ni, and the second metal is selected from Pt, Co, or Au.

[0169] In some embodiments, the first and / or second metal is in the form of an oxide, hydride, halide, hydroxide, salt, carbide, organometallic complex, complex, alloy, or cluster.

[0170] In some embodiments, the second metal is in the form of an oxide, hydride, halide, carbide, complex, alloy, or cluster.

[0171] In some embodiments, the second metal is deposited on the surface by evaporation under reduced pressure using a physical vapor deposition (PVD) method that includes E-beam, pulsed laser deposition, sputtering, magnetron sputtering, and physical evaporation of the deposited layer metal by a thermal filament.

[0172] In some embodiments, the second metal is deposited on the surface structure by reduction or oxidation. Reduction or oxidation can be carried out chemically or electrochemically. Alternatively, the material can be coated by a physical deposition process such as chemical vapor deposition (CVD), physical vapor deposition or thermal vapor deposition, or plasma CVD. Alternatively, these materials can be deposited by cathode arc deposition, electron beam PVD, vapor deposition, closed-space sublimation, pulsed laser deposition, or pulsed electrodeposition. These materials can be coated by a series of non-vacuum methods including sublimation, spray coating, dip coating, spin coating, coating, rotary gravure coating, wet impregnation, slurry, use of organometallic cluster precursors, reductive precipitation, electroless plating, reverse micelle synthesis, and dendrimer-supported synthesis.

[0173] In some embodiments, the conductive solution comprises an electrolyte and a salt of a second metal, the second metal being electrochemically deposited on at least some of the surface structures when a bias voltage or current is applied. In some embodiments, the current or bias voltage is the current or bias voltage that forms the composite. In some embodiments, the current or bias voltage precedes the current or bias that forms the composite.

[0174] In some embodiments, the conductive solution comprises an electrolyte and a salt of a second metal, the second metal being electrochemically deposited on the edges and / or vertices when a current or bias voltage is applied.

[0175] In some embodiments, the potential difference set between the first electrode and the second electrode is sufficient to form a composite, alloy, or intermetallic compound. In some embodiments, the potential difference set between the first electrode and the second electrode is approximately -20V to +20V. In some embodiments, it is approximately -10V to +10V. In some embodiments, it is approximately -5V to +5V. In some embodiments, it is approximately -1V to +1V.

[0176] In some embodiments, the potential difference set between the first electrode and the second electrode is approximately + / -20V to + / -0.5V. In some embodiments, it is approximately + / -10V to + / -0.5V. In some embodiments, it is + / -7V to + / -0.5V. In some embodiments, it is + / -6V to + / -1V.

[0177] In some embodiments, the voltage is approximately -20 volts to approximately +20 volts, or + / -20 volts to approximately + / -0.5 volts, or approximately + / -10 volts to approximately + / -0.5 volts.

[0178] In some embodiments, the current applied between the first and second electrodes, as an average across the first and / or second electrodes, is sufficient to form a composite, alloy, or intermetallic compound. In some embodiments, the current applied between the first and second electrodes is at least about 0.1 A / cm² on average across the first and / or second electrodes. 2 ; at least about 0.2 A / cm² 2 ; at least about 0.3 A / cm² 2 ; at least about 0.5 A / cm² 2 ; at least about 0.7 A / cm² 2 ; at least about 1 A / cm 2 ; at least about 1.5 A / cm²2 That is the case.

[0179] In some embodiments, the current applied between the first electrode and the second electrode is approximately 500 A / cm² on average to the first electrode and / or the second electrode. 2 Less than approximately 100 A / cm² 2 Less than approximately 50 A / cm² 2 Less than approximately 20 A / cm² 2 Less than approximately 15 A / cm² 2 Less than approximately 10 A / cm² 2 Less than approximately 8 A / cm² 2 Less than approximately 5 A / cm² 2 Less than approximately 4 A / cm² 2 Less than approximately 3 A / cm² 2 Less than approximately 2 A / cm² 2 It is less than.

[0180] In some embodiments, the current applied between the first electrode and the second electrode is, on average across the first and / or second electrode, about 0.1 to about 500 A / cm². 2 , about 0.1~about 50A / cm 2 , about 0.1~about 20A / cm 2 , about 0.2~about 20A / cm 2 , about 0.2~about 15A / cm 2 , about 0.5~about 500A / cm 2 , about 0.5~about 50A / cm 2 , about 0.5~about 20A / cm 2 , about 0.5~about 10A / cm 2 , about 0.5~about 8A / cm 2 , about 0.5~about 5A / cm 2 , about 0.5~about 4A / cm 2 ;Approx. 1~4A / cm 2 That is the case.

[0181] In some embodiments, the current density is 0 A / cm². 2 Super ~ about 10A / cm 2 , about 1A / cm 2 ~About 5A / cm 2 It is, or approximately 2 A / cm². 2 That is the case.

[0182] In some embodiments, the current applied between the first electrode and the second electrode is substantially constant. In some embodiments, the current applied between the first electrode and the second electrode is applied as a gradient, pulsed, wave-like, oscillating, or as a cycle between oxidation and reduction potentials.

[0183] In some embodiments, the current density at the edges and / or vertices is approximately 1 to approximately 100 A / cm². 2 That is the case.

[0184] In some embodiments, the second electrode structure is planar or wire.

[0185] In some embodiments, the second electrode has a larger surface area than the first electrode.

[0186] In some embodiments, the second electrode has a surface area approximately 10 times larger than that of the first electrode.

[0187] In some embodiments, the second electrode comprises the support substrate and surface structure described herein with respect to the first electrode.

[0188] In some embodiments, the second electrode includes a support substrate, a surface structure protruding from the surface of the support substrate which is formed or coated with the first metal, and the second metal deposited on the surface structure.

[0189] In some embodiments of the array formation method, the current is applied / conducted for a time sufficient to form a composite, alloy, or intermetallic compound. In some embodiments of the electrocatalyst array formation method, the current is applied for at least about 1 second, at least about 1 minute, at least about 5 minutes, at least about 10 minutes, or at least about 0.5 hours. In some embodiments of the array formation method, the current is applied for about 1 second to about 1 week, about 1 second to about 24 hours, about 1 minute to about 24 hours, about 5 minutes to about 24 hours, about 10 minutes to about 24 hours, or about 0.5 hours to about 24 hours. In some embodiments of the array formation method, the current is applied for about 1 hour to about 12 hours.

[0190] In some embodiments, the time for which the current is applied is approximately 0.5 hours to approximately 200 hours, or approximately 1 hour to approximately 10 hours, or approximately 3 hours to approximately 9 hours.

[0191] In some embodiments, the second material is in contact with the first material to form a composite, alloy, or intermetallic compound.

[0192] In some embodiments, the second material forms a layer on the first material.

[0193] In some embodiments, the second material forms an intermittent layer on the first material.

[0194] In some embodiments, the second material is deposited on top of at least some of the surface structures so as to be embedded in or incorporated into the first material.

[0195] In some embodiments, the second material is deposited as a layer on the surface structure. In some embodiments, the layer has a thickness of about 0.2 nm to 100,000 nm. In some embodiments, the layer has a thickness of about 1 nm to 500 nm. In some embodiments, the layer has a thickness of about 1 nm to 200 nm. In some embodiments, the layer has a thickness of about 1 nm to 150 nm. In some embodiments, the thickness is about 1 nm to 100 nm, or about 1 nm to 80 nm, about 1 nm to 50 nm, about 1 nm to 40 nm, 1 nm to 30 nm, about 1 nm to 20 nm, about 1 nm to about 15 nm, or about 5 nm to about 15 nm.

[0196] In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 1000 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 500 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 200 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 150 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 100 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 80 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 50 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 40 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 30 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 20 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 15 nm. In some embodiments, the thickness of the second layer is a single layer of atoms or molecules.

[0197] In some embodiments, the thickness of the second material layer is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 26, 37, 38, 39, or 40 nm.

[0198] In some embodiments, the second material is deposited as an intermittent layer on the surface structure. In some embodiments, the intermittent layer has a thickness of about 0.2 nm to 100,000 nm. In some embodiments, the intermittent layer has a thickness of about 1 nm to 500 nm. In some embodiments, the intermittent layer has a thickness of about 1 nm to 200 nm. In some embodiments, the intermittent layer has a thickness of about 1 nm to 150 nm. In some embodiments, the thickness is about 1 nm to 100 nm, or about 1 nm to 80 nm, about 1 nm to 50 nm, about 1 nm to 40 nm, 1 nm to 30 nm, about 1 nm to 20 nm, about 1 nm to about 15 nm, or about 5 nm to about 15 nm.

[0199] In some embodiments, the thickness of the intermittent layer of the second material is greater than 0 nm but less than about 1000 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 500 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 200 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 150 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 100 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 80 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 50 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 40 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 30 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 20 nm. In some embodiments, the thickness of the second material layer is greater than 0 nm but less than about 15 nm. In some embodiments, the thickness of the second layer is a single layer of atoms or molecules.

[0200] In some embodiments, the thickness of the second material layer is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 26, 37, 38, 39 or 40 nm.

[0201] In some embodiments, the second material is deposited on the upper surface of the support substrate. In some embodiments, the second material is incorporated into the upper surface of the support substrate.

[0202] In some embodiments, the second material is deposited as a layer that substantially covers the entire upper surface of the support substrate. In some embodiments, the second material is incorporated as a layer that substantially covers the entire upper surface of the support substrate.

[0203] In some embodiments, the second material is deposited on the edges and / or vertices of the surface structure.

[0204] In some embodiments, the second material is deposited or incorporated at about 100% to about 10 -9 % of the structure / surface in top view. In some embodiments, the second material is deposited at less than about 100% to about 0.0000001% of the surface in top view. In some embodiments, the second material is deposited at less than about 100% to about 0.0001% of the surface in top view. In some embodiments, the second material is deposited at about 50% to about 0.000001% of the structure in top view. In some embodiments, the second material is deposited at about 50% to about 0.0001% of the surface in top view. In some embodiments, the second material is deposited at about 30% to about 0.0001% of the surface of the array in top view. In some embodiments, the second material is deposited at about 10% to about 0.1% of the surface in top view.

[0205] In some embodiments, the second material is deposited or incorporated at less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 1%, less than about 0.01%, less than about 0.001%, less than about 0.0001%, less than about 0.00001%, less than about 0.000001% of the surface area. It will be clear that the smallest surface area possible is a single atom on the surface structure.

[0206] In some embodiments, the second metal is deposited on the upper surface of the support substrate.

[0207] In some embodiments, the second metal is deposited or incorporated as a layer substantially covering the entire upper surface of the support substrate.

[0208] In some embodiments, the second metal is deposited or incorporated at the edges and / or vertices of the surface structure.

[0209] In some embodiments, the second metal, when viewed from above, accounts for about 100% to about 10% of the structure. -9 It is deposited or incorporated in %. In some embodiments, the second metal is deposited in a top view of less than 100% to about 0.0000001% of the surface. In some embodiments, the second metal is deposited in a top view of less than 100% to about 0.0001% of the surface. In some embodiments, the second metal is deposited in a top view of about 50% to about 0.000001% of the structure. In some embodiments, the second metal is deposited in a top view of about 50% to about 0.0001% of the surface. In some embodiments, the second metal is deposited in a top view of about 30% to about 0.0001% of the array surface. In some embodiments, the second metal is deposited in a top view of about 10% to about 0.1% of the surface.

[0210] In some embodiments, the second metal is deposited or incorporated in amounts of less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 1%, less than 0.01%, less than 0.001%, less than 0.0001%, less than 0.00001%, and less than 0.000001% of the surface area. It will be clear that the smallest possible surface area is a single atom on the surface structure.

[0211] In some embodiments, one or more additional materials are deposited on top of at least some of the surface structures, distinct from the first and / or second materials.

[0212] In some embodiments, one or more additional materials are in contact with the first material and / or the second material, and / or other additional materials in a continuous or intermittent layer.

[0213] In some embodiments, further materials are deposited on at least some of the surface structures and / or on the first material and / or the second material and / or other further materials.

[0214] In some embodiments, the additional material is deposited on at least some of the surface structures and / or on the first material and / or the second material and / or the preceding additional material, so as to be embedded in or incorporated into the first material and / or the second material and / or the preceding additional material.

[0215] In some embodiments, one or more additional materials are selected from polymers, organic compounds, inorganic compounds, and metals.

[0216] In some embodiments, further materials include s-block elements (groups 1 and 2 of the periodic table), p-block elements (groups 13, 14, 15, 16, or 17 of the periodic table), or d-block metals (transition metals).

[0217] In some embodiments, further materials are selected from alkali metals (Group 1), alkaline earth metals, transition metals, and metalloids.

[0218] In some embodiments, further materials are selected from C, O, B, As, P, Ga, Al, I, Li, Bi, At, Si, Xe, N, Au, Pt, GaAs, GaP, GaN, GaS, CaT, CaS, I, and Br.

[0219] In some embodiments, there are 1 to 1000 further materials. In some embodiments, there are 1 to 50 further materials. In some embodiments, there are 1 to 20 further materials. In some embodiments, there are 1 to 10 further materials. In some embodiments, there is 1 further material. In some embodiments, there are 2 further materials. In some embodiments, there are 3 further materials. In some embodiments, there are 4 further materials. In some embodiments, there are 5 further materials. In some embodiments, there are 6 further materials. In some embodiments, there are 7 further materials. In some embodiments, there are 8 further materials. In some embodiments, there are 9 further materials. In some embodiments, there are 10 further materials. In some embodiments, there are 100 further materials.

[0220] The further material is in contact with at least one of the first material, the second material, or one or more other further materials.

[0221] In some embodiments, the first, second, and further materials are all different materials. In some embodiments, some of the first, second, and further materials are identical, for example, the first and further materials are identical while the second material is different, or they are alternating stacks of materials.

[0222] In some embodiments, further materials are deposited as layers on the surface structure. In some embodiments, the further material layer has a thickness of about 0.2 nm to 100,000 nm. In some embodiments, the further material layer has a thickness of about 1 nm to 500 nm. In some embodiments, the further material layer has a thickness of about 1 nm to 2000 nm. In some embodiments, the further material layer has a thickness of about 1 nm to 150 nm. In some embodiments, the further material layer has a thickness of about 1 nm to 100 nm, or about 1 nm to 80 nm; about 1 nm to 50 nm; about 1 nm to 40 nm; 1 nm to 30 nm; about 1 nm to 20 nm; about 1 nm to about 15 nm; or about 5 nm to about 15 nm.

[0223] In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 500 microns. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 1000 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 500 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 200 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 150 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 100 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 80 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 50 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 40 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 30 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 20 nm. In some embodiments, the thickness of the further material layer is greater than 0 nm but less than about 15 nm. In some embodiments, the thickness of the second layer is a single layer of atoms or molecules.

[0224] In some embodiments, the thickness of the additional material layer is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 26, 37, 38, 39, 40 nm.

[0225] In some embodiments, the additional material is deposited as a layer that substantially covers the entire upper surface of the support substrate.

[0226] In some embodiments, the additional material is deposited on the edges and / or vertices of the surface structure.

[0227] In some embodiments, the additional material is deposited or incorporated at 100% to about 10 -9 % of the structure, as viewed from above. In some embodiments, the additional material is deposited at less than about 100% to about 0.0000001% of the surface, as viewed from above. In some embodiments, the additional material is deposited at less than about 100% to about 0.0001% of the surface, as viewed from above. In some embodiments, the additional material is deposited at about 50% to about 0.000001% of the structure, as viewed from above. In some embodiments, the additional material is deposited at about 50% to about 0.0001% of the surface, as viewed from above. In some embodiments, the additional material is deposited at about 30% to about 0.0001% of the surface of the array, as viewed from above. In some embodiments, the additional material is deposited at about 10% to about 0.1% of the surface, as viewed from above.

[0228] In some embodiments, the additional material is deposited or incorporated at less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 1%, less than about 0.01%, less than about 0.001%, less than about 0.0001%, less than about 0.00001%, less than about 0.000001% of the surface area. It will be apparent that the smallest surface area possible is a single atom on the surface structure / substrate.

[0229] In some embodiments, the additional material is deposited in contact with the second material. In some embodiments, the additional material is deposited or incorporated in contact with the first material.

[0230] In some embodiments, the combined thickness of the second material and the further material is approximately 1 atom to approximately 1 mm. In some embodiments, the combined thickness of the second material and the further material is approximately 1 atom to approximately 100 μm. In some embodiments, the combined thickness of the second material and the further material is approximately 1 atom to approximately 50 μm.

[0231] In some embodiments, further materials are deposited on the surface by evaporation under reduced pressure using material deposition processes, physical vapor deposition (PVD) processes, physical vapor deposition, thermal vapor deposition, plasma-accelerated chemical vapor deposition, cathode arc deposition, electron beam PVD, vapor deposition, closed-space sublimation, pulsed laser deposition, and pulsed electrodeposition. In some embodiments, further materials are deposited by sublimation, spray coating, dip coating, spin coating, coating, rotary gravure coating, wet impregnation, slurry, use of organometallic cluster precursors, reductive precipitation, electroless plating, reverse micelle synthesis, and dendrimer-supported synthesis.

[0232] In some embodiments, additional materials are deposited on the surface structure by reduction or oxidation. Reduction or oxidation can be carried out chemically or electrochemically.

[0233] In some embodiments, the conductive solution comprises one or more further materials, and when an electric current or bias is applied, the one or more further materials are electrochemically deposited on at least some of the surface structures. In some embodiments, the electric current or bias is a current or bias that forms a composite. In some embodiments, the electric current or bias precedes the current or bias that forms the composite.

[0234] In some embodiments, the conductive solution comprises one or more additional materials, and when an electric current is applied, the one or more additional materials are electrochemically deposited on the edges and / or vertices.

[0235] In some embodiments, the method further includes the step of depositing, incorporating, or embedding one or more additional materials in or on the array after the formation of the composite or alloy.

[0236] In some embodiments, the method further includes the step of depositing, incorporating, or embedding one or more additional materials in or on the array by diffusion or ion implantation after the formation of the composite or alloy.

[0237] In some embodiments, one or more additional materials are metals.

[0238] In some embodiments, one or more additional metals different from the first and / or second metals are deposited on at least some of the surface structures.

[0239] In some embodiments, there are 1 to 100 additional metals. In some embodiments, there are 1 to 50 additional metals.

[0240] In some embodiments, there are 1 to 1000 further metals. In some embodiments, there are 1 to 50 further metals. In some embodiments, there are 1 to 20 further metals. In some embodiments, there are 1 to 10 further metals. In some embodiments, there is 1 further metal. In some embodiments, there are 2 further metals. In some embodiments, there are 3 further metals. In some embodiments, there are 4 further metals. In some embodiments, there are 5 further metals. In some embodiments, there are 6 further metals. In some embodiments, there are 7 further metals. In some embodiments, there are 8 further metals. In some embodiments, there are 9 further metals. In some embodiments, there are 10 further metals. In some embodiments, there are 100 further metals.

[0241] The further metal is in contact with at least one of the first material, the second material, or one or more other further metals.

[0242] In some embodiments, one or more additional metals are different from the first and / or second metals, such as Ni, Ti, V, Cr, Fe, Co, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, R h、 The following can be selected: Pd, Ag, Cd, In, Sb, Sn, Cs, Ba, La, Ce, Pr, Nd, W, Os, Ir, Au, Pb, Bi, Ra, U, Pt, Au.

[0243] In some embodiments, the further metals are in the form of oxides, hydrides, halides, complexes, or clusters.

[0244] In some embodiments, further metals are deposited on a surface by evaporation under reduced pressure or by other material deposition processes such as chemical vapor deposition (CVD), physical vapor deposition or thermal vapor deposition or plasma CVD or cathode arc deposition, electron beam PVD, deposition, closed-space sublimation, pulsed laser deposition or pulsed electrodeposition. These materials can be coated by a series of non-reduced-pressure methods including sublimation, spray coating, dip coating, spin coating, coating, rotary gravure coating, wet impregnation, slurry, use of organometallic cluster precursors, reductive precipitation, electroless plating, reverse micelle synthesis, and dendrimer-supported synthesis.

[0245] In some embodiments, further metals are deposited on the surface structure by reduction or oxidation. Reduction or oxidation can be carried out chemically or electrochemically.

[0246] In some embodiments, the conductive solution contains one or more additional metals, and when a current or bias is applied, the one or more additional metals are electrochemically deposited on at least some of the surface structures. In some embodiments, the current or bias voltage is the current or bias voltage that forms the composite. In some embodiments, the current or bias voltage is applied before the current or bias voltage that forms the composite.

[0247] In some embodiments, the conductive solution comprises one or more further metal salts, and the one or more further metals are electrochemically deposited on the edges and / or vertices when a current or bias voltage is applied.

[0248] In some embodiments, the surface structure comprises a surface substructure including a composite material.

[0249] In some embodiments, the surface structure forms a uniform, discontinuous array on the surface structure.

[0250] In some embodiments, the surface structure is a repeating pattern.

[0251] In some embodiments, the surface structure is of uniform size.

[0252] In some embodiments, the surface structures are uniformly arranged. Alternatively, the surface structures are randomly arranged on the support substrate.

[0253] In some embodiments, the arrays or each array are arranged in a geometrically uniform pattern. In some embodiments, the arrays or each array is a pattern in which groups of surface structures are arranged in sequence.

[0254] In some embodiments, the surface structure is one or more of the following: i. Heights from the surface of the support substrate that are the same, different, or dissimilar ii. Geometric shapes that are identical, different, or dissimilar to other surface structures. iii. Regular or irregular geometric shapes iv. Equal or uneven spacing between them v. Densities that are identical, different, or dissimilar, vi. A group of multiple surface structures having one or more of the surface structures from i to v.

[0255] In some embodiments, the surface structure is composed of electrically and / or spatially isolated areas or regions of the surface structure.

[0256] In some embodiments, the surface structures are of substantially similar heights such that the distal tip of the surface structure is substantially flat.

[0257] In some embodiments, the surface structure is substantially flat such that the distance to the surface (e.g., the counter electrode surface) is substantially uniform across the array of surface structures.

[0258] In some embodiments, the surface structure is composed of a distal tip portion, the distal tip portion being furthest from the surface from which the surface structure extends, and the distal tip portion having a pointed, apex, spike, point, tip, or ridged shape.

[0259] In some embodiments, the cross-sectional area of ​​the surface structure decreases along an axis perpendicular to the upper surface of the support substrate. In some embodiments, the surface structure has a triangular, convex, semicircular, or papillary cross-section along a plane perpendicular to the upper surface of the support substrate. In some embodiments, the upper portion of the surface structure has an angle of about 90° or less at its vertices. In some embodiments, the surface structure is pointed or ridged. In some embodiments, the surface structure is conical, cone-shaped, ridged, pointed, spiked, cylindrical, regular pentahedron, pentahedron with a planar top, pentagonal or hexagonal, or a combination thereof. Any such structure may have edges, vertices, ridges, or a combination of two or more such features. In some embodiments, the surface structure has a substantially triangular, substantially circular or dome-shaped, or substantially square cross-section along a plane parallel to the upper surface of the support substrate.

[0260] In some embodiments, the upper or distal tip of the surface structure is substantially similar in width to, or reduced in width to, the bottom or proximal tip of the surface structure, where distal and proximal are relative to the surface of the support substrate to which the surface structure is related or protrudes.

[0261] In some embodiments, the width of the surface structure connected to the support substrate is approximately 1 nm to approximately 5000 μm. In some embodiments, the width of the surface structure connected to the support substrate is approximately 5 nm to approximately 5000 μm. In some embodiments, the widths are approximately 20 nm to approximately 5000 μm, approximately 40 nm to approximately 4000 μm, approximately 55 nm to approximately 3000 μm, approximately 75 nm to approximately 2500 μm, approximately 100 nm to approximately 4000 μm, approximately 250 nm to approximately 3500 μm, approximately 20 nm to approximately 3500 μm, approximately 20 nm to approximately 4000 μm, approximately 20 nm to approximately 3000 μm, or approximately 20 nm to approximately 2000 μm. In some embodiments, the width of the surface structure connected to the support substrate is approximately 5 nm to 750 μm, approximately 5 nm to 500 μm, and approximately 5 nm to 100 μm.

[0262] In some embodiments, the width of the surface structure on the nanometer scale is approximately 25 nm. In some embodiments, the width of the surface structure on the micrometer scale is approximately 50 μm. In some embodiments, the width of the surface structure on the nanometer scale is approximately 250 nm. In some embodiments, the width of the surface structure on the nanometer scale is approximately 750 nm. In some embodiments, the width of the surface structure on the nanometer scale can be approximately 25 nm, or at a minimum of approximately 1 nm.

[0263] In some embodiments, the width of the surface structure connected to the support substrate on a micrometer scale is approximately 1 μm to approximately 5000 μm. In some embodiments, the width of the surface structure on a micrometer scale is approximately 50 μm.

[0264] In some embodiments, the length of the surface structure connected to the support substrate on a micrometer scale is approximately 1 μm to approximately 5000 μm. In some embodiments, the length of the surface structure on a micrometer scale is approximately 50 μm.

[0265] In some embodiments, the width of the surface structure connected to the support substrate on a nanometer scale is approximately 2 nm to approximately 5000 nm. In some embodiments, the width of the surface structure on a nanometer scale is approximately 250 nm.

[0266] In some embodiments, the length of the surface structure connected to the support substrate on a nanometer scale is approximately 2 nm to approximately 5000 nm. In some embodiments, the length of the surface structure on a nanometer scale is approximately 250 nm.

[0267] In some embodiments, the height of the surface structure (i.e., the height of projection from or onto the support substrate or the surface of the support substrate) is approximately 1 nm to approximately 5000 μm. In some embodiments, the height of the surface structure (i.e., the height of projection from or onto the support substrate or the surface of the support substrate) is approximately 5 nm to approximately 5000 μm. In some embodiments, the height of the surface structure is approximately 40 nm to approximately 4000 μm, approximately 55 nm to approximately 3000 μm, approximately 75 nm to approximately 2500 μm, approximately 100 nm to approximately 4000 μm, approximately 250 nm to approximately 3500 μm, approximately 20 nm to approximately 3500 μm, approximately 20 nm to approximately 4000 μm, approximately 20 nm to approximately 2500 μm, approximately 20 nm to approximately 4000 μm, approximately 20 nm to approximately 3000 μm, or approximately 20 nm to approximately 2000 μm. In some embodiments, the height of the surface structure is approximately 1 nm to 750 μm, approximately 1 nm to 500 μm, or approximately 1 nm to 100 μm.

[0268] In some embodiments, the height of the surface structure connected to the support substrate on a micrometer scale is approximately 1 μm to approximately 500 μm. In some embodiments, the height of the surface structure on a micrometer scale is approximately 50 μm.

[0269] In some embodiments, the height of the surface structure connected to the support substrate on a nanometer scale is approximately 5 nm to approximately 5000 nm. In some embodiments, the length of the surface structure on a nanometer scale is approximately 250 nm.

[0270] In some embodiments, the surface structure has a base width and / or length of, for example, about 1 μm to about 500 μm on a micrometer scale. In some embodiments, the surface structure has a height of, for example, about 1 μm to about 500 μm on a micrometer scale. In some embodiments, the tip of the surface structure is, for example, about 1 nm to about 1000 μm on a nanometer or micrometer scale.

[0271] In some embodiments, the surface structure is 100 / cm 2 It exists on the surface of the support.

[0272] In some embodiments, the micrometer-scale surface structure is provided with a functional surface, or has a functional surface formed therefrom, at a density of about 180,000 to about 1,800 vertices or tips per square centimeter.

[0273] In some embodiments, the surface structure is provided with approximately 1 to approximately 2000 vertices or tips per square centimeter (e.g., on a millimeter scale), and densities of approximately 1 to approximately 1000, approximately 1 to approximately 500, and approximately 1 to approximately 100 per square centimeter.

[0274] In some embodiments, the nanometer-scale surface structure is provided with or has a functional surface formed thereon, with a density of approximately 160,000,000 to approximately 16,000,000,000 vertices or tips per square centimeter. In some embodiments, the nanometer-scale surface structure is provided with or has a functional surface formed thereon, with a density of approximately 1,600,000,000 vertices or tips per square centimeter. In some embodiments, the surface structure is provided with a density of 50,000,000,000,000 surface structures or tips per square centimeter.

[0275] In some embodiments, the surface structure has parallel or substantially parallel sidewalls. In some embodiments, the surface structure has inclined sidewalls terminating at the apex or vertex as described herein. In some embodiments, the angle is formed by sidewalls sharing the apex or vertex, measured in cross-section of the surface structure. In some embodiments, such angles are substantially about 0° to about 180°, or about 5° to about 175°, or about 20° to about 90°, or less than about 90°, or about 50°. In some embodiments, the angle may be formed by anisotropic etching of the underlying substrate, or by a master used to form the surface structure, such as about 54.7° for silicon.

[0276] In some embodiments, the composite is formed at least partially on the edges and / or vertices of the surface structure.

[0277] For example, in one embodiment, if the structure has a regular pyramidal shape, the vertex is the point of the pyramid, while the edge is the point where adjacent faces meet as they move toward the vertex. Similarly, in another exemplary example, if the structure is dome-shaped, the point at the top of the dome may be the vertex, but the structure has no edge because the walls defining the sides of the dome are continuous and rounded.

[0278] In some embodiments, the intermetallic compound is formed at least partially at the edges and / or vertices of the surface structure.

[0279] In some embodiments, the alloy is formed at least partially on the edges and / or vertices of the surface structure.

[0280] In some embodiments, the edges and / or vertices are functional surfaces.

[0281] In some embodiments, the functional surface is the vertex or periphery of the surface structure.

[0282] In some embodiments, the functional surface is the vertex or periphery of the surface structure, where the width of each vertex of the surface structure is approximately 1 nm to approximately 5000 μm. In some embodiments, the vertex or tip of each surface structure is atomic scale, for example, a single atom. In some embodiments, this is approximately 10 nm to approximately 10 μm, or approximately 20 nm to approximately 2 μm, or approximately 30 nm to approximately 1 μm. In some embodiments, this is approximately 1 nm to approximately 1000 nm, or approximately 1 nm to approximately 500 nm, or approximately 1 nm to approximately 100 nm, or approximately 1 nm to approximately 50 nm. The width of each vertex of the surface structure is shorter than the portion that connects to the support substrate.

[0283] In some embodiments, the functional surface is the vertices or periphery of the surface structure, where the vertices of the surface structure are spaced apart from each other at intervals of approximately 5 nm to 1000 μm; 10 nm to 1000 μm; 25 nm to 1000 μm; 5 nm to 750 μm; 5 nm to 500 μm; and 5 nm to 100 μm. In some embodiments, the intervals between vertices are approximately 5 nm to 2000 nm; 5 nm to 1000 nm; and 5 nm to 500 nm.

[0284] In some embodiments, the edges and / or vertices constitute about 50%, 40%, 30%, 20%, 10%, 1%, 0.01%, 0.001%, 0.0001%, 0.00001%, and 0.0000001% of the surface area. In some embodiments, the edges and / or vertices constitute about 0.00000001% or about 0.000001% to about 50% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and vertices constitute about 0.0001% to about 50% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and vertices constitute about 0.0001% to about 50% of the surface area of ​​the structure when viewed from above.

[0285] In some embodiments, the functional surface constitutes less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 1%, less than about 0.01%, less than about 0.001%, less than about 0.0001%, less than about 0.00001%, and less than about 0.0000001% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and / or vertices constitute about 0.00000001% or about 0.000001% to about 50% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and vertices constitute about 0.0001% to about 50% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and vertices constitute about 0.1% to about 50% of the surface area of ​​the structure when viewed from above.

[0286] In some embodiments, the conductive solution comprises water and / or an organic solvent. In some embodiments, the organic solvent is selected from alcohols (e.g., ethanol), ethers, acetonitrile, ethyl acetate, acetone, and / or DMSO (dimethyl sulfoxide).

[0287] In some embodiments, the conductive solution is a solution.

[0288] In some embodiments, the conductive solution includes an electrolyte.

[0289] In some embodiments, the electrolyte is selected from buffers, salts (e.g., NaCl), alkali metals, or acidic and basic solutions (e.g., H2SO4, HNO3, NaOH, KOH).

[0290] In some embodiments, the salt contains halide ions and / or metal ions (e.g., NaCl, copper²⁺ ions).

[0291] In some embodiments, the electrolyte concentration is about 0.05 M to about 20 M. In some embodiments, the electrolyte concentration is about 0.1 M to about 15 M. In some embodiments, the electrolyte concentration is about 0.1 M to about 12 M.

[0292] In some embodiments, the solution comprises a buffer solution containing alkali metal chloride ions and copper²⁺ ions.

[0293] In some embodiments, the conductive solution has a temperature below 100°C. In some embodiments, the temperature is below about 90°C, below about 80°C, below about 70°C, below about 60°C, below about 30°C, and below 20°C.

[0294] In some embodiments, an inert or passivation layer may be deposited between the surface structures. In some embodiments, the thickness of the inert or passivation layer may be about 5% and about 95% of the height of the surface structures. In some embodiments, the passivation layer is deposited on a support substrate to cover the lower portion of the surface structure and expose the upper portion. In some embodiments, the passivation layer on the functional surface in the upper portion of the surface structure is removed by applying an electric current or voltage to focus the charge density (voltage or current).

[0295] In some embodiments, the method includes a reference electrode, which can be used to monitor and control the voltage at the first electrode.

[0296] In the 27th embodiment, a method for carrying out a reaction is provided, which includes the step of contacting an array of the 1st, 2nd, 3rd, 4th, 5th, 6th, 7th, 8th, 16th, 17th, 18th, 19th, 20th or 21st embodiment, or an array formed by the method of the 9th, 10th, 11th, 12th, 13th, 14th, 15th, 19th, 20th, 22nd, 23rd, 24th, 25th or 26th embodiment, with at least one reactive species, wherein the array acts as a catalyst.

[0297] In some embodiments, the reaction involves active species in a gaseous or liquid state.

[0298] In the 28th embodiment, a method for carrying out an electrochemical reaction, the method comprising the step of applying a current between an electrocatalyst array formed by the first, second, third, fourth, fifth, sixth, seventh, eighth, sixteenth, seventeenth, eighteenth, nineteenth, nineteenth, twentyth or twenty-first embodiment, or by the method of the ninth, tenth, eleventh, twelfth, thirteenth, fifteenth, nineteenth, twentyth, twenty-second, twenty-third, twenty-fourth, twenty-fifth or twenty-sixth embodiment, and a counter electrode in a conductive solution.

[0299] To avoid misunderstanding, the following are embodiments of the 24th or 25th aspect.

[0300] In some embodiments, this reaction involves active species in a gaseous or liquid state.

[0301] In some embodiments, the conductive liquid may be an active species.

[0302] In some embodiments, the electrochemical reaction is selected from hydrogenation, dehydrogenation, reforming, and oxidation reactions.

[0303] In some embodiments, the electrochemical reaction is selected from the following: generation of hydrogen from water, generation of oxygen from water, generation of hydrogen from water, generation of hydrogen from protons, oxidation of hydrogen to water, oxidation of hydrogen to protons, oxidation of hydrogen to hydrogen peroxide, reduction of oxygen to water, reduction of oxygen to peroxides, carbon monoxide from carbon dioxide, methanol from carbon dioxide, carboxylic acids (e.g., formic acid) from carbon dioxide, aldehydes and / or ketones from carbon dioxide, methane, ethane, propane and / or higher carbon chains of C21 or less from carbon dioxide, oxidation of methane to methanol, hydrazine from nitrogen, ammonia from nitrogen, ammonia cleavage to hydrogen and nitrogen, methanol from methane, nitrogen from nitrates or ammonia from nitrates.

[0304] In some embodiments, this reaction involves active species in a gaseous or liquid state.

[0305] In some embodiments, the conductive liquid is an active species.

[0306] In some embodiments, the active species may be a gas passed through a conductive liquid.

[0307] In some embodiments, the gas may be selected from air, hydrogen, oxygen, nitrogen, methane, carbon monoxide and / or carbon dioxide, or air, or a mixture of two or more of these.

[0308] In some embodiments, the active species is a liquid, such as water, methanol, ethanol, propanol, acetone, ammonia, or a liquid short-chain hydrocarbon (e.g., C1). 21 The following are possible:

[0309] In some embodiments, when the active species is water, the conductive solution is also preferably water containing an electrolyte or organic solvent.

[0310] In some embodiments, this method may include a reference electrode.

[0311] In some embodiments, the shape of the counter electrode may reflect the shape of the surface structure. In some embodiments, the counter electrode has a surface structure opposite to that of the electrocatalyst array. In some embodiments, the counter electrode has a surface structure that is dissimilar in size, geometric shape, or pattern to that of the electrocatalyst array.

[0312] In some embodiments, the counter electrode may include a support substrate and surface structure as defined in the above embodiments and models.

[0313] In some embodiments, the counter electrode is formed from a material selected from the group consisting of inert conductive materials, conductive materials, metals, Pt, gold, carbon, graphite, graphene, carbon fibers, carbon nanotubes, fullerenes, or conductive polymers such as polypyrrole (Ppy), polyalanine (PA), or polyacetylene (Pacetylene).

[0314] In some embodiments, the counter electrode comprises a 3D surface feature portion configured to (a) be fixed in orientation with respect to a surface structure, (b) be attached to an electrode array, (c) be held in an orientation that minimizes the difference in distance between surface structures of the array, (d) be on the top surface of the array, or (e) facilitate the positioning of charge density (voltage or current) on the electrocatalyst array.

[0315] In some embodiments, the counter electrode is parallel to the electrolytic catalyst array.

[0316] In some embodiments, the potential difference set between the counter electrode or reference electrode and the electrolytic catalyst is approximately -20V to +20V. In some embodiments, it is approximately -1V to +1V. In some embodiments, the potential difference is approximately -200mV to -1V. In some embodiments, the potential difference for oxidation is approximately 0mV to 1.8V.

[0317] Preferred embodiments of this disclosure will be described as merely examples with reference to the following figures. [Brief explanation of the drawing]

[0318] [Figure 1a] Figure 1a shows SEM images of electrodes A to E before treatment, illustrating the shape of their surface structures. [Figure 1b] Figure 1b shows SEM images of electrodes A to E before treatment, illustrating the shape of their surface structures. [Figure 1c] Figure 1c shows SEM images of electrodes A to E before treatment, illustrating the shape of their surface structures. [Figure 2] Figure 2 shows EDX analysis illustrating the formation of a Pt peak (2.05 keV) in untreated sample 2, and the formation of a new "gold" shoulder (2.22 keV) in treated sample 4. [Figure 3a] Figure 3a shows SEM images of samples 1-5. [Figure 3b] Figure 3b shows SEM images of samples 1-5. [Figure 3c] Figure 3c shows SEM images of samples 1-5. [Figure 4] Figure 4 shows linear sweep voltammetry of submicron electrodes (samples 1-5) in the reduction region where hydrogen formation is observed. [Figure 5] Figure 5 shows linear sweep voltammetry of submicron electrodes (samples 1-5) in the region related to oxygen reduction. [Figure 6] Figure 6 shows the linear sweep voltammetry of submicron electrodes (Samples 1-5) in the oxidizing region, which includes (A) oxygen generation and (B) nickel oxide reduction. [Figure 7] Figure 7 shows EDS data for the region corresponding to the "zinc" signal that appears after pretreatment of Pt-coated nickel. A is the nickel control after pretreatment, and B is the Pt-coated nickel after pretreatment. [Figure 8]Figure 8 shows EDS data for the region corresponding to the "zinc" signal that appears after pretreatment of Au-coated nickel. A is the nickel control after pretreatment, B is the Au-coated nickel pretreated with 12M, C is the Au-coated nickel pretreated with 6M, and D is the Au-coated nickel pretreated with 0.5M. [Figure 9a] Figure 9a shows SEM images of sample 25 (untreated) and samples 26-28 (treated). [Figure 9b] Figure 9b shows SEM images of sample 25 (untreated) and samples 26-28 (treated). [Figure 10] Figure 10 shows linear sweep voltammetry of Co-coated samples 25–28 in the region related to oxygen generation. [Figure 11] Figure 11 shows linear sweep voltammetry of Co-coated samples 25–28 in the region related to oxygen reduction. [Figure 12] Figure 12 shows the EDS data for the Co / Ni electrode both before (solid line) and after (dashed line) pretreatment, where the circles indicate the peak position at 6.4 keV. [Figure 13] Figure 13 (including Figures 13A, 13B, 13C, 13D, 13E, 13F, 13G, 13H, 13I, 13J, 13K, and 13L) shows a schematic of the array of the present invention. Figures 13H, 13I, 13J, 13K, and 13L show embodiments of the array before and after pretreatment. [Figure 14] Figure 14 shows examples of the effects of pretreatment on 250 nm × 250 nm surface structures (A and B) and 750 nm × 750 nm surface structures (C and D) on nickel electrodes coated with 10 nm Pt (before pretreatment (A and C) and after pretreatment (B and D)). [Modes for carrying out the invention]

[0319] The present invention relates to the development of an array used, for example, as a catalyst. In particular, the present invention provides an array comprising a support substrate and a surface structure protruding from the surface of the support substrate formed or coated with a first material. A second material is deposited on at least some of the surface structures. The first and second materials at least partially form a composite, alloy, or intermetallic compound.

[0320] Alternatively, the present invention provides an array comprising a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with a first material, and a second material deposited on at least some of the surface structures such that the second material is in contact with the first material. The first material, the second material, or the first and second materials are conductive or semiconductive. The first and second materials form at least partially a composite.

[0321] Alternatively, the present invention provides a support substrate having a surface structure protruding from the surface of the support substrate; and an array comprising a composite material formed on at least a portion of the surface structure. The composite material is an electrolytic reaction product of a first material and a second material. The first material, the second material, or the first material and the second material are conductive or semiconducting.

[0322] Alternatively, the present invention provides a catalyst array comprising a support substrate, a surface structure protruding from the surface of the support substrate, and a surface substructure in each of the surface structures. The surface substructure comprises a composite material. The composite material is formed from at least a first material and a second material during the pretreatment of the catalyst array. The composite material exhibits a modified electronic structure compared to a mixture of the first material and the second material before pretreatment.

[0323] Alternatively, the present invention provides a support substrate having a surface structure protruding from the surface of the support substrate; and a catalyst array comprising a composite material formed on at least a portion of the surface structure. The composite material is an electrolytic reaction product of a first material and a second material. The surface structure comprises a pyramidal structure having a height of less than 100 microns to about 10 microns and a base dimension of about 10 microns to about 100 microns; and / or a circular or elongated dome-shaped structure having a height of about 1000 nm to about 1 nm and a diameter of about 1000 nm to about 1 nm.

[0324] Alternatively, the present invention provides a catalyst array comprising a support substrate and a surface structure that protrudes from and is integral with the support substrate. The surface structure includes a composite material formed from at least a first material and a second material. The composite material exhibits a modified electronic structure compared to a mixture of the first material and the second material.

[0325] Alternatively, the present invention provides an array comprising a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with a first material, and a second material deposited on at least some of the surface structures such that the second material is in contact with the first material. The first material, the second material, or the first and second materials are conductive or semiconductive. There is variation in the orbital overlap of the electronic structures of the first material, the second material, or the first and second materials.

[0326] Alternatively, the present invention provides a method for forming an array. The method includes the step of applying an electric current between a first electrode and a second electrode in a conductive solution. The first electrode includes a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with a first material, and a second material deposited on at least some of the surface structures in contact with the first material. The first material, the second material, or the first and second materials are conductive or semiconducting. The applied current density is sufficient to form a composite at least at the interface between the first and second materials.

[0327] Alternatively, the present invention provides a method for forming a composite. This method includes a structure having edges and / or vertices, and the step of conducting an electric current between a first material and a second material at the edges and / or vertices. The first material and the second material are in contact. The first and / or second materials are conductive or semiconducting. The current density at the edges and / or vertices is sufficient to form a composite at the interface between the first material and the second material.

[0328] Alternatively, the present invention provides a method for pre-treating a catalyst array. The method includes applying a current between a first electrode and a second electrode in a conductive solution sufficient to form a composite from a first material and a second material in a first electrode, a second electrode, or both of the first and second electrodes. The catalyst array includes a first electrode, a second electrode, or both of the first and second electrodes.

[0329] Alternatively, the present invention provides a method for forming an alloy array. This method includes the step of applying an electric current between a first electrode and a second electrode in a conductive solution. The first electrode includes a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with a first alloy component, and a second alloy component deposited on the surface structure. The applied current density is sufficient to form at least partially an alloy of the first and second alloy components on the surface structure. The alloy array is formed on the first electrode.

[0330] Alternatively, the present invention provides a method for forming an array. This method includes the step of applying an electric current between a first electrode and a second electrode in a conductive solution. The first electrode includes a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with a first material, and a second material deposited on the surface structure such that the second material is in contact with the first material. The first material, the second material, or the first and second materials are conductive or semiconducting. The applied current density is sufficient to distort the energy of the outer shell electrons of the first and second materials when the current is removed.

[0331] Alternatively, the present invention provides a method for pre-treating a catalyst array. The method includes the steps of providing a catalyst array, contacting an electrolyte solution with the catalyst array, and applying a bias to the array with a voltage and current for a specific time to form a pre-treated array. The material in the pre-treated array has a modified electronic structure compared to the material before the bias is applied. In this method, the array includes a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with a first material, and a second material deposited on at least some of the surface structures such that the second material is in contact with the first material.

[0332] Alternatively, the present invention provides a method for carrying out a reaction. This method includes contacting an array of the present invention or an array formed by the method of the present invention with at least one reactive species. The array acts as a catalyst.

[0333] Alternatively, the present invention provides a method for carrying out an electrochemical reaction. This method includes the step of applying an electric current in a conductive solution between the electrocatalyst array of the present invention or an electrocatalyst array formed by the method of the present invention and a counter electrode.

[0334] The inventors of this application have previously conducted research on electrodes having surface topology in the form of a surface structure (see International Publication No. 2018106128). Surprisingly, the inventors have found that when multiple materials are applied to an array surface having a surface structure, and a relatively large current is applied as a "pretreatment step," the properties of the materials change.

[0335] Energy-dispersive X-ray spectroscopy (e.g., EDS, EDX, EDXS, XEDS, EDXA, EDXMA, XPS) analysis of the array subjected to this pretreatment shows, in some cases, unexpected shifts that the EDS software indicates the presence of different elements. Although different elements are not clearly formed, this shift appears to indicate that the energy of the outer shell electrons of the material is distorted, so that the EDS software considers the electromagnetic radiation here to be close to the characteristics of a different element. Energy-dispersive X-ray spectroscopy (EDS) analysis appears to indicate the formation of a new species (referred to herein as a composite, intermetallic compound, or alloy). Energy-dispersive X-ray spectroscopy therefore indicates that, upon completion of the pretreatment step and with no further current applied, the electronic structure of the composite / alloy has been altered, and / or the orbital overlap of the electronic structures of the first material, the second material, or the first and second materials has been altered, and / or there is distortion in the energy of the outer shell electrons of the first and second materials.

[0336] In some cases, SEM analysis also reveals changes in the surface structure. However, in some cases, neither EDS nor / or SEM imaging shows significant changes, but when the array is used as an electrocatalyst, linear sweep or cyclic voltammetry shows changes in activation energy and / or kinetics and / or total reaction energy compared to an electrocatalyst made of the same material that has not been subjected to the pretreatment step, demonstrating that the material has still transformed into a composite, intermetallic compound, or alloy.

[0337] This “pretreatment” step is achieved in a conductive fluid (e.g., a basic supporting electrolyte, typically 0.5 M to 12 M KOH) in a two-electrode setup (e.g., cathode and anode) or a three-electrode setup (using a reference electrode). At least one of the two electrodes is equipped with topography (e.g., a surface structure). In a patent application by the same inventors (e.g., International Publication No. 2018 / 106128), it is understood that there is a voltage and / or current focusing effect induced by the topography (i.e., the applied current and / or measured voltage are not applied uniformly across the entire surface). Surprisingly, when relatively large currents are applied to the array, despite the anticipated adverse effects on the topography (such as loss of structure or other decomposition), the materials constituting these structures, or the materials applied to these structures, combine to form composites, alloys, or intermetallic compounds, depending on the materials used.

[0338] As used herein, the term “composite” means a material that is a combination of two or more distinct parent materials having different properties (e.g., electronic: stability, selectivity, activity, strain, or physical: hardness, impact resistance, wear, thermal characteristics) or different morphologies. It is not simply a stacking of two or more materials.

[0339] As an example, the pretreatment step may be performed on a base metal layer (supporting substrate and surface structure) on which subsequent layers (metallic and nonmetallic, second material and further material) are deposited (e.g., by evaporation, electrochemical deposition, or posttreatment by bombardment or electrochemical cycling). The surface topography (surface structure) in the surface structure may consist of a series of sharp tips or ridges, all preferably of the same height and preferably having sharp tips. By applying a relatively large current between the first and second electrodes in a conductive environment (e.g., concentrated KOH solution), the current and voltage are focused to the apex of the tips, and the materials (metallic and nonmetallic) mainly at the tips are locally hybridized (alloyed, combined, or composite formed). In this process, the degree to which hybrid / composite / alloy material is formed can be controlled by adjusting the atomic arrangement (e.g., layering) composition, topography, current density, voltage, solution resistance, and time. • Dimetallic catalysts often exhibit unique electronic and chemical properties that surpass those of the parent metal in terms of selectivity, activity and stability[1], It is understood that diffusion to and from the tip may be up to 1,000,000 times faster than with planar electrodes.[2]

[0340] As a result, the combination described herein yields a catalytic surface in which the active region is precisely and orderly located at the apex of the most active site. Furthermore, these structures are substantially equivalent, thereby avoiding the problem of the electrode surface being concentrated in a certain area, and the entire electrode surface exhibits evenly balanced and high-performance catalytic activity.

[0341] The array produced by this pretreatment step can be used as a supported catalyst or as an electrocatalyst in a wide variety of reactions.

[0342] Materials used Whether a composite, alloy, or intermetallic compound is formed depends on the material on which the surface structure is formed or coated, and the second material deposited on the surface structure. It will be apparent to those skilled in the art that the first and second materials will be different in order to form a composite, alloy, or intermetallic compound.

[0343] In some cases, the only difference between the first material and the second material may be the crystal structure. In some embodiments, the first material is a first metal having a first crystal structure, and the second material is the same metal as the first metal but having a different crystal structure.

[0344] At least one of the first material and the second material is conductive or semiconductive.

[0345] In some embodiments, the first material is a metal. In such cases, the metal forms or is applied to the surface structure. The support substrate can also be formed from the same metal. Such a configuration, in which the support substrate and the surface structure are formed from the same metal, simplifies manufacturing.

[0346] In some embodiments, both the first and second materials are metals. In such cases, it is conceivable that an alloy or intermetallic compound is formed. It will be apparent to those skilled in the art that an alloy or intermetallic compound can also be formed from the first metal and the second material, which is a nonmetal such as carbon.

[0347] When an alloy array is formed, the first and second alloy components can be selected from a first material, a second material, a first metal, or a second metal capable of forming an alloy, where at least one of the first and second alloy components is a metal. In some embodiments, the first alloy component is a metal. Nonmetallic elements capable of forming alloys with metals are known to those skilled in the art; these include (but are not limited to) metalloids (carbon, silicon, phosphorus, etc.). The descriptions herein relating to the first material, the second material, and further materials, such as the descriptions of the thickness, surface area, and region of the applied layers, also apply to the first and second alloy components.

[0348] In some embodiments, the second material is an s-block element (groups 1 and 2 of the periodic table), a p-block element (groups 13, 14, 15, 16, or 17 of the periodic table, excluding noble gases, group 18), or a d-block metal (transition metal). In some embodiments, further materials are selected from alkali metals (group 1), alkaline earth metals, transition metals, and metalloids. Other first and second materials can be single elements, such as C, S, or Si, organometallic elements such as purfilin, or carbonaceous materials such as graphene, fullerenes (buckyballs, or carbon nanotubes).

[0349] The second material can be deposited, incorporated, or embedded on the surface structure by reduction or oxidation. Reduction or oxidation can be carried out chemically or electrochemically.

[0350] Materials (e.g., gases) can be coated using physical deposition processes such as chemical vapor deposition (CVD), physical vapor deposition, thermal vapor deposition, or plasma CVD. Other methods include cathode arc deposition, electron beam PVD, vapor deposition, closed-space sublimation, pulsed laser deposition, and pulsed electrodeposition. These materials can also be coated using a range of non-reduced-pressure methods, including sublimation, spray coating, dip coating, spin coating, coating, and rotary gravure coating.

[0351] The second layer / material can also be an organic compound (e.g., a self-forming single layer, a paint layer, a spray-coated layer) that is thermally decomposed on the surface by conducting an electric current.

[0352] Other methods for applying second and further materials include wet impregnation, slurry, use of organometallic cluster precursors, reductive precipitation, electroless plating, reverse micelle synthesis, and dendrimer-supported synthesis.

[0353] The second material may be deposited before and / or during the pretreatment step. For example, the conductive solution may contain the second material (e.g., a solution, mixture, or gas to be permeated), and the second material is preferably deposited electrochemically on at least some of the surface structures, at the edges and / or vertices of the structure, when a current or bias voltage is applied. Thus, the deposition of the second material can be carried out immediately before or in the same step as the pretreatment, for example, the current or bias voltage applied in the pretreatment step may also be used for the deposition of the second material, or the second material may be deposited using a smaller current or bias voltage, and then the pretreatment step may be performed with an increased bias voltage or current.

[0354] For example, carbon can be deposited when the conductive solution contains a carbon-containing gas or solvent (e.g., CO2, methane, ethane, propane, formic acid, formaldehyde, acetone, benzene, toluene, acetic acid, ethanol, ethyl acetate, carbon-containing solvents, alcohols, aldehydes, ketones, carboxylic acids and / or corresponding salts). Other second materials can be deposited, for example, when the conductive solution contains O2, O3, NH2, Ar, and N2.

[0355] In some embodiments, the conductive solution comprises a second material, which, upon application of an electric current, is electrochemically deposited at the edges and / or vertices. To avoid misunderstanding, references to “deposited” should include “embedded” or “integrated.”

[0356] Assay structure Refer to Figure 13, which schematically shows the array of the present invention.

[0357] In Figure 13A, the surface structure X is formed from the first material 1 and is integral with the support substrate S. The second material 2 is deposited as a layer covering the entire surface structure and support surface. A composite, alloy, or intermetallic compound is shown as Y.

[0358] In Figure 13B, the surface structure X is coated with the first material 1. The surface structure X is integral with the support substrate S. The second material 2 is deposited as a layer covering the entire surface structure and support surface.

[0359] In Figure 13C, the surface structure X is formed from a first material 1. The surface structure X is made of a different material from the support substrate S. The second material 2 is deposited as a uniform layer covering the entire surface structure and the support substrate. A substantially uniform thickness of such a layer can be achieved by techniques such as electron beam deposition with a rotating array. A composite, alloy, or intermetallic compound is shown as Y. In this embodiment, both the surface structure and the support substrate are conductive materials so that the surface structure is electrically connected.

[0360] In Figure 13D, the second material is deposited as layers of varying thicknesses that cover the entire surface structure and support substrate. This type of layer can be achieved using techniques such as electron beam deposition without rotating the array, or magnetron sputtering.

[0361] In Figure 13E, the second material is deposited on the edges and / or apex of the surface structure. This type of layer can be achieved by electrochemical deposition, which is discussed further below.

[0362] In Figure 13F, an additional material 3 is deposited on the surface structure. This additional material 3 is deposited on top of the second material 2.

[0363] Figure 13G shows a dome-shaped surface structure X formed from a first material 1, with a second material 2 deposited substantially on the upper or dome-shaped portion of the dome-shaped surface structure X. The deposition of material 2 can be carried out by any of the methods outlined herein.

[0364] In Figure 13H, the substrate S is shown having a surface structure X which may be formed of the same material as the substrate S, or of a different material as described herein (i.e., shown in Figure 13C). In some embodiments, a first layer of material 1 and a second layer of material 2 are deposited, followed by additional or multiple layers of material n. In some embodiments, the first, second and additional or multiple layers of materials 1, 2 and n may be the same or different materials described herein. Further additional or multiple layers of material n may all be the same or different materials described herein, and may include any number of materials described herein, such as up to about 500 layers of material n.

[0365] Figure 13H shows an example of one embodiment before and after the pretreatment described herein. For example, the superstructure may be the above structure before performing the pretreatment process (such as a pretreatment process for forming a composite, alloy, or intermetallic compound as described herein). The arrows in Figure 13H indicate the pretreatment process, and the lower structure in Figure 13H shows the same structure after the pretreatment process. In this example, the composite, alloy, or intermetallic compound Y (shown as a shaded area) is substantially formed at the vertices of the surface structure X and may be formed at some or all of the multilayer boundaries of materials 1, 2, and n.

[0366] In Figures 13I-13L, the substrate S is shown having a surface structure X. The first material 1 is shown as the surface structure X. The second material 2, 2', or 2'' is shown substantially toward the tip or apex of the surface structure X and may be a continuous or discontinuous film or layer of the material. Alternatively, the second material 2, 2', or 2'' may be provided as a series of particles, atoms, nanostructures, or smaller surface structures. A further material 3 may be deposited as a layer covering the second material 2, 2', or 2'', however, it will be understood that the further material 3 may be provided in other forms (such as a discontinuous film or particles).

[0367] Figure 13L specifically shows a substrate S and surface structure X formed from a first material 1. Multiple different second materials 2, 2', or 2'' (represented here by different shapes, i.e., dome 2, square 2', and triangular 2'', respectively) are provided substantially toward the tips or vertices of the surface structure X. These second materials may be the same or different, and are provided in the same or different shapes, or in the arrangement or crystalline structures described herein. Further material 3 is provided in this example, comprising the second material, however, it will be understood that this further material 3 is optional. Alternatively, the further material 3 can be provided as discontinuous layers or as particles, as described above.

[0368] The arrows in Figures 13I-L indicate the transition from the first state to the second pre-treated state (i.e., after the pre-treatment process described herein), in which the composite, alloy, or intermetallic compound Y is formed and shown as a shaded region Y. It will be understood that the composite, alloy, or intermetallic compound Y can be formed at the interface between 1 and 2, 2', or 2'', depending on the material used.

[0369] Figures 13I-13L show examples of different second materials (each of which is represented by a different shape, i.e., dome 2, square 2', or triangle 2"), illustrating how different second materials can be scattered or arranged on the surface structure X, yet still be spatially isolated from one another. The second materials 2, 2', or 2") can be electrically connected via superimposed materials such as further material 3, or via the surface structure 1, or via an underlying material (not shown).

[0370] The support substrate is provided with a base on which the surface structure is arranged such that it protrudes from the support substrate, for example, so that the surface structure forms a uniform, discontinuous array on the support substrate. As discussed above, the support substrate and the surface structure can be made of the same or different materials.

[0371] In some embodiments, the surface structure is integral with the support substrate and / or formed integrally with the support substrate and / or is made of the same material as the support substrate. In some embodiments, the surface structure may also be formed from the first material.

[0372] Alternatively, the surface structure can be applied to the support substrate and may be made of a different material.

[0373] If the support substrate is made of a different material from the surface structure, the support substrate may include polymers, ceramics, metals, silica, or glass.

[0374] The surface structure must be electrically connected in order to be used as an electrode. If it is not electrically connected, this can be achieved by a support substrate made of a conductive material.

[0375] metal The present invention is particularly useful for forming alloys or intermetallic compounds. These are formed when the first material is an alloy and the second material is a metal or material capable of forming an alloy.

[0376] Alloys can be extremely useful as catalysts and for other applications. For example, "exotic" alloys, which are often difficult to form, have found applications as catalysts.

[0377] In particularly useful embodiments of the present invention, the present invention may provide composites, alloys, or intermetallic compounds formed at the reactive sites in already highly reactive catalysts or electrocatalysts. It is already known that the topology of these electrodes makes the electrocatalysts highly reactive due to the focusing of voltage and / or current in the structure. Herein, the pretreatment steps described in this application can further enhance this reactivity.

[0378] In one embodiment of the present invention, an array is provided comprising a support substrate and a surface structure protruding from the surface of the support substrate. The surface structure is formed or coated with a first metal. A second metal is deposited on at least some of the surface structure. The first and second metals form at least partially an alloy.

[0379] In another aspect of the present invention, a method for forming an array is provided, comprising the step of applying an electric current between a first electrode and a second electrode in a conductive solution. The first electrode comprises a support substrate and a surface structure protruding from the surface of the support substrate, which is formed or coated with a first metal. The second metal is deposited on the surface structure. The current density applied between the first electrode and the second electrode is sufficient to form an alloy at least partially on the surface structure.

[0380] In another aspect of the present invention, a method for pre-treating an array is provided. This method includes applying a current between the first electrode and the second electrode in a conductive solution sufficient to form an intermetallic compound from the first and second metals in the first electrode, the second electrode, or both the first and second electrodes. The array includes the first electrode, the second electrode, or both the first and second electrodes. In some embodiments, the first electrode and / or the second electrode includes a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with the first metal, and a second metal deposited on at least some of the surface structures forming an interface between the first and second metals.

[0381] As described above, previous studies completed by the inventors demonstrated current focusing effects at the edges and / or vertices of surface structures. Therefore, it is believed that alloys are formed at least partially at the edges and / or vertices of surface structures. SEM images provided in the Examples section support this. In particular, this is shown in Figure 14 in nickel arrays coated with Pt of 250 nm × 250 nm (Figures 14A and B) and 750 nm × 750 nm (Figures 14C and D), both before (Figures 14A and C) and after (Figures 14B and D). Figure 14B shows structural changes at the vertices, and Figure 14D shows the “mushroom” effect at the vertices. These substructures, including composites / alloys, are formed during the pretreatment step.

[0382] In some embodiments, the composite, alloy, or intermetallic compound is formed at the interface between the first and second materials. The composite, alloy, or intermetallic compound may be formed in the upper layer or in layers within the first, second, and / or further layers, so as to affect the catalyst on the surface.

[0383] In some embodiments, the first metal and / or the second metal and / or further metals are selected from transition metals or post-transition metals. In some embodiments, the first metal and / or the second metal and / or further metals are Ni, Ti, V, Cr, Fe, Co, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, R h、 Selected from Pd, Ag, Cd, In, Sb, Sn, Cs, Ba, La, Ce, Pr, Nd, W, Os, Ir, Au, Pb, Bi, Ra, U, Pt, and Au.

[0384] In some embodiments, the first material is Ni and the second material is Pt, or the first material is Pt and the second material is Ni. In some embodiments, the first metal is selected from Ni, Cu, Zn, Co, Al, and Ti, and the second metal is selected from Pt, Co, Au, Ni, Ag, Ti, Cr, Cu, Mg, Mn, Fe, and Zn. In some embodiments, the first metal is Ni and the second metal is selected from Pt, Co, or Au.

[0385] In some embodiments, the second and / or further metals are in the form of oxides, hydrides, halides, hydroxides, salts, carbides, organometallic complexes, complexes, alloys, or clusters.

[0386] In some embodiments, a second metal and / or further metals are deposited on a surface by evaporation under reduced pressure using a physical vapor deposition (PVD) method, which includes E-beam, pulsed laser deposition, sputtering, magnetron sputtering, and physical evaporation of the deposited layer metal by a thermal filament.

[0387] In some embodiments, a second metal and / or further metals are deposited on the surface structure by reduction or oxidation. Reduction or oxidation can be carried out chemically or electrochemically.

[0388] In some embodiments, the conductive solution contains a second metal and / or further metals, and the second metal and / or further metals are electrochemically deposited on at least some of the surface structures, preferably on the edges and / or vertices of the structures, when an electric current is applied. Thus, the deposition of the second and / or further metals can be carried out immediately before or in the same step as the pretreatment. For example, the current applied in the pretreatment step is also used for the deposition of the second and / or further metals, or a smaller current is used to deposit the second and / or further metals, and then the pretreatment step is performed with an increased bias / voltage or current.

[0389] In this configuration, the second and / or further metals exist in the conductive solution as metal salts, such as halides, acetates (e.g., acetate or trifluoroacetate), sulfates, nitrates, or amino salts. For example, when platinum is deposited, the salts used can be platinum(IV) chloride, Pt(II)Br, Pt(II)I, or diaminotetrachloroplatinum(IV); for silver, examples are AgCl3 and AgNO3; for gold, examples are AuCl, AuI, AuBr3, silver acetate, and silver trifluoroacetate; for copper, examples are copper chloride, copper sulfate, and copper nitrate; for zinc, examples are zinc sulfate and zinc chloride; for iron, an example is iron chloride; and for tungsten, an example is tungsten chloride, although others may also be used.

[0390] The concentration of metal salts in conductive solutions / fluids can range from approximately 0.0001 to approximately 10 M, or from approximately 0.0001 M to approximately 5 M, or from approximately 0.0001 M to approximately 2 M.

[0391] The high current density used in the pretreatment step, and the focusing of voltage / current at the vertices and / or edges or periphery of the surface structure, allow the second and / or further metals to be deposited reductively at a higher density at a single and / or multiple vertices and / or edges. This provides a method for selectively positioning alloys / composites on the surface structure in the pretreatment step. Furthermore, the applied voltage is highly reductive, and therefore the process allows for simultaneous reduction and alloying of different metal combinations. This method provides a combination of site-selective functionality, alloying, and minimization of the required amount of high-value metals by selectively applying metals to reactive sites at a single and / or multiple vertices.

[0392] Alternatively, the materials can be coated by physical deposition processes such as chemical vapor deposition (CVD), physical vapor deposition, thermal vapor deposition, or plasma CVD. Alternatively, the materials can be deposited by cathode arc deposition, electron beam PVD, vapor deposition, closed-space sublimation, pulsed laser deposition, or pulsed electrodeposition. These materials can be coated by a series of non-vacuum methods including sublimation, spray coating, dip coating, spin coating, coating, rotary gravure coating, wet impregnation, slurry, use of organometallic cluster precursors, reductive precipitation, electroless plating, reverse micelle synthesis, and dendrimer-supported synthesis.

[0393] Cell parameters The average current applied between the first and second electrodes is relatively high, higher than that typically used in electrochemical reactions. Furthermore, as mentioned above, the current is concentrated at the edges and / or vertices of the surface structure, so the current density at the edges and / or vertices is considered to be even higher.

[0394] In some embodiments, the current applied between the first electrode and the second electrode, as an average across the first electrode and / or the second electrode, is sufficient to form a composite or an alloy or an intermetallic compound. In some embodiments, the current applied between the first electrode and the second electrode is, on average across the first electrode and / or the second electrode, at least about 0.1 A / cm 2 , at least about 0.2 A / cm 2 , at least about 0.3 A / cm 2 , at least about 0.5 A / cm 2 , at least about 0.7 A / cm 2 , at least about 1 A / cm 2 or at least about 1.5 A / cm 2 .

[0395] In some embodiments, the current applied between the first electrode and the second electrode is an average across the first electrode and / or the second electrode, and is less than about 500 A / cm 2 , less than about 100 A / cm 2 , less than about 50 A / cm 2 , less than about 20 A / cm 2 , less than about 15 A / cm 2 , less than about 10 A / cm 2 , less than about 8 A / cm 2 , less than about 5 A / cm 2 , less than about 4 A / cm 2 , less than about 3 A / cm 2 , less than about 2 A / cm 2 .

[0396] In some embodiments, the current applied between the first electrode and the second electrode is an average across the first electrode and / or the second electrode, and is about 0.1 to about 500 A / cm 2 , about 0.1 to about 50 A / cm 2 , about 0.1 to about 20 A / cm<00001​​​​​​​​​2 , about 0.5~about 10A / cm 2 , about 0.5~about 8A / cm 2 , about 0.5~about 5A / cm 2 , about 0.5~about 4A / cm 2 , about 1~4A / cm 2 That is the case.

[0397] However, the average current and / or voltage across the first and / or second electrodes sufficient for the formation of a composite / alloy will depend on the size of the surface structure and / or the sharpness of its edges and / or vertices due to current and / or voltage focusing at the edges and / or vertices. For example, smaller surface structures require less current due to the high current density focused at the edges and / or vertices, while larger surface structures require more current due to the lower current density focused at the edges and / or vertices.

[0398] In some embodiments, the current applied between the first electrode and the second electrode is substantially constant, increasing and / or decreasing, or pulsed.

[0399] The reference for the application of bias or bias voltage should be the application of electrical bias or reducing or oxidizing voltage.

[0400] In some embodiments, the potential difference set between the first electrode and the second electrode is sufficient to form a composite, alloy, or intermetallic compound. In some embodiments, the potential difference set between the first electrode and the second electrode may be about -20V to +20V, about -10V to +10V, about -5V to +5V, or about -1V to +1V.

[0401] In some embodiments, the potential difference set between the first electrode and the second electrode is approximately + / -20V to + / -0.5V (for example, approximately +20V to +0.5V, or approximately -20V to -0.5V). In some embodiments, it is approximately + / -10V to + / -0.5V. In some embodiments, it is + / -7V to + / -0.5V. In some embodiments, it is + / -6V to + / -1V.

[0402] However, the resistance can be varied in various ways, for example, by changing the conductivity of the fluid (for example, by changing the concentration of the electrolyte), and / or by adding a membrane between the first electrode and the second electrode, and / or by increasing the distance between the electrodes.

[0403] Second electrode in pretreatment step The second electrode used in the pretreatment step can have the same or similar structure as the first electrode, for example, having a surface structure, or it can be a standard electrode. Suitable standard electrodes will be known to those skilled in the art.

[0404] The second electrode can be a plane, a wire, or other shape. However, if the second electrode has a different shape, it is preferable that there is a sufficient distance between it and the first electrode to ensure uniform pretreatment between them. For example, if a wire is close to the first electrode, pretreatment may only occur on a portion of the first electrode.

[0405] The second electrode can be selected so as not to be the rate-limiting step in the pretreatment method; for example, the size of the second electrode can be larger than that of the first electrode.

[0406] Timing of the pre-processing step In some embodiments of the array formation method, an electric current is applied for a sufficient time to form a composite, alloy, or intermetallic compound. The time varies depending on the electric current, the amount of the first, second, and further materials, and the size and shape of the surface structure.

[0407] It is possible to apply a larger current and / or voltage for a shorter time than a smaller current and / or voltage in order to form a composite, alloy, or intermetallic compound.

[0408] As discussed above, the size and shape of the surface structure affect the current and / or voltage concentrated at the edges and / or vertices. Smaller structures and / or sharper edges and / or vertices require shorter processing times to form composites, alloys, or intermetallic compounds than larger structures and / or structures with more rounded edges and / or vertices.

[0409] Some of the first, second, and further materials are more reactive and / or conductive than others, and therefore the time for which an electric current is applied to form a composite, alloy, or intermetallic compound also varies.

[0410] In some embodiments of the method for forming an electrocatalyst array, the current is applied for at least about 1 second, at least about 1 minute, at least about 5 minutes, at least about 10 minutes, and about 0.5 hours. In some embodiments of the method for forming the array, the current is applied for about 1 second to about 1 week, about 1 second to about 24 hours, about 1 minute to about 24 hours, about 5 minutes to about 24 hours, about 10 minutes to about 24 hours, and about 0.5 hours to about 24 hours. In some embodiments of the method for forming the array, the current is applied for about 1 hour to about 12 hours.

[0411] In some embodiments, the pretreatment step can be performed multiple times. For example, multiple pretreatments may be performed, optionally involving further addition of material during cycling. Furthermore, each material posttreatment or pretreatment step may be carried out by CV annealing, ion introduction (e.g., Li), or atomic bombardment (e.g., K, B, P).

[0412] Arrangement of second and / or further materials The second material is in contact with the first material to form a composite, alloy, or intermetallic compound. In some embodiments, the second material forms a layer on the first material. In some embodiments, the second material forms an intermittent layer on the first material. In some embodiments, the second material is deposited on at least some surface structures so as to be embedded in or incorporated into the first material; for example, if the first material is porous, the second material is deposited in the pores. References to “deposited” should be understood to include “embedded” or “incorporated.”

[0413] In some embodiments, the second, third, or subsequent / further materials form structures on the surface structure, each having a surface structure containing one, two, or further different materials in contact with each other. See, for example, Figure 13. The second, third, or other subsequent materials may be deposited in uniform layers or layers of varying thickness. These may be deposited in different regions or in continuous regions. The only limitation is that there is an interface between at least two different materials, which may be completely different materials or identical materials with different crystal structures, but the conduction of current through the layers will result in a change in the electronic or orbital structure, which is shown by the change in the linear sweep voltammetry of the array before and after conducting current (i.e., pretreatment).

[0414] Thickness of the layer In some embodiments, the second material and / or further material are deposited as layers on the surface structure. In some embodiments, the layers have a thickness of about 0.2 nm to about 100,000 nm. In some embodiments, the layers have a thickness of about 1 atom to about 200 nm. In some embodiments, the layers have a thickness of about 1 nm to 150 nm. In some embodiments, the layers have thicknesses of about 1 nm to 100 nm, about 1 nm to 80 nm, about 1 nm to 50 nm, about 1 nm to 40 nm, about 1 nm to 30 nm, about 1 nm to 20 nm, about 1 nm to about 15 nm, and about 5 nm to about 15 nm.

[0415] In some embodiments, the thickness of the second material and / or further material layer is greater than 0 nm but less than about 500 microns, greater than 0 nm but less than about 1000 nm, greater than 0 nm but less than about 500 nm, greater than 0 nm but less than about 200 nm, greater than 0 nm but less than about 150 nm, greater than 0 nm but less than about 100 nm, greater than 0 nm but less than about 80 nm, greater than 0 nm but less than about 50 nm, greater than 0 nm but less than about 40 nm, greater than 0 nm but less than about 30 nm, greater than 0 nm but less than about 20 nm, or greater than 0 nm but less than about 15 nm.

[0416] In some embodiments, the combined thickness of the second material and the further material is approximately 1 atom to approximately 1 mm. In some embodiments, the combined thickness of the second material and the further material is approximately 1 atom to approximately 100 μm. In some embodiments, the combined thickness of the second material and the further material is approximately 1 atom to approximately 50 μm. The upper limit varies depending on the applied current.

[0417] Surface area and region covered by the second and further materials In some embodiments, the second material and / or further material is deposited as a layer that substantially covers the entire upper surface of the support substrate in a top view, i.e., covering about 100% of the support substrate and surface structure.

[0418] In other embodiments, a second or further material is selectively deposited on the edges and / or vertices of the surface structure. This can be cost-effective, especially when the second or further material is expensive (e.g., a precious metal). This can be achieved in various ways that will be apparent to those skilled in the art. For example, a masking layer (e.g., a self-forming single layer (SAM)) can be applied to the support substrate and the surface structure, and then a voltage can be applied to selectively desorb the SAM from the edges and / or vertices of the structure. This is described, for example, in International Publication No. 2018 / 106128. The second material can then be applied only to the exposed edges and / or vertices. In further examples (as demonstrated with platinum in International Publication No. 2018 / 106128), the material can be selectively applied to the edges and / or vertices by electrochemical deposition without a masking step.

[0419] In some embodiments, the second material and / or further material is deposited covering about 100% to about 0.0000001% of the structure in a top view. In some embodiments, the second material is deposited covering less than 100% to about 0.0001% of the surface in a top view. In some embodiments, the second material is deposited covering about 50% to about 0.000001% of the structure in a top view. In some embodiments, the second material is deposited covering about 50% to about 0.0001% of the surface in a top view. In some embodiments, the second material is deposited covering about 30% to about 0.0001% of the array surface in a top view. In some embodiments, the second material is deposited covering about 10% to about 0.1% of the surface in a top view.

[0420] In some embodiments, the second material and / or further material is deposited on less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 1%, less than about 0.01%, less than about 0.001%, less than about 0.0001%, less than about 0.00001%, or less than about 0.000001% of the surface area. It will be clear that the smallest possible surface area is a single atom on the surface structure.

[0421] In some embodiments, the second material / metal and / or further material is deposited over approximately 100% to approximately 0.0000001% of the structure in a top view. In some embodiments, the second material / metal is deposited over less than approximately 100% to approximately 0.0001% of the surface in a top view. In some embodiments, the second material / metal is deposited over approximately 50% to approximately 0.000001% of the structure in a top view. In some embodiments, the second material / metal is deposited over approximately 50% to approximately 0.0001% of the surface in a top view. In some embodiments, the second material / metal is deposited over approximately 30% to approximately 0.0001% of the array surface in a top view. In some embodiments, the second material / metal is deposited over approximately 10% to approximately 0.1% of the surface in a top view.

[0422] In some embodiments, the second material / metal and / or further material is deposited on less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 1%, less than about 0.01%, less than about 0.001%, less than about 0.0001%, less than about 0.00001%, or less than 0.000001% of the surface area. It will be clear that the smallest possible surface area is a single atom on the surface structure. Small amounts of the second material and / or further material may be considered dopants.

[0423] Third and further materials In some embodiments, one or more additional materials different from the first and / or second materials are deposited on top of at least some of the surface structures.

[0424] In some embodiments, one or more further materials are in contact with the first material and / or the second material and / or other further materials in a continuous or intermittent layer. In some embodiments, the further materials are deposited on at least some of the surface structures so as to be embedded or incorporated into the first material and / or the second material and / or the further materials, for example, these materials are porous and the further materials are deposited in the pores. References to “deposited” should therefore include “embedded or incorporated.”

[0425] In some embodiments, one or more additional materials are selected from polymers, organic compounds, inorganic compounds, and metals. The additional materials may be selected from one or more s-block elements (groups 1 and 2 of the periodic table), p-block elements (groups 13, 14, 15, 16, or 17 of the periodic table), or d-block metals and transition metals. The additional materials may be selected from one or more alkali metals (group 1), alkaline earth metals, transition metals, and metalloids. For example, the additional materials may be selected from one or more of C, O, B, As, P, Ga, Al, I, Li, Bi, At, Si, Xe, N, Au, Pt, GaAs, GaP, GaN, GaS, CaT, CaS, I, and Br.

[0426] In some embodiments, there are 1 to 1000 additional materials. In some embodiments, there are 1 to 50 additional materials. In some embodiments, there are 1 to 20 additional materials. In some embodiments, there are 1 to 10 additional materials. In some embodiments, there are 1 to 5 additional materials. In some embodiments, there is 1 additional material. In some embodiments, there are 2 additional materials. In some embodiments, there are 3 additional materials. In some embodiments, there are 4 additional materials. In some embodiments, there are 5 additional materials. In some embodiments, there are 6 additional layers. In some embodiments, there are 7 additional layers. In some embodiments, there are 8 additional layers. In some embodiments, there are 9 additional layers. In some embodiments, there are 10 additional layers. In some embodiments, there are 1000 additional layers.

[0427] In some embodiments, the first, second, and further materials are all different materials. In some embodiments, some of the first, second, and further materials are identical, for example, the first and further materials are identical, and the second material is different (alternating stacking of materials).

[0428] In some embodiments, a further material is deposited in contact with a second material. In some embodiments, a further material is deposited in contact with a first material. In some embodiments, a further material is deposited in contact with both a first and a second material.

[0429] Further materials may be deposited on the surface or incorporated by techniques described for the first and / or second material or metal. Alternatively, the materials may be coated by chemical vapor deposition (CVD), physical vapor deposition, or physical vapor deposition (PVD) processes such as thermal vapor deposition or plasma CVD. Alternatively, these materials may be deposited by cathode arc deposition, electron beam PVD, vapor deposition, closed-space sublimation, pulsed laser deposition, or pulsed electrodeposition. These materials may be coated by a series of non-vacuum methods including sublimation, spray coating, dip coating, spin coating, coating, rotary gravure coating, wet impregnation, slurry, use of organometallic cluster precursors, reductive precipitation, electroless plating, reverse micelle synthesis, and dendrimer-supported synthesis.

[0430] Further materials may be deposited, incorporated, or embedded before and / or during or after the pretreatment step. Small amounts of further materials may be used, for example, as doping agents / dopants.

[0431] Further materials may be deposited or incorporated before or during the pretreatment step, as described for the second material or second metal. For example, a conductive solution may contain further materials (e.g., a solution, mixture, or gas to be permeated), and the further materials are electrochemically deposited / incorporated onto at least some of the surface structures when a current or bias is applied. Thus, the deposition of further materials can be carried out immediately before or in the same step as the pretreatment, for example, the current or bias voltage applied in the pretreatment step may also be used for the deposition of further materials, or a smaller current or bias may be used to deposit the further materials, and then the bias voltage or current may be increased to carry out the pretreatment step.

[0432] For example, if the conductive solution contains carbon-containing gases or solvents such as CO2, methane, ethane, propane, formic acid, formaldehyde, acetone, benzene, toluene, acetic acid, ethanol, ethyl acetate, carbon-containing solvents, alcohols, aldehydes, ketone carboxylic acids and / or corresponding salts, carbon may be deposited or incorporated. Other further materials may be deposited / incorporated, for example, if the conductive solution contains one or more of O2, O3, NH2, Ar, and N2. In some embodiments, the conductive solution contains further materials, and these further materials are electrochemically deposited at the edges and / or vertices when an electric current is applied.

[0433] Further materials may be deposited or incorporated after the pretreatment step (after the composite or alloy has been formed). For example, diffusion or ion implantation may be performed on the array after the composite / alloy has been formed. This is especially true when dealing with small amounts of further materials (e.g., dopants). Examples of further materials / dopants include one or more of the following: C, O, B, As, P, Ga, Al, I, Li, Bi, At, Si, Xe, N, Au, Pt, GaAs, GaP, GaN, GaS, CaT, CaS, I, Br.

[0434] In some embodiments, one or more further materials are metals. In some embodiments, one or more further metals are different from the first and / or second metals, and include Ni, Ti, V, Cr, Fe, Co, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, R h、 One or more of the following metals are selected: Pd, Ag, Cd, In, Sb, Sn, Cs, Ba, La, Ce, Pr, Nd, W, Os, Ir, Au, Pb, Bi, Ra, U, Pt, Au. In some embodiments, the further metals are in the form of oxides, hydrides, halides, complexes, or clusters.

[0435] In some embodiments, additional metals are deposited on the surface by the techniques described for the first and / or second metals.

[0436] Shape, size, and arrangement of surface structures In some embodiments, the surface structure forms a uniform, discontinuous array on the surface structure. The surface structure may be of uniform size and uniformly arranged, or alternatively, the surface structure may be randomly arranged on the support substrate.

[0437] In some embodiments, the surface structure may form a repeating pattern or array or a series of patterns or arrays of the surface structure.

[0438] In some embodiments, the arrays or each array may form a uniform pattern of geometrically arranged surface structures, for example, as a pattern of groups of surface structures arranged in sequence.

[0439] In some embodiments, the surface structure may consist of electrically and / or spatially isolated areas or regions of the surface structure. For example, discontinuous areas of the surface structure or arrays of surface structures may be electrically and / or spatially separated and arranged on a support substrate. In one exemplary embodiment, each of the discontinuous areas of the surface structure may include a different shape and / or material.

[0440] In some embodiments, the surface structures are of substantially similar height, and / or they are substantially equivalent in shape, such that the distal tip of the surface structure is substantially flat.

[0441] In some embodiments, the surface structure is substantially flat such that the distance to the surface (e.g., the counter electrode surface) is substantially uniform across the array of surface structures. In other words, in some embodiments, the array of surface structures may protrude from the support substrate at a uniform height from the surface of the support substrate.

[0442] In some embodiments, the surface structure may be a height that is the same as, different from, or dissimilar to, the same as, different from, or dissimilar to, other surface structures, a regular or irregular geometric shape, equal or uneven spacing from one another, a density that is the same as, different from, or dissimilar to, or any combination thereof.

[0443] In some embodiments, the cross-sectional area of ​​the surface structure decreases along an axis perpendicular to the upper surface of the support substrate. In some embodiments, the surface structure consists of a distal tip portion, which is furthest from the surface from which the surface structure extends. The distal tip portion may be pointed, apex, spike, vertex, tip, or ridged. Alternatively, the distal tip portion may have a dome-shaped or circular cross-section, or a triangular, conical, convex, semicircular, dome, or papillary cross-section, along a plane perpendicular to the upper surface of the support substrate.

[0444] In some embodiments, the upper portion of the surface structure may have an angle of about 90° or less at the apex or distal tip, as described herein.

[0445] In some embodiments, the surface structure may be pointed or ridged, and may take the form of a cone, cone, ridged, pointed, spike, cylindrical, regular pentahedron, pentahedron with a planar top, pentagon or hexagon, or any combination thereof. Any such structure may have edges, vertices, ridges, or any combination of two or more such features. In some embodiments, the surface structure has a substantially triangular, substantially circular or dome-shaped or substantially square cross-section along a plane parallel to the upper surface of the support substrate.

[0446] In some embodiments, the upper or distal tip of the surface structure may be substantially similar in width to, or less than, the bottom or proximal tip of the surface structure. In the exemplary embodiments described herein, distal and proximal are relative to the surface of the support substrate to which the surface structure is associated or protrudes.

[0447] In some embodiments, the width of the surface structure connected to the support substrate (i.e., the base of the support substrate, or the proximal tip closest to the surface of the support substrate) may be approximately 5 nm to approximately 5000 μm. In some embodiments, the width of the surface structure connected to the support substrate is approximately 40 nm to approximately 4000 μm; approximately 55 nm to approximately 3000 μm, approximately 75 nm to approximately 2500 μm, approximately 100 nm to approximately 4000 μm, approximately 250 nm to approximately 3500 μm, approximately 20 nm to approximately 3500 μm, approximately 20 nm to approximately 4000 μm, approximately 20 nm to approximately 2500 μm, approximately 20 nm to approximately 4000 μm, approximately 20 nm to approximately 3000 μm, and approximately 20 nm to approximately 2000 μm. In some embodiments, the width of the surface structure connected to the support substrate is approximately 5 nm to 750 μm, approximately 5 nm to 500 μm, and approximately 5 nm to 100 μm.

[0448] In some embodiments, the width of the surface structure on the micrometer scale may be about 50 μm. In some embodiments, the width of the surface structure on the nanometer scale may be about 250 nm. In some embodiments, the width of the surface structure on the nanometer scale may be about 750 nm. In some embodiments, the width of the surface structure on the nanometer scale may be about 25 nm, or at least about 1 nm.

[0449] In some embodiments, the width of the surface structure connected to the support substrate on a micrometer scale can be approximately 5 μm to approximately 5000 μm. In some embodiments, the width of the surface structure on a micrometer scale can be approximately 50 μm.

[0450] In some embodiments, the length of the surface structure connected to the support substrate on a micrometer scale can be approximately 5 μm to approximately 5000 μm. In some embodiments, the length of the surface structure on a micrometer scale can be approximately 50 μm.

[0451] In some embodiments, the width of the surface structure connected to the support substrate on a nanometer scale may be about 2 nm to about 5000 nm. In some embodiments, the width of the surface structure on a nanometer scale may be about 250 nm.

[0452] In some embodiments, the length of the surface structure connected to the support substrate on a nanometer scale may be approximately 2 nm to approximately 5000 nm. In some embodiments, the length of the surface structure on a nanometer scale may be approximately 250 nm.

[0453] In some embodiments, the height of the surface structure (i.e., the height of the projection from or onto the support substrate or the surface of the support substrate) may be approximately 5 nm to approximately 5000 μm. In some embodiments, it may be approximately 40 nm to approximately 4000 μm, approximately 55 nm to approximately 3000 μm, approximately 75 nm to approximately 2500 μm, approximately 100 nm to approximately 4000 μm, approximately 250 nm to approximately 3500 μm, approximately 20 nm to approximately 3500 μm, approximately 20 nm to approximately 4000 μm, approximately 20 nm to approximately 2500 μm, approximately 20 nm to approximately 4000 μm, approximately 20 nm to approximately 3000 μm, or approximately 20 nm to approximately 2000 μm. In some embodiments, the height of the surface structure is approximately 1 nm to approximately 750 μm, approximately 1 nm to approximately 500 μm, or approximately 1 nm to approximately 100 μm.

[0454] In some embodiments, the height of the surface structure connected to the support substrate on a micrometer scale can be about 1 μm to about 500 μm. In some embodiments, the height of the surface structure on a micrometer scale can be about 50 μm.

[0455] In some embodiments, the height of the surface structure connected to the support substrate on a nanometer scale may be approximately 5 nm to approximately 5000 nm. In some embodiments, the length of the surface structure on a nanometer scale may be approximately 250 nm.

[0456] In some embodiments, the surface structure may have a base width and / or length of, for example, about 1 μm to about 500 μm on a micrometer scale. In some embodiments, the surface structure may have a height of, for example, about 1 μm to about 500 μm on a micrometer scale. In some embodiments, the tip of the surface structure described herein may be, for example, about 1 nm to about 10,000 nm on a nanometer scale. In one exemplary embodiment, the pyramidal or other shaped surface structure described herein may consist of inclined sidewalls extending to a relatively broad base region on a micrometer scale and converging to a pointed or tapered ridge or apex on a nanometer scale.

[0457] In any of the embodiments disclosed herein, it will be understood that the height, width, and length of a surface structure or array of surface structures may be determined by the required shape or size, such as a specific angle of the apex or tip or distal tip of the surface structure.

[0458] In some embodiments, the surface structure may be relatively large, for example, with a height and / or width and / or length of up to about 10 cm. In such embodiments, the vertices or tips of the surface structure may be on a micrometer or nanometer scale, allowing for suitable current focusing and achieving the pretreatment described herein.

[0459] In some embodiments, the micrometer-scale surface structure may be provided with or have a functional surface formed thereon, with a density of about 180,000 to about 1,800 vertices or tips per square centimeter. In some embodiments, the micrometer-scale surface structure may be provided with or have a functional surface formed thereon, with a low density of about 18,000 vertices or tips per square centimeter. In some embodiments, the surface structure may be provided with vertices or tips of about 1 to 2,000, about 1 to about 1,000, about 1 to about 500, or about 1 to about 100 per square centimeter.

[0460] In some embodiments, the nanometer-scale surface structure may have a functional surface provided or formed therefrom, with a density of approximately 160,000,000 to approximately 16,000,000,000 vertices or tips per square centimeter. In some embodiments, the nanometer-scale surface structure may have a functional surface provided or formed therefrom, with a density of approximately 1,600,000,000 vertices or tips per square centimeter. In some embodiments, the surface structure may have 50,000,000,000,000 surface structures or tips per square centimeter (i.e., 1 cm 2 For each 1 nm surface structure, where the spacing between adjacent surface structures is 1 nm, 5 × 10 13 It is provided at a density of the tip or structure.

[0461] In some embodiments, the surface structure may have parallel or substantially parallel sidewalls. In some embodiments, the surface structure may have inclined sidewalls terminating at the apex or vertex or distal tip, as described herein. In some embodiments, angles may be formed by sidewalls sharing the apex or vertex, measured or observed in a cross-section of the surface structure. Such angles may be substantially about 0° to about 180°, about 5° to about 175°, about 20° to about 90°, or about 50°.

[0462] The angles of the vertices, tips, or distal tips of the surface structures described herein may be formed by anisotropic etching of the underlying substrate or by a master used to form the surface structure, such as approximately 54.7° for silicon. It will be understood that such a process may provide a suitable angle for forming the vertices, tips, or edges, depending on the orientation of the crystal planes of the underlying substrate.

[0463] In some embodiments, the surface structure may include a top that is planar or columnar in shape, having either substantially parallel sidewalls or inclined sidewalls as described herein (e.g., a truncated pyramid). In one exemplary embodiment, such a structure may be on a micrometer, nanometer, or millimeter scale and may include additional smaller subsurface structures exposed on the top of the surface structure.

[0464] Size / shape of edges and vertices In some embodiments, the composite, alloy, or intermetallic compound is formed at least partially at the edges and / or vertices of the surface structure.

[0465] The edges and / or vertices of a surface structure are thought to be more reactive than other areas of the surface structure or supporting substrate, even before the pretreatment step. Therefore, they are considered particularly beneficial for the formation of composites, alloys, or intermetallic compounds at the edges and / or vertices. While we do not wish to be bound by theory, it is believed that voltage and / or current focusing effects exist at the edges and / or vertices (i.e., the applied current and / or measured voltage are not applied uniformly across the entire surface).

[0466] In some embodiments, the edges and / or vertices may be functional surfaces. In some embodiments, the functional surfaces may be the vertices or periphery of the surface structure.

[0467] In some embodiments, the functional surface may be the vertices or periphery of a surface structure, where the width of each vertex of the surface structure is approximately 1 nm to approximately 5000 μm. In some embodiments, the vertices or tips of each surface structure may be on an atomic scale, such as a single atom. In some embodiments, this is approximately 10 nm to approximately 10 μm, or approximately 20 nm to approximately 2 μm, or approximately 30 nm to approximately 1 μm. In some embodiments, this is approximately 1 nm to approximately 1000 nm, or approximately 1 nm to approximately 500 nm, or approximately 1 nm to approximately 100 nm, or approximately 1 nm to approximately 50 nm. The width of each vertex of the surface structure is shorter than the portion connected to the support substrate.

[0468] In some embodiments, the functional surface is the vertices or periphery of the surface structure, where the vertices of the surface structure are spaced apart from each other at intervals of approximately 1 nm to 1000 μm, 5 nm to 1000 μm, 10 nm to 1000 μm, 25 nm to 1000 μm, 5 nm to 750 μm, 5 nm to 500 μm, and 5 nm to 100 μm. In some embodiments, the intervals between the vertices are approximately 5 nm to 2000 nm; 5 nm to 1000 nm; and 5 nm to 500 nm.

[0469] In some embodiments, the edges and / or vertices constitute about 50%, 40%, 30%, 20%, 10%, 1%, 0.01%, 0.001%, 0.0001%, 0.00001%, and 0.0000001% of the surface area. In some embodiments, the edges and / or vertices constitute about 0.00000001% or about 0.000001% to about 50% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and / or vertices constitute about 0.0001% to about 50% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and / or vertices constitute about 0.0001% to about 50% of the surface area of ​​the structure when viewed from above.

[0470] In some embodiments, the functional surface constitutes less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 1%, less than about 0.01%, less than about 0.001%, less than about 0.0001%, less than about 0.00001%, and less than about 0.0000001% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and / or vertices constitute about 0.00000001% or about 0.000001% to about 50% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and / or vertices constitute about 0.0001% to about 50% of the surface area of ​​the structure when viewed from above. In some embodiments, the edges and / or vertices constitute about 0.1% to about 50% of the surface area of ​​the structure when viewed from above.

[0471] conductive fluid Conductive solutions are typically liquids, such as water and / or organic solvents. If a liquid is not sufficiently conductive in its pure form (e.g., pure water), a solution can be used, and the liquid may contain an electrolyte, for example. Suitable electrolytes are known to those skilled in the art, for example, in some embodiments, and the electrolyte is selected from buffers, salts (e.g., NaCl), alkali metals, or acidic and basic solutions (e.g., H2SO4, HNO3, NaOH, KOH). In some embodiments, the salt contains halide ions and / or metal ions (e.g., NaCl, copper²⁺ ions).

[0472] In some embodiments, the electrolyte concentration is about 0.05 M to about 20 M. In some embodiments, the electrolyte concentration is about 0.1 M to about 15 M. In some embodiments, the electrolyte concentration is about 0.1 M to about 12 M.

[0473] In some embodiments, the solution includes a buffering solution. The buffering solution may be useful in avoiding strongly acidic or basic conditions.

[0474] In some embodiments, the conductive liquid has a temperature below 100°C. In some embodiments, the temperature is below about 90°C, below about 80°C, below about 70°C, below about 60°C, below about 30°C, and below 20°C. The first electrode and / or the second electrode generate surprisingly little heat, even when relatively large currents are used. However, if the temperature of the conductive liquid rises, it is possible to lower the temperature to the desired temperature using cooling.

[0475] passivation layer In some embodiments, an inert or passivation layer may be deposited between the surface structures. In some embodiments, the thickness of the inert or passivation layer is about 10 times the height of the surface structure. -6 The percentage can be % and approximately 95%. In some embodiments, the passivation layer is deposited on a support substrate to cover the lower portion of the surface structure while exposing the upper portion. In some embodiments, the passivation layer on the functional surface in the upper portion of the surface structure is removed by applying a current or voltage to focus the charge density (voltage or current).

[0476] The passivation layer may be an oxide layer grown or positioned by the application of a chemical oxidizing agent or by reactive ion etching. This may be a self-forming single layer or a polymer, the latter of which may be applied by spin coating, spray coating, etc.

[0477] Use of catalyst formed in pretreatment step The catalyst arrays formed in the pretreatment step can be used in a variety of reactions. For example, a series of reactions using these arrays are discussed in W. Yu, et al. Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts, Chem. Rev. 2012, 112, 5780-5817.

[0478] In some embodiments, the pre-treated catalyst array is used in a reaction selected from hydrogenation, dehydrogenation, reforming, and oxidation reactions.

[0479] Hydrogenation can include C=C hydrogenation, C=O hydrogenation, N=O and C=N hydrogenation. Dehydrogenation reactions can include NH bond cleavage (e.g., ammonia dehydrogenation) and / or CH bond cleavage. Reformation of oxygenated products can include the reforming of alcohols and polyols. Other reactions include CO oxidation, water-gas shift reactions, and methane conversion.

[0480] In some embodiments, the reaction is selected from the following: generation of hydrogen from water, generation of oxygen from water, generation of hydrogen from water, generation of hydrogen from protons, oxidation of hydrogen to water, oxidation of hydrogen to protons, oxidation of hydrogen to hydrogen peroxide, reduction of oxygen to water, reduction of oxygen to peroxides, carbon monoxide from carbon dioxide, methanol from carbon dioxide, carboxylic acids (e.g., formic acid) from carbon dioxide, aldehydes and / or ketones from carbon dioxide, methane, ethane, propane and / or higher carbon chains of C21 or less from carbon dioxide, oxidation of methane to methanol, hydrazine from nitrogen, ammonia from nitrogen, cleavage of ammonia to hydrogen and nitrogen, methanol from methane, nitrogen from nitrates, and ammonia from nitrates.

[0481] In some embodiments, the reaction involves an active species in a gaseous or liquid state. In some embodiments, the conductive liquid is the active species. In some embodiments, the active species is a gas passed through the conductive liquid. In some embodiments, the gas is selected from air, hydrogen, oxygen, nitrogen, methane, carbon monoxide and / or carbon dioxide or air, or a mixture of two or more of these. In some embodiments, the active species is a liquid. In some embodiments, the liquid can be one or more of water, methanol, ethanol, propanol, acetone, ammonia, or liquid short-chain hydrocarbons (e.g., C21 or less). If the active species is water, the conductive solution is also preferably water containing an electrolyte or organic solvent. The organic solvent may be added to assist in solubility or involvement in the oxidizing or reducing process.

[0482] Electrocatalysts are a specific type of catalyst, where the catalyst functions as an electrode in an electrochemical reaction. Electrocatalysts have many applications, including fuel cells, the electrolysis of water into hydrogen, and chemical synthesis.

[0483] In particularly beneficial embodiments of the present invention, the present invention may provide a composite, alloy, or intermetallic compound formed on the reactive site of an already highly reactive electrocatalyst. It is already known that the topology of these electrodes makes the electrocatalyst highly reactive due to the focusing of current and / or voltage in the surface structure. Herein, the pretreatment step described in this application can further enhance this catalytic activity.

[0484] In one embodiment of the present invention, a method for carrying out a reaction is provided, which includes the step of contacting an array of the present invention or an array formed by a method of the present invention with at least one reactive species, wherein the array acts as a catalyst.

[0485] In one embodiment of the present invention, a method for carrying out an electrochemical reaction is provided. This method includes the step of applying an electric current between an electrocatalyst array described herein or an electrocatalyst array formed by the method described herein and a counter electrode in a conductive solution.

[0486] In some embodiments, the electrochemical reaction is selected from one or more of the following: hydrogenation, dehydrogenation, reforming, oxidation, generation of hydrogen from water, generation of oxygen from water, generation of hydrogen from water, generation of hydrogen from protons, oxidation of hydrogen to water, oxidation of hydrogen to protons, oxidation of hydrogen to hydrogen peroxide, reduction of oxygen to water, reduction of oxygen to peroxides, carbon monoxide from carbon dioxide, methanol from carbon dioxide, carboxylic acids (e.g., formic acid) from carbon dioxide, aldehydes and / or ketones from carbon dioxide, methane, ethane, propane and / or higher carbon chains of C21 or less from carbon dioxide, oxidation of methane to methanol, hydrazine from nitrogen, ammonia from nitrogen, ammonia cleavage to hydrogen and nitrogen, methanol from methane, nitrogen from nitrates, and ammonia from nitrates.

[0487] It will be apparent to those skilled in the art that catalysts can also be useful in other reactions. For example, catalyst alloys and a series of reactions in which they are used are studied in W. Yu, et al. Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts, Chem. Rev. 2012, 112, 5780-5817.

[0488] In some embodiments, the reaction involves an active species in a gaseous or liquid state. In some embodiments, the conductive liquid may be the active species. In some embodiments, the active species may be a gas passed through the conductive liquid. In some embodiments, the gas may be selected from air, hydrogen, oxygen, nitrogen, methane, carbon monoxide and / or carbon dioxide or air, or a mixture of two or more of these. In some embodiments, the active species may be a liquid, such as water, methanol, ethanol, propanol, acetone, ammonia, or a liquid short-chain hydrocarbon (e.g., C21 or less). If the active species is water, the conductive solution is also preferably water containing an electrolyte or an organic solvent. The organic solvent may be added to assist in solubility or involvement in the oxidizing or reducing process.

[0489] In some embodiments, this method may include a reference electrode. The reference electrode may be used to monitor and control the voltage at the working electrode (first electrode).

[0490] The counter electrode performs a charge equilibrium redox (oxidation or reduction) process and complements the redox (oxidation or reduction) process generated in the electrocatalyst array.

[0491] The counter electrode may be of various forms, shapes, and sizes, including woven fabrics, planes, perforated sheets, fibers, meshes, or arrays (e.g., pyramidal arrays, cone-shaped, cone-shaped, conical, or ribbed arrays).

[0492] In some embodiments, the counter electrode has a surface structure such as those described herein. In some embodiments, the shape of the counter electrode may reflect the shape of the surface structure. In some embodiments, the counter electrode has a surface structure opposite to that of the electrocatalyst array. In some embodiments, the counter electrode has a surface structure that is dissimilar in size, geometric shape, or pattern to that of the electrocatalyst array.

[0493] In some embodiments, the counter electrode may include a support substrate and surface structure as defined herein.

[0494] In some embodiments, the counter electrode is formed from a material selected from the group consisting of inert conductive materials, conductive materials, metals, Pt, gold, carbon, graphite, graphene, carbon fibers, carbon nanotubes, fullerenes, or conductive polymers such as polypyrrole (Ppy), polyalanine (PA), or polyacetylene (Pacetylene). Suitable materials for the counter electrode will be obvious to those skilled in the art.

[0495] In some embodiments, the counter electrode may (a) be fixed in orientation with respect to the surface structure, or (b) be attached to the electrode array, or (c) be held in an orientation that minimizes the difference in distance between the surface structures of the array, or (d) be on the top surface of the array, or (e) have 3D surface feature portions configured to facilitate the positioning of charge density (voltage or current) on the electrocatalyst array, such as a series of tips that reflect the tips of the electrocatalyst array. In some embodiments, the counter electrode is parallel to the electrocatalyst array.

[0496] In some embodiments, the potential difference set between the counter electrode or reference electrode and the electrolytic catalyst is approximately -20V to +20V. In some embodiments, it is approximately -1V to +1V. In some embodiments, the potential difference is approximately -200mV to -1V. Preferably, the potential difference is approximately 0mV to 1.8V for oxidation.

[0497] In some embodiments, this method includes a reference electrode. The reference electrode can be used to monitor and control the voltage acting on the electrocatalyst.

[0498] Various embodiments are described with reference to the drawings. Throughout the drawings and specification, the same reference numerals may be used to refer to the same or similar elements, and redundant descriptions thereof may be omitted.

[0499] Catalyst application As described above, the devices and arrays described herein can be used as electrochemical catalysts. However, the disclosure is not limited thereto. Arrays can be used as more classical catalysts for a wide variety of processes, including but not limited to hydrogenation, dehydrogenation, reforming, and oxidation. In such uses, the microstructure may have intermetallic materials such as alloys formed thereon as described above, or the microstructure may contain one or more metals without alloying, or the microstructure may contain oxides, hydrides, halides, hydroxides, alkali metals, alkaline earth metals, salts, carbides, organometallic complexes, complexes, alloys, or clusters.

[0500] That is, the structure may include, but is not limited to, a single metallic material such as Ag, Au, Co, Cr, Cu, Fe, Ga, Ge, Ir, Mn, Mo, Ni, Os, Pt, Pd, Re, Rh, Ru, Sn, Ti, V, or W, or, but is not limited to, a double metallic material such as Ni / Pt, Ni / Au, Pt / Au, Pt / Ag, Pt / Cu, Pt / Fe, Pt / Co, Pt / Cr, Pt / Sn, Pt / Ir, Pt / Mn, Pt / Mo, Pt / Pd, Pt / Re, Pt / Rh, Pt / Ru, Pt / Ti, Pt / V, Pt / W, Pt / Re, Pt / Os, Pt / Ru, or W / C. It will certainly be understood that a certain material / metal fill level can be kept low in the pre-treated structured surface array described herein. When these materials / metals are particularly expensive (i.e., Pt, Pd, and Au), a smaller packing amount can significantly reduce the cost of the catalytic process mediated by the pre-treated catalyst.

[0501] The structure of the catalyst array can be formed from a first metal, polymer, or ceramic. For example, the surface structure may be prepared from a first metal, and a large surface area catalyst of a single metal can be prepared by the microstructure provided as described above. Alternatively, the substrate may be a different material, i.e., a different metal, polymer, ceramic, etc., and the first metal is then coated on top of it. The catalyst may also contain a second metal (or more) as a dimetallic (or polymetallic) structure. In such a case, the second metal may be deposited on or in close proximity to the first metal so that each metal can exhibit catalytic function. As described above, the first and second metals may be the same metal but have different crystalline structures. For example, the (111) crystalline structure may form one layer, while (10) may form another. The catalyst may also contain a substrate having catalytic or supporting properties separately from the metal. For example, the substrate may be an alumina-, silica-, or titania-based ceramic material, or a graphite material. In some embodiments, the substrate may be γ-alumina.

[0502] The array structure is formed as described herein, and the array structure is subjected to pretreatment / pre-treatment which includes the step of conducting current through the array for a sufficient time to modify the electronic structure of the metal (or other material) by voltage, current density throughout the device (current density in the structure in the device), and by pre-treating the array to alter the electronic structure of the metal (or other material) through changes in orbital overlap. Pretreatment / pre-treatment also depends on the specific surface structure employed.

[0503] The surface structure (i.e., microstructure) provides a large surface area that influences the catalyst. Therefore, the microstructure improves contact with the target species for catalysis, while simultaneously resulting in a larger recoverable material after catalysis is complete. Microstructured monometallic, dimetallic, or polymetallic catalysts can be used in batch processes, where the catalyst is formed on or attached to the reactor wall, or as a solid object within the reactor. The catalyst is then easily recoverable from the reactor wall or from the reaction solution.

[0504] Microstructured monometallic, dimetallic, or polymetallic catalysts can also be used in flow processes, where the catalyst is formed in a tubular structure through which the reactants flow, or on the walls of the reactor as part of a large surface area system through which the reactants flow. In some embodiments, when a microstructured catalyst is used in a flow system, at least one of the reactants may be in the gas phase.

[0505] Accordingly, and in other embodiments, catalyst arrays are provided comprising a support substrate, a surface structure protruding from the surface of the support substrate formed or coated with a first metal. In such embodiments, the cross-sectional area of ​​the surface structure decreases along an axis perpendicular to the upper surface of the support substrate. In some such embodiments, the surface structure has a triangular, convex, semicircular, or papillary cross-section along a plane perpendicular to the upper surface of the support substrate. In some embodiments, the upper portion of the surface structure has an angle of about 90° or less at its apex. In some embodiments, the surface structure is pointed or ridged. In some embodiments, the surface structure is conical, cone-shaped, ridged, pointed, spiked, cylindrical, pentahedron, pentahedron with a planar top, pentagonal or hexagonal, or a combination thereof. Any such structure may have edges, apex, ridges, or a combination of two or more such features. In some embodiments, the surface structure has a substantially triangular, substantially circular or dome-shaped, or substantially square cross-section along a plane parallel to the upper surface of the support substrate.

[0506] In other embodiments, the second metal may be deposited on at least some of the surface structures to form a dimetallic catalyst structure. In some such embodiments, the second metal is deposited on the edges and / or apex of the surface structures.

[0507] A wide variety of specific general reactions can be catalyzed by pre-treated microstructured catalysts.

[0508] Some examples are given here. For instance, hydrogenation from alkynes to alkenes, hydrogenation from alkenes to alkanes, aromatic hydrogenation, hydrogenation from CO to aldehydes, and hydrogenation of NO and CN, depending on the desired reaction, may be Pt-Ni, Pt-Co, Pt-Sn, Pt-Ru, Pt-Rh, Pt-Au, Pt-Fe, or Pt-Pd on an alumina or silica substrate for the hydrogenation reaction. Depending on the specific metal selected, the specificity of the hydrogenation reaction can be improved as described in Yu et al. Chem. Rev. 112, 5780-5817 (2012). Dehydrogenation reactions may be carried out with dimetallic systems such as Pt / Ni, Pt / Sn, Pt / Au, Pt / Bi, Pt / Re, Pt / Pd, Pt / In, and Pt / Fe. Id. Reforming reactions, CO oxidation reactions, water-gas shift reactions, and methane conversion reactions can also be carried out in a pre-treated array.

[0509] Specific examples may include C=C hydrogenation carried out on a Ni layer having a Pt layer on top of it. The Ni layer may be a substrate or a layer on a substrate formed from a different material. For example, the substrate may be alumina, or more specifically, a γ-alumina substrate. Other metal combinations possible for C=C hydrogenation include Pt-Co and Pt-Cu on similar substrates. Another example of hydrogenation includes C≡C hydrogenation (i.e., acetylene to ethylene). Specific metal combinations useful for such hydrogenation include Pt-Ni on a γ-alumina substrate. Hydrogenation of aromatic compounds such as benzene involves Pt-Ni or Pt-Co on a γ-alumina substrate. However, activated carbon / graphite, silica, or titania substrates may be used depending on the desired activity. For Pt-Co dimetallic catalysts, depending on the substrate, the activity for benzene hydrogenation is generally known to decrease in the order of activated carbon >> SiO2 > γ-alumina > TiO2. Pt-Pd can also be used for the hydrogenation of aromatic compounds, and these can be accelerated by the presence of fluorine. Specific catalysts for C=O hydrogenation include Pt-Ni or Pt-Co on silica, γ-alumina, or titania substrates, exemplified by the hydrogenation of propanol, acetaldehyde, and acetone, in addition to aldehydes and ketones. Furthermore, changing the ratio of metals in the structured support array can affect the selectivity of hydrogenation in the presence of mixed environmental groups. For example, Pt-Au on silica is known to be active in the hydrogenation of α,β-unsaturated compounds. Pt-Sn is also known to be active in the hydrogenation of α,β-unsaturated aldehydes to form unsaturated alcohols, where the selectivity depends on the Pt-to-Sn ratio. Pt-Sn is also known for the selective C=O reduction of crotonaldehydes when supported on silica or α-alumina, when other more positively charged materials such as Co, Ge, Fe, Ga, or Ni are added. Certain N=O and C≡N hydrogenations include the hydrogenation of butyronitrile by Pt-Rh on activated carbon, and the hydrogenation of o-chloronitrobenzene to o-chloroaniline is mediated by Pt-Ru. Pt-Cu on γ-alumina can also be used for the reduction of nitrates and nitrites in nitrogen for treating drinking water.

[0510] Dehydrogenation can also be carried out using structured arrays. For example, a Pt-Ni catalyst can be used to dehydrogenate H2NNH2 to H2 and N2. Dehydration of alkanes is a key component of industrial processes used to produce polymers, ethers, and gasoline. Another detergent-like use of dehydrogenation is the storage of hydrogen in chemicals with a higher deposition energy density than hydrogen, and then dehydrogenating this chemical when hydrogen is needed. For example, cyclohexene can be dehydrogenated to benzene using a Pt-Au catalyst array, and Pt-Ni on activated carbon or γ-alumina is known to catalyze the conversion of cyclohexane to benzene. The addition of metals such as Bi, Re, Pd, In, and Fe can also accelerate dehydrogenation reactions.

[0511] The oxygenation reforming reactions of methanol, ethanol, ethylene glycol, or glycerol to CO and hydrogen can also be mediated by array catalysts described herein. For example, Pt-Ni, Pt-Fe, and Pt-Ni can be used for conversion at high turnover frequencies (TOF). The use of Re, Au, Rh, Sn, Pd, and Ru can provide choices for selectivity for hydrogen reforming and production for fuel cells. Various support materials can also be considered, including alumina, silica, activated carbon, titania, and zirconia. With respect to methanol reforming, the following activity order is observed: Pt-Fe > Pt-Ru > Pt-Pd > Pt-Au. With respect to CO oxidation, catalytic processes can be carried out to remove CO from a hydrogen stream for fuel cells. Pt-Ni alloys, Pt-Fe, Pt-Cr, Pt-Mn, Pt-Co, Pt-Zn, Pt-Sn, Pt-Ge, Pt-Tl, Pt-Cu, Pt-Pd, Pt-Rh, Pt-Re, and others can be used together with alumina, silica, titania, zirconia, cerium oxide, or activated carbon, in particular, as supports for removing CO from supplied H2. The water-gas-shift reaction can be mediated by Pt-Re, Pt-Co, Pt-Mo, Pt-Sn, or Pt-Cu on an alumina, silica, or titania support, with the use of co-catalysts such as Re, Co, or Au.

[0512] The conversion of methane to hydrogen is another important industrial reaction that can be mediated by the catalyst arrays described herein. Pt-Co is particularly effective, as are Pt-Pd on γ-alumina, activated carbon, zeolites (such as β-zeolite) and / or MgAl2O4.

[0513] In fuel cells, the oxygen reduction reaction (ORR) can be promoted at the cathode using a Pt-Ru and Pt-Rh array.

[0514] As described above, numerous dimetallic compositions can be used as catalyst arrays to mediate a wide range of reactions. Trimetallic (and higher-grade) compositions can also be used. Reforming reactions can employ a Pt-Ir-Sn catalyst on Al2O3, the hydrolysis and dehydrogenation of ammonia borane can be mediated by an Au-Co-Fe trimetallic catalyst, and Pt-Ag-Rh exhibits high activity in hydrogenation, particularly with respect to methyl acrylates. [Examples]

[0515] 1. Basic procedures for electrode manufacturing The structure (for example, one that can be used as an electrode) can be manufactured from a master (a structure with an inverted arrangement compared to the surface structure).

[0516] The master can be formed from various materials, such as silicon or metal.

[0517] In the following example, an inverted pyramidal array was fabricated in three steps from a Si wafer coated with silicon nitride (Si3N4). The Si3N4 coating was patterned by photolithography to define the base dimensions and spacing of the pyramidal feature portions. Isotropic etching of the Si3N4 layer was performed in buffered hydrofluoric acid, followed by anisotropic etching of Si using a KOH solution.

[0518] For example, it is possible to control the angle of the surface structure using anisotropic etching. Using anisotropic etching, we fabricated an array of inverted pyramidal microstructures with an angle of 54.7°. This angle corresponds to the orientation of the crystal planes in the silicon wafer. Using this approach, we fabricated a 50 μm × 50 μm inverted pyramidal silicon master array.

[0519] A nickel master was formed using a silicon master. A pyramidal nickel master was prepared by sputtering a thin layer of Ni (e.g., <100 nm) onto a Si master. The Ni-coated substrate was then electroplated in a nickel sulfamate solution containing nickel chloride. Once the thickness of the electroplated Ni reached a suitable thickness (e.g., about 350 μm), the electroplated or electroformed Ni was separated from the Si master. The electroplated Ni can then be used as a Ni master, or it can be inverted using a process similar to the one described above to form an inverted pyramidal array Ni master similar to the Si master. This process may include two or more inversion processes depending on the desired product and the structure of the initial master.

[0520] Using either of the above Ni forms, such as Ni pyramidal microstructures or Ni inverted pyramidal microstructures, or a master, an electroplated microstructure array described herein, which is used as an electrode in the following embodiments, can be formed. Alternatively, such a Ni microstructure can be used as a stamper to form the microstructure array described herein by stamping, for example, by hot embossing.

[0521] While the above examples illustrate the formation of Ni pyramidal microstructures, it will be understood that the same or similar techniques can be used to form submicron masters of other shapes and in other materials. For example, similar processes can be used to form nanostructured pyramidal shapes in Ni or other metals.

[0522] Alternatively, the nanostructured domes or tips described herein may be formed using a similar process. These nanostructures may be formed in Ni or other metals or materials. In such embodiments, an initial Si master may be formed using a Ni nanostructured master by interference lithography, and then formed by the electroplating process as described above.

[0523] The Ni microstructures or nanostructures obtained in the above examples were used as 3D nickel electrodes in the series of experiments described below.

[0524] The shape and structure of the 3D Ni electrode are shown in Table 1 and in Figure 1.

[0525] [Table 1]

[0526] 2. Basic procedure for applying the second metal to the electrode Metals can be deposited onto electrodes using various techniques known to those skilled in the art.

[0527] In this embodiment, the structure was coated with a thin metal film using either an electron beam evaporator or a DC magnetron sputter coater. The thickness was controlled using a quartz crystal digital thickness monitor (Inficon).

[0528] 3. Basic procedure for electrode "pretreatment" and tests performed on pretreated electrodes A two-electrode cell was constructed with metal-coated Ni electrodes as both the cathode and anode. The electrodes were placed in a cell that held them parallel to each other with a distance of 1 cm between them. In all cases, both the cathode and anode were equivalent in terms of 3D structure and metal coating. The cell was filled with an electrolyte solution and a current was applied for a predetermined time. While it is generally undesirable for the cathode and anode to have equivalent dimensions, this allowed for the investigation of the effects on both the anode and cathode. In other cases, the counter electrode can be made larger than the working electrode (e.g., 10 times larger) to reduce limitations on current flow.

[0529] To test the effectiveness of the pretreatment, the following tests were performed on the electrodes: • Visually evaluate any changes in the structure using a scanning electron microscope (SEM); • Elemental analysis of electrode structure by energy-dispersive X-ray spectroscopy (EDS); and The effect of pretreatment on the electrocatalytic behavior of the structure is evaluated using cyclic voltammetry (CV) or linear sweep (LS).

[0530] Figure 14 shows an example of the effect of pretreatment on a nickel tip electrode coated with Pt at 10 nm, both before (Figures 14A and C) and after (Figures 14B and D). In both cases, pretreatment resulted in the formation of nanoscale feature regions growing from the tip (apex) surface.

[0531] EDS characterizes elements by exciting electrons with X-rays and then matching the electromagnetic emission to a bank of characteristic spectra for various elements. In these experiments, EDS often showed peaks for novel elements, such as gold or zinc, that were clearly not present. These novel peaks indicate the presence of a substance that the EDS software considers to be most similar to the characteristic emission of gold or zinc (or any of the elements showing the novel peaks). The formation of these novel peaks indicates a change in the energy level of electrons in the structure.

[0532] The initial series of pretreatment experiments were performed using nickel electrodes with a 250 nm × 250 nm dome coated with 10 nm platinum. Table 2 lists the various conditions investigated. In each case, the temperature of the electrolyte solution was monitored, and cooling was performed if it exceeded 60°C. The voltage was also recorded during each pretreatment experiment.

[0533] [Table 2]

[0534] By changing the electrolyte concentration, the resistance of the solution can be altered, thereby changing the voltage required to obtain current. This effect could also be achieved by changing the distance between the cathode and anode. This could also be altered by introducing a membrane between the electrodes.

[0535] The results are summarized in Table 5.

[0536] In summary, the results showed that the preferred conditions for this combination of metal and structure are as follows: 1.6M electrolyte concentration (although this effect is thought to have also been achievable by changing the electrode spacing); 2.2 A / cm 2 The average current density (the average current density tested was 0.5~2A / cm²) 2 ) all showed some change in LS indicating a change in structure, but 0.5 A / cm 2 Only one showed a very small change; 3.4 hours of preprocessing time (although all the times we tried showed some change in LS); and 4. The oxide layer had little effect.

[0537] 4. Thickness of the second metal (see Table 5FA) Under the conditions listed in Table 3, a series of experiments were conducted using a 250 nm × 250 nm dome electrode to evaluate the effect of Pt thickness during pretreatment with an electrolyte concentration of 6 M KOH.

[0538] [Table 3]

[0539] Samples 1 and 2 were included for reference. In Sample 1, no platinum was deposited on the nickel electrode. In Sample 2, platinum was deposited on the electrode, but it was not subjected to the "pretreatment" step.

[0540] The results are summarized in Table 5 (Section 5A).

[0541] In summary, the results were as follows: • In samples 3 and 4, the EDX analysis of the pre-treated cathodes showed the appearance of a shoulder peak adjacent to the Pt peak (see Figure 2, which compares the EDX analysis showing the formation of a Pt peak (2.05 keV) in unpre-treated sample 2 and the formation of a new "gold" shoulder (2.22 keV) in pre-treated sample 4). This was nominally identified as "gold" by the software, with 10 nm Pt containing the largest amount of "gold" (Au). This peak has been previously identified as corresponding to a Ni / Pt alloy (see Zhang and J. Fang, A General Strategy for Preparation of Pt 3d-Transition Metal (Co,Fe,Ni) Nanocubes, JACS 2009 18543-18547). Beyond 10 nm, there was no indication of alloying in the EDS for this combination of metal and structure. • SEM (Figure 3) showed an increased presence of nanometer-sized feature regions in electrodes coated with 5 and 10 nm Pt (Samples 3 and 4), which was not observed in the plain nickel (Sample 1), nickel coated with untreated Pt (Sample 2), or the 15 nm coated sample (Sample 5). The linear sweep (LS) of the alloy-containing electrode showed a significant shift in the peaks corresponding to hydrogen formation, oxygen reduction, nickel oxide reduction, and oxygen generation when compared to the electrode coated with untreated Pt (Sample 2). Examples of LS are shown in Figures 4, 5, and 6. Figures 4, 5, and 6 show the LS (Low-Speed) ranges of Pt-coated electrodes (Sample 2) and uncoated electrodes (Sample 1) (both including those with and without pretreatment). In each case, pretreatment had a significant effect: • Hydrogen formation at -0.7 to -1.2V (Figure 4) showed that the voltage was slightly lower in the 15nm pre-treated sample (Sample 5) compared to the unpre-treated Pt-coated electrode (Sample 2); • Oxygen reduction at 0.0V to -1.0V (Figure 5) showed that all three pre-treated samples (Samples 3, 4, and 5) exhibited a maximum turn-on current reduction of 65mV and a significant increase in the total current conducted. Interestingly, both Samples 3 and 4, which were shown to be alloys in EDS, showed additional sharp peaks at -0.23V and -0.18V, respectively, but Sample 5 did not; and The reduction of nickel oxide and the generation of oxygen at 0.0V to 0.6V (Figure 6) showed that the alloyed samples (3, 4, and 5) exhibited improved catalyst turnover compared to the untreated sample (Sample 2).

[0542] Table 4 summarizes the electrochemical data for electrode samples 1-5 and shows the shift compared to nickel coated with untreated Pt (sample 2).

[0543] [Table 4]

[0544] One further result related to the pretreatment was the appearance of a peak at 1.02 keV in the EDS, which was interpreted as "Zn" (Figure 7, line B). This was not observed in the control of nickel only that had been pretreated (Figure 7, line A).

[0545] Sample 5 showed no changes in the outer structure in the SEM image and no "gold" peak in the EDS, yet it still showed a dramatic improvement in catalyst turnover in LS. While we do not wish to be bound by theory, this is likely because an alloy was formed as a boundary layer between the nickel-based substrate and the platinum coating, similar to that in dimetallic core-shell structures.

[0546] 5. Pretreatment for gold-coated nickel (see Table 5F) The effect of pretreatment on gold-coated nickel was investigated using a 250 nm × 250 nm dome with 10 nm of gold at different electrolyte concentrations (0.5 M, 6 M, and 12 M). The results are summarized in Table 5 (Section 5F).

[0547] The main effect of changing the electrolyte concentration was to affect the voltage at the electrode surface required to pass the necessary current. The voltages measured at different electrolyte concentrations were as follows: 0.5M required 6.2V, 6M required 3.2V, and 12M required 2.9V.

[0548] The EDS of the pre-treated sample showed the appearance of a "zinc" peak at 1.02 keV, but this peak increased as the electrolyte concentration decreased (Figure 8), which is thought to be due to the higher voltage at lower electrolyte concentrations.

[0549] The LS of gold-coated structures before and after pretreatment showed that this process had little effect on redox properties with respect to cycling in KOH solution and redox cycling of water, oxygen, and hydrogen. However, gold / nickel is thought to be able to enhance other reactions.

[0550] 6. Pretreatment of cobalt-coated nickel (see Table 5G) Figure 9 shows SEM images of a 250 nm × 250 nm dome coated with 10 nm Co, pre-treated with various electrolyte concentrations (Samples 27, 28, and 29), compared to an untreated Co sample (Sample 27).

[0551] Pretreatment with 0.5M KOH (Sample 27) and 6M KOH (Sample 28) resulted in small cactus-like structures at the vertices of the 3D structure, which consequently enlarged the overall footprint. EDS analysis showed the presence of Co, but it was reduced in Sample 28.

[0552] Pretreatment in 12M KOH (Sample 29) resulted in the formation of relatively large nanorods at the vertices of the 3D structure.

[0553] Figures 10 and 11 show linear sweep voltammetry of Co-coated 3D electrodes with and without various pretreatments. Figure 10 focuses on the portion related to O2 generation and shows that the activity of Co increases in the order of 30 > 29 > 28 > 27, as indicated by the reduction in overpotential.

[0554] Figure 11 shows linear sweep voltammetry in the region related to oxygen reduction. The results are for sample 29 pretreatment (6M 2A / cm²). 2 The results show that O2 reduction is promoted compared to the initial state of Co (Sample 27). However, Samples 28 and 30 showed a decrease in O2 reduction activity compared to the initial state of Co.

[0555] Typically, Pt-coated electrodes are used as anodes in fuel cells, so Figure 11 also includes the relative positions of oxygen reduction using 3D structures coated with untreated Pt. As can be seen in the figure, the effect of pretreatment is to increase the activity of Co beyond that of Pt, and the possibility of using less expensive pretreated Co instead of Pt in O2 reduction, such as in fuel cells, is being emphasized.

[0556] Figure 12 shows EDS data for the region corresponding to the "iron" peak that appeared after pretreatment of a Co-coated (10 nm) Ni electrode in a 0.5 M electrolyte for 4 hours. The solid line represents the Co / Ni control before pretreatment, and the dashed line represents the Co / Ni alloy after pretreatment. The circles indicate the peak position at 6.4 keV.

[0557] 7. Pretreatment for nickel coated with Pt having different lattice structures (see Table 5H) Nickel crystallinity can be controlled by changing the electroforming growth conditions. Approximately 70% 2θ(200) is obtained in a sulfamic acid nickel bath. Adding chloride resulted in approximately 70% 2θ(111). The effect of pretreatment on Pt-coated nickel with different crystallinity levels was investigated using a 250 nm × 250 nm dome with 10 nm Pt and an electrolyte concentration of 6 M. The results are summarized in Table 5 (Section H), showing that Ni 2θ(200) is slightly better than Ni 2θ(111) in terms of increased electrocatalytic performance under standard conditions.

[0558] 8. Pretreatment of Pt-coated nickel with different 3D structures (see Table 5I) The effects of pretreatment on Pt-coated nickel with different 3D structures, summarized in Table 1, were investigated using 10 nm Pt and a 6 M electrolyte concentration. The results are summarized in Table 5 (Section 5I), showing that the sharper the tip, the better the electrocatalytic turnover under standard conditions.

[0559] 9. Pretreatment of CoPt and PtCo on nickel (see Table 5J) The effects of pretreatment on nickel substrates coated with PtCo and CoPt were investigated using a 250nm x 250nm dome with 10nm Pt and an electrolyte concentration of 6M. The results are summarized in Table 5 (Section J), showing that the formation of the alloy / composite significantly increases the electrocatalytic activity compared to the parent metal.

[0560] 10. Pretreatment of PtNi multilayer structures on nickel (see Table 5K) The effect of pretreatment of multiple Pt(5nm)Ni(5nm) layers on a nickel substrate was investigated using a 250nm × 250nm dome with 10nm Pt and an electrolyte concentration of 6M. The results are summarized in Table 5 (Section 5K), demonstrating that electrocatalytic activity can be increased by adding multiple layers under standard pretreatment conditions.

[0561] 11. Summary of the results of the pretreatment experiment. Table 5 lists the pretreatment experiments, including those mentioned above, and is grouped by the type of experiment described in each heading. This table shows that the EDS or LS data exhibits a significant effect brought about by the pretreatment, and lists the shift at the working electrode in the LS data compared to the untreated Pt-coated electrode (Sample 2).

[0562] In Table 5, A, B, and C correspond to the shifts in the onset of hydrogen formation, oxygen reduction, and oxygen evolution compared to an untreated Pt-coated electrode (Sample 2). The table lists these shifts, which are then compared to a Pt-coated Ni standard (Sample 2) (whose actual values ​​are A-1100mV, B-150mV, and C 460mV).

[0563] The EDS peaks are related to a value of 1.01 keV for "Zn" corresponding to the appearance of a shift in the nickel peak (usually 0.851 keV), and to a value of 2.12 keV for "Au" corresponding to the appearance of a shift in the platinum peak (usually 2.05 keV).

[0564] [Table 5]

[0565] [Table 6]

[0566] [Table 7]

[0567] [Table 8]

[0568] [Table 9]

[0569] [Table 10]

[0570] [Table 11]

[0571] [Table 12]

[0572] [Table 13]

[0573] [Table 14]

[0574] [Table 15]

[0575] [Table 16]

[0576] 12. A method for applying a second metal and performing "pretreatment" in one step. The nickel 3D electrode was washed with IPA and water and set up as the working electrode in an electrochemical cell containing a nickel counter electrode, an Ag / AgCl reference electrode, and a 6M KOH electrolyte. Platinum(IV) chloride (1 mM) was added, and the reduction potential was set to 2 A / cm² at the working electrode. 2 The current density was applied for 1 hour. The 3D electrode was washed with water and analyzed by SEM and EDS.

[0577] As shown in Figure 14D, Pt deposition and alloying occurred mainly at or around the apex of the surface structure. The EDS showed a structure composed of Ni, Pt, and Ni / Pt alloys.

[0578] To achieve high current density and voltage / current focusing at or around the apex of the surface structure, Pt was reductively deposited at a higher density at the apex. This provides a method for selectively arranging alloys on the surface structure. The applied voltage is highly reductive, and therefore, the process simultaneously achieves reduction and alloying of different metal combinations.

[0579] This combines the ability to impart selective functionality to specific parts, alloying, and minimizing the amount of high-value metals required.

[0580] References W.Yu,MDPorosoff,JGChen,Review of Pt-Based Bimetallic Catalysis:From Model Surfaces to Supported Catalysts,Chem.Rev.2012,112,5780-5817 J. Das, I. Ivanov1, L. Montermini, J. Rak, EHSargent and SOKelley, An electrochemical clamp assay for direct, rapid analysis of circulating nucleic acids in serum, Nature Chemistry VOL 7, 2015, 569-575.

[0581] general As used herein, "approximately" will be understood by those skilled in the art and will vary to some extent depending on the context in which it is used. Where there is a use of the term that is not obvious to those skilled in the art, "approximately" will mean up to 10 percent above or below a given term, depending on the context in which it is used.

[0582] The term "micron" refers to a micrometer (μm).

[0583] The use of the terms “a,” “an,” and “the,” and similar references in the context describing elements (in particular, in the context relating to the claims below), should be interpreted as including both singular and plural forms, unless otherwise specified in the specification or unless the context would clearly contradict them. References to ranges of values ​​in this specification are intended merely as abbreviations to individually refer to each of the individual values ​​within that range, unless otherwise specified in this specification, and each of the individual values ​​is incorporated into the specification as if it were individually cited herein. All methods described herein may be implemented in any preferred order, unless otherwise specified in this specification or unless the context would clearly contradict them. Any and all use of example or illustrative language (e.g., “etc.”) in this specification is intended merely to further illustrate the embodiments and does not limit the scope of the claims unless otherwise specified. Language in the specification should not be interpreted as indicating that any unclaimed element is essential.

[0584] While certain embodiments have been illustrated and described, it should be understood that modifications and alterations can be made according to those skilled in the art without departing from the broader aspects of the art defined in the following claims.

[0585] The embodiments described herein as exemplary may be suitably carried out in the absence of any one or more elements or limitations not specifically disclosed herein. Therefore, terms such as “comprising,” “including,” and “containing” are to be interpreted broadly and without limitation. Furthermore, these terms and expressions used herein are for illustrative purposes only and are not restrictive; in using such terms and expressions, it is not intended to exclude any equivalent or part thereof of any of the shown and described feature elements, and it is recognized that various modifications are possible within the scope of the claimed technology. Also, the phrase “consisting essentially of” is to be understood to encompass the specifically mentioned elements and any additional elements that do not substantially affect the basic and novel features of the claimed technology. The phrase “consisting of” excludes any unspecified elements.

[0586] This disclosure should not be limited to the specific embodiments described herein. As will be apparent to those skilled in the art, many modifications and variations are possible without departing from its spirit and scope. In addition to those enumerated herein, functionally equivalent methods and compositions within the scope of this disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. This disclosure should be limited only by the full scope of the appended claims and the equivalents authorized by such claims. It should be understood that this disclosure is not limited to specific methods, reagents, chemical compositions or biological systems, which may naturally vary. It should also be understood that the terminology used herein is intended solely to describe specific embodiments and is not intended to be limiting.

[0587] In addition, if any feature or aspect of the present disclosure is described in terms of the Markush group, a person skilled in the art will recognize that the present disclosure is also described by any individual component or subgroup of components of the Markush group.

[0588] As will be understood by those skilled in the art, all scopes disclosed herein also encompass any and all possible sub-scopes, and combinations thereof, in part with respect to any and all of the purposes, particularly in terms of providing written descriptions. Any enumerated scope is readily recognizable as sufficiently described, and the same scope is divisible into at least two, three, four, five, ten, etc. As a non-limiting example, each of the scopes considered herein is readily divisible into a lower third, a middle third, and an upper third, etc. As will also be understood by those skilled in the art, all terms such as “at most,” “at least,” “greater than,” “less than,” etc., include the number mentioned and refer to scopes that are subsequently divisible into sub-scopes as described above. Finally, as will be understood by those skilled in the art, the scope includes each of the individual components.

[0589] All publications, patent applications, issued patents, and other documents referenced in this specification are incorporated by reference in this specification as if each individual publication, patent application, issued patent, or other document were specifically and individually incorporated in whole. Definitions contained in the texts incorporated by reference are excluded to the extent that they conflict with the definitions in this disclosure.

[0590] Other embodiments are described in the following claims.

[0591] Attributes and embodiments of the present invention: The following sections describe aspects and embodiments of the present invention, but these are not claims.

[0592] Section 1: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first material; The second material is deposited on at least some of the surface structures such that the second material is in contact with the first material. An array including, Here, the first material, the second material, or the first material and the second material are conductive or semiconductive; Here, the first material and the second material form a composite at least partially.

[0593] Section 2: A support substrate having a surface structure that protrudes from the surface of the support substrate; and Composite material formed on at least a portion of the surface structure An array including, Here: The composite material is the product of the electrolytic reaction of the first material and the second material. The first material, the second material, or the first material and the second material are conductive or semiconducting.

[0594] Section 3: A method for forming an array, the method is Steps include applying an electric current between a first electrode and a second electrode in a conductive solution. Includes, The first electrode is: Support substrate; Surface structures protruding from the surface of a support substrate formed or coated with a first material; and A second material deposited on at least some of the surface structures in contact with the first material. Includes, Here: The first material, the second material, or the first and second materials are conductive or semiconductive; The applied current density is sufficient to form a composite at the interface.

[0595] Section 4: A method for forming a composite, comprising a structure having edges and / or vertices, and the step of conducting an electric current between a first material and a second material at the edges and / or vertices, wherein the first material and the second material are in contact, wherein the first and / or second materials are conductive or semiconducting, and wherein the current density at the edges and / or vertices is sufficient to form a composite at the interface between the first material and the second material.

[0596] Section 5: A method for pretreatment of a catalyst array, the method being Steps include applying a current between the first electrode and the second electrode in a conductive solution sufficient to form a composite from the first material and the second material in the first electrode, the second electrode, or both the first electrode and the second electrode. Includes, Here, the catalyst array includes a first electrode, a second electrode, or both the first electrode and the second electrode.

[0597] Section 6: A method for forming an alloy array, the method is Steps include applying an electric current between a first electrode and a second electrode in a conductive solution. Includes, The first electrode is: Support substrate; Surface structures protruding from the surface of a support substrate formed or coated with a first alloy component; and Second alloying component deposited on the surface structure Includes, Here, the applied current density is sufficient to at least partially form an alloy of the first alloy component and the second alloy component on the surface structure; Here, the alloy array is formed on the first electrode.

[0598] Section 7: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first material; The second material is deposited on at least some of the surface structures such that the second material is in contact with the first material. An array including, Here, the first material, the second material, or the first material and the second material are conductive or semiconductive; Here, there is a change in the orbital overlap of the electronic structures of the first material, the second material, or the first material and the second material.

[0599] Section 8: A method for forming an array, the method is Steps include applying an electric current between a first electrode and a second electrode in a conductive solution. Includes, The first electrode is: Support substrate; A surface structure protruding from the surface of a support substrate formed or coated with a first material; The second material is deposited on the surface structure such that it is in contact with the first material. Includes, Here, the first material, the second material, or the first material and the second material are conductive or semiconductive; Here, the applied current density is sufficient to distort the energy of the outer shell electrons of the first and second materials when the current is no longer applied.

[0600] Section 9: A support substrate having a surface structure that protrudes from the surface of the support substrate; and Composite material formed on at least a portion of the surface structure A catalyst array comprising, Here: The composite material is the product of the electrolytic reaction of the first material and the second material; and The surface structure is: Pyramidal structures having a height of less than 100 microns to approximately 10 microns, and a base dimension of approximately 10 microns to approximately 100 microns; and / or It has a circular or elongated dome-shaped structure with a height of approximately 1000 nm to 1 nm and a diameter of approximately 1000 nm to 1 nm.

[0601] Section 10: A method for pretreatment of a catalyst array, the method comprising: Support substrate; Surface structures protruding from the surface of a support substrate formed or coated with a first metal; and The second metal is deposited on at least some of the surface structures such that the second metal is in contact with the first metal. A step of providing a catalyst array including; Steps include contacting the electrolyte solution with the catalyst array; A step of applying a bias to the array with a voltage and current for a specific time to form a pre-processed array. Includes, Here: The metal in the pre-treated array has a modified electronic structure compared to the metal before the bias was applied.

[0602] Item 11: The method described in Item 10, wherein the modified electronic structure has altered orbital overlaps of the metal compared to the metal before the bias is applied.

[0603] Paragraph 12: The method described in Paragraph 10, wherein the specific time is approximately 0.5 hours to approximately 20 hours.

[0604] Paragraph 13: The method described in Paragraph 10, wherein the specific time is approximately 1 hour to approximately 10 hours.

[0605] Paragraph 14: The method described in Paragraph 10, wherein the specific time is approximately 3 hours to approximately 9 hours.

[0606] Item 15: The method described in Item 10, wherein the voltage is approximately -20 volts to approximately +20 volts.

[0607] Item 16: The method described in Item 10, wherein the voltage is approximately + / -20 volts to approximately + / -0.5 volts.

[0608] Item 17: The method described in Item 10, wherein the voltage is approximately + / -10 volts to approximately + / -0.5 volts.

[0609] Item 18: The method described in Item 10, wherein the current density is 0 A / cm². 2 Super ~ about 10A / cm 2 That is the case.

[0610] Item 19: The method described in Item 10, wherein the current density is approximately 1 A / cm². 2 Approximately 5A / cm 2 That is the case.

[0611] Item 20: The method described in Item 10, wherein the current density is approximately 2 A / cm². 2 That is the case.

[0612] Paragraph 21: The method according to paragraph 10, wherein the electrolyte is an alkaline electrolyte.

[0613] Item 22: The method according to item 10, wherein the electrolyte comprises a metal oxide or a metal hydroxide.

[0614] Item 23: The method according to item 22, wherein the electrolyte comprises a metal hydroxide containing NaOH or KOH.

[0615] Paragraph 24: The method described in Paragraph 23, wherein NaOH or KOH is present in the electrolyte at approximately 0.5 M to approximately 10 M.

[0616] Paragraph 25: The method described in Paragraph 23, wherein NaOH or KOH is present in the electrolyte at approximately 2 M to approximately 8 M.

[0617] Item 26: The method described in item 23, wherein NaOH or KOH is present in the electrolyte at approximately 4 M to approximately 6 M.

[0618] Paragraph 27: The method described in Paragraph 10, wherein the modified electronic structure is indicated by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0619] Paragraph 28: The method described in Paragraph 27, wherein the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0620] Item 29: The method according to Item 10, wherein the second metal is present in thicknesses of approximately 1 nm to approximately 1 μm, approximately 1 nm to approximately 500 nm, approximately 5 nm to approximately 250 nm, approximately 5 nm to approximately 100 nm, approximately 5 nm to approximately 50 nm, approximately 5 nm to approximately 30 nm, approximately 5 nm to approximately 25 nm, approximately 5 nm to approximately 15 nm, or approximately 10 nm in thickness.

[0621] Item 30: The method according to item 10, wherein the array further comprises alternating layers of a first metal and a second metal, wherein there are no more than 200 layers of each metal.

[0622] Section 31: The method described in Section 30, wherein each layer of the array has a thickness of 1 to 10 nm.

[0623] Item 32: The method described in item 10, wherein the array comprises first and second metal layers, the layers being Ni / Pt;Ni / Au;Ni / Co;Ni-supported Co / Pt;Ni-supported Pt / Co;Ni-supported Pt / Ni; and Ni-supported Pt / Ni / Pt / Ni / Pt / Ni / Pt.

[0624] Section 33: Support substrate; A surface structure that protrudes from the surface of the support substrate and is integral with the support substrate; and A surface structure having catalytic properties and comprising a composite material formed from at least a first material and a second material. A catalyst array comprising, Here, the composite material exhibits a modified electronic structure compared to a mixture of the first and second materials; and Here, the surface structure is 100 / cm on the supporting surface. 2 It exists in a superhuman state.

[0625] Paragraph 34: The array described in paragraph 33, wherein the first material is the same as the material constituting the substrate, or the first material is a different material from the substrate.

[0626] Item 35: The array described in item 33 or 34, wherein the composite is prepared by pre-treating the array by applying a bias to the first and second materials.

[0627] Paragraph 36: The array described in paragraph 35, wherein the modified electronic structure is shown by observing the change in the linear sweep voltammetry of the array before and after the application of a bias.

[0628] Paragraph 37: The array described in paragraph 36, wherein the change in the linear sweep voltammetry of the array includes an oxidation or reduction shift to a more positive or negative voltage after pretreatment of the array.

[0629] Section 38: Support substrate; and Surface structures that protrude from the surface of the support substrate; Surface substructures in each of the surface structures A catalyst array comprising, The surface substructure includes a composite material having catalytic properties; Here, The composite material is formed from at least a first material and a second material during the pretreatment of the catalyst array; The composite material exhibits a modified electronic structure compared to the mixture of the first and second materials before pretreatment; and The surface structure is 100 / cm² on the supporting surface. 2 It exists in a superhuman state.

[0630] Paragraph 39: A method for forming a catalyst array, the method is Steps include applying an electric current between a first electrode and a second electrode in a conductive solution. Includes, The first electrode is: Support substrate; and Surface structure that protrudes from the surface of the support substrate and includes a composite material having catalytic properties. Equipped with, and Here: The composite material is formed from a combination of a first material and a second material; The applied current density is sufficient to form a composite material at the interface; and The composite material exhibits a modified electronic structure compared to the combination containing the first and second materials before the application of current.

Claims

1. An electrocatalyst array for use in hydrogenation, dehydrogenation, reforming, and oxidation reactions, comprising: Support substrate; A plurality of surface structures protruding from the surface of the support substrate and formed or coated with a first material, wherein the first material is a polymer, an organic compound, an inorganic compound, or a metal, and the plurality of surface structures include edges and / or vertices; A second material deposited on at least a portion of the plurality of surface structures, wherein the second material is in contact with the first material; The second material described above is a polymer, an organic compound, an inorganic compound, or a metal. The first material, the second material, or the first and second materials are conductive or semiconductive; The first material and the second material form a composite at least partially, An array in which the density of composites formed at the edges and / or vertices of the surface structure is higher than the density of composites formed in other parts of the surface structure.

2. The array according to claim 1, wherein the composite is an electrolytic reaction product of the first material and the second material, and / or the electronic structure of the composite is modified compared to the electronic structures of the first material and the second material.

3. The array according to claim 1 or 2, wherein the composite is formed on a plurality of surface structures as substructures having a cross-sectional area smaller than the cross-sectional area of ​​the surface structures.

4. The array according to claim 3, wherein the second material comprises one or more of a series of particles, atoms, or substructures.

5. The array according to any one of claims 1 to 4, wherein a plurality of the second materials are spatially isolated from one another.

6. The array according to any one of claims 1 to 5, wherein the composite is selected from intermetallic compounds, polymer-metal composites, organic-inorganic composites, alloys, and polymetallic compounds.

7. The array according to any one of claims 1 to 6, wherein the second material is embedded in or incorporated into the first material and / or, in a top view, covers less than 50% of the surface.

8. The array according to any one of claims 1 to 7, wherein the thickness of the second material is 5 nm or more and 50 nm or 5 nm or more and 10 nm.

9. The array according to any one of claims 1 to 8, wherein one or more additional materials different from the first and / or second materials are present on at least a portion of the surface structure, and the one or more additional materials are selected from polymers, organic compounds, inorganic compounds, and metals.

10. The array according to any one of claims 1 to 9, wherein the support substrate and the surface structure are formed from the first material.

11. The array according to any one of claims 1 to 10, wherein the plurality of surface structures are arranged at equal intervals from each other, or are of uniform size from each other, or are uniformly arranged, or are of the same shape from each other.

12. A method for forming an electrocatalytic array for use in hydrogenation, dehydrogenation, reforming, and oxidation reactions, comprising: A step of applying an electric current between a first electrode and a second electrode in a conductive solution; The first electrode is: Support substrate; A plurality of surface structures protruding from the surface of the support substrate and formed or coated with a first material, wherein the first material is a polymer, an organic compound, an inorganic compound, or a metal, and the plurality of surface structures include edges and / or vertices; A second material deposited on at least a portion of the plurality of surface structures, wherein the second material is in contact with the first material; The second material described above is a polymer, an organic compound, an inorganic compound, or a metal. The first material, the second material, or the first and second materials are conductive or semiconductive; The applied current density is sufficient to form a composite at least at the interface between the first material and the second material. A method wherein the density of the composite formed at the edges and / or vertices of the surface structure is higher than the density of the composite formed in other parts of the surface structure.

13. The method according to claim 12, wherein the applied current density is sufficient to form the composite as an electrolytic reaction product of the first material and the second material and / or the composite having a modified electronic structure compared to the electronic structure of the mixture of the first material and the second material before the composite was formed.

14. The composite is selected from intermetallic compounds, polymer-metal composites, organic-inorganic composites, alloys, and / or polymetallic compounds. The first material is a metal and / or, The second material is a metal and / or, The method according to claim 12 or 13, wherein the first and / or second material is a metal and is in one or more forms of oxides, hydrides, halides, hydroxides, salts, carbides, organometallic complexes, complexes, alloys, and clusters.

15. The method according to any one of claims 12 to 14, wherein the second material is embedded in or incorporated into the first material and / or deposited on less than 50% of the surface when viewed from above.

16. The method according to any one of claims 12 to 15, wherein the deposition density of the second material at the edges and / or vertices of the plurality of surface structures is higher than the deposition density of the second material at other parts of the plurality of surface structures.

17. The method according to any one of claims 12 to 16, wherein one or more further materials different from the first and / or second materials are deposited on at least some of the surface structures, and the one or more further materials are selected from polymers, organic compounds, inorganic compounds, and metals.

18. The method according to any one of claims 12 to 17, wherein the plurality of surface structures are arranged at equal intervals from each other, are of uniform size from each other, are uniformly arranged, or have the same shape from each other.

19. The method according to any one of claims 12 to 18, wherein the conductive solution comprises the second material, and the second material is electrochemically deposited on at least some of the surface structures when an electric current is applied, and / or is electrochemically deposited at the edges and / or vertices at a higher density than elsewhere when an electric current is applied.

20. The method according to any one of claims 12 to 19, wherein the thickness of the second material or the discontinuous layer is 5 nm or more and less than 50 nm, or 5 nm or more and less than 10 nm.

21. The method according to any one of claims 12 to 20, wherein the potential difference set between the first electrode and the second electrode is -20V to +20V.

22. The current applied between the first electrode and the second electrode is 0.3 A / cm² on average across the first electrode and / or the second electrode. ２ The method according to any one of claims 12 to 21.

23. The method according to any one of claims 12 to 22, wherein the current is applied for a period of time from one minute to 24 hours, which is sufficient to form a composite.

24. The method according to any one of claims 12 to 23, wherein the conductive solution comprises water, an organic solvent, or an electrolyte.

25. The method according to any one of claims 12 to 24, wherein the applied current density is sufficient to form a substructure having a cross-sectional area smaller than the cross-sectional area of ​​the surface structure.

26. A method for carrying out a reaction, comprising the step of contacting an array according to any one of claims 1 to 11, or an array formed by the method according to any one of claims 12 to 25, with at least one reactive species, wherein the array acts as a catalyst.

27. A method for carrying out an electrochemical reaction, comprising the step of applying an electric current between an electrocatalyst array according to any one of claims 1 to 11, or an electrocatalyst array formed by the method according to any one of claims 12 to 25, and a counter electrode.

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