Functionalized tetragonal transition metal disulfide and application thereof

Abstract

The invention discloses a functionalized tetragonal transition metal disulfide and application thereof, and belongs to the field of process chemistry, the functionalized tetragonal transition metal disulfide is of a tetragonal system structure, and the space group is P4 / nmm; in the process of catalytic reduction of CO2, Ni-FeS, Cu-FeS and Ni-CoS tend to two-electron process CO2 + 2H + + 2e-> HCOOH, Fe-CoS, Co-FeS and Co-CoS tend to eight-electron process CO2 + 8H + + 8e-> CH4 + 2H2O, and the material has good activity and selectivity, and can be used as a CRR electrode candidate material in the method of electrocatalytic reduction of carbon dioxide.

Description

Technical Field

[0001] The invention relates to the technical field of process chemistry, and in particular to a functionalized tetragonal transition metal disulfide and application thereof. Background Art

[0002] With the advancement of global industrial production and the acceleration of urbanization, energy demand has increased dramatically, especially the demand for fossil fuels. The consumption of fossil energy produces a large amount of greenhouse gases, among which the sharp increase in carbon dioxide concentration leads to climate change, threatening the ecological environment. [1] Against this backdrop, there is great enthusiasm for reducing CO2 concentrations and even replacing the burning of fossil fuels.

[0003] Among various technologies, electrocatalytic CO2 reduction reaction (CRR) is a promising route to convert CO2 into valuable hydrocarbon products. [2] , which will help control the concentration of carbon dioxide in the air. According to previous studies, among various pure metals, copper is the best material for catalyzing the conversion of carbon dioxide into hydrocarbon CH4. [3,4] However, the high dissociation energy of CO2 activation and the high overpotential of CO2 protonation are two major obstacles to CO2 conversion. [5,6] This becomes a challenge for the design of CRR catalyst materials and hinders the in-depth understanding of the complete CRR mechanism.

[0004] Transition metal dichalcogenides (TMDs) are a class of two-dimensional materials with excellent physical and chemical properties for electrocatalytic applications. For example, Pu et al. found that Sc and Ti adsorbed on vacancy-defective TMD monolayers are suitable for electrochemical CRR, and the reactivity is further enhanced when biaxial tensile strain is applied. [7] In addition, Linghu et al. proposed that the adsorption of Ru on WS2 would enhance the CRR performance for CH4 production with a limiting potential of −0.47 V and limit the competing HER [8] Similarly, Sun and Liu found that HCOOH is the favored product when CO2 is loaded with iron or copper by PtS2, where the limiting potentials of Fe-PtS2 and Cu-PtS2 are 0 V and 0.25 V, respectively, even exceeding that of Cu(211) [9] .

[0005] In addition to the above TMDs, a new class of tetragonal transition metal chalcogenides with unique layered structures and tunable electronic properties has been recently synthesized.

[10] Borg et al. reported that K was removed by hydrothermal deintercalation under alkaline and reducing conditions. x Fe 2-y Tetragonal FeS was prepared from S2 crystals

[11] In addition, Huang et al. deposited a single layer of tetragonal FeSe on SrTiO3 and performed post-growth annealing to obtain FeSe / SrTiO3

[12] Similarly, CoS and CoSe were successfully prepared from KCo2S2 and KCo2Se2 by topological chemical deintercalation.

[13] In addition, Zhong et al. synthesized CoSe by a simple topological chemical intercalation method.

[14] Interestingly, the atomic arrangement of the tetragonal phase is different from that of conventional TMDs. The basal plane of the former is composed entirely of exposed chalcogenide sites, each chalcogenide atom is connected to four transition metal atoms, and the chalcogenide atoms are located at the top of the pyramid structure.

[0006] This material with good electron conductivity is very important in HER [15-17] 、OER [18,19] , ORR

[20] and NRR

[21] For example, Lin et al. compared the HER performance of tetragonal and hexagonal CoSe and found that the overpotential of the former was 175 mV and the Tafel slope was 36.3 mVdec. -1 , better than the latter

[17] Cheng et al. found that tetragonal FeSe can catalyze OER at an overpotential of 1.16 V.

[19] In addition, the authors also found the feasibility of tetragonal FeSe in ORR applications with a corresponding overpotential of 0.73 V, which means it is a bifunctional OER / ORR electrocatalyst.

[20] In addition, with the generation of S / Se vacancies, FeS-V S and FeSe-V Se Provides excellent NRR performance with low overpotentials of 0.49 and 0.68 V

[21] However, the above-mentioned tetragonal transition metal disulfides are still unclear as CRR cathode materials. Therefore, it is of great significance to study and develop catalysts with inherent basal activity and high stability for electrocatalytic CO2 reduction.

[0007] References

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[21] H.Yin,A.Du,Small Structures,2022,3,2200107. Summary of the invention

[0029] In view of the shortcomings of the prior art that tetragonal transition metal disulfides are still unclear as cathode materials for electrocatalytic carbon dioxide reduction, in order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a functionalized tetragonal transition metal disulfide and its application, which makes it possible to efficiently catalyze the reduction of carbon dioxide under normal temperature and pressure and strong adsorption.

[0030] In order to solve the problems of the prior art, the technical solution adopted by the present invention is:

[0031] A functionalized tetragonal transition metal disulfide has a tetragonal crystal structure and comprises at least one surface with a (001) crystal plane. The structural space group of the functionalized tetragonal transition metal disulfide is a P4 / nmm configuration, and transition metal atoms are adsorbed at hollow sites.

[0032] As an improvement, the substrate of the functionalized tetragonal transition metal disulfide is iron sulfide or cobalt sulfide, and the transition metal atom is iron, cobalt, nickel or copper.

[0033] A further improvement is that the functionalized tetragonal transition metal disulfide is one or more of Ni-FeS, Cu-FeS, Ni-CoS, Fe-CoS, Co-FeS, and Co-CoS.

[0034] The present application also discloses the use of any of the above-mentioned functionalized tetragonal transition metal disulfides in the electrocatalytic reduction of carbon dioxide. The electrolytic cell for the electrocatalytic reduction of carbon dioxide is composed of an anode cell compartment and a cathode cell compartment. The electrolytic cell for the electrocatalytic reduction of carbon dioxide specifically includes a cathode, an anode, an electrolyte solution and at least one proton source. The anode and the cathode are located in two different compartments of the anode cell compartment and the cathode cell compartment or in the same compartment.

[0035] As an improvement, the electrolyte solution is a liquid electrolyte, specifically an aqueous electrolyte solution and / or an electrolyte containing an organic solvent.

[0036] As an improvement, the electrolyte solution is an acidic, neutral or alkaline aqueous electrolyte solution.

[0037] As a further improvement, the aqueous electrolyte solution is composed of one or more of soluble salts, alkali metals, alkaline earth metal oxides and one or more of organic acids, inorganic acids, organic solvents, and organic solvents miscible with water.

[0038] As an improvement, the protons of the proton source are protons in an acidic medium and protons from water decomposition in a neutral or alkaline environment.

[0039] A further improvement is that the temperature of the electrocatalytic carbon dioxide reduction is 0°C to 50°C.

[0040] As an improvement, the cathode reaction in the electrolytic cell can be expressed as:

[0041] CO2+8H + +8e – →CH4+2H2O.

[0042] Beneficial effects:

[0043] Compared with the prior art, the functionalized tetragonal transition metal disulfide and its application in the present invention have the following beneficial effects:

[0044] 1. The functionalized tetragonal transition metal disulfide provided in this application can attach carbon dioxide molecules under strong adsorption, and its CRR activity is generally better than that of common catalysts such as defective graphene, N-doped graphene, Fe-MoS2, Co-MoS2, etc.;

[0045] 2. The electrolysis reaction of the functionalized tetragonal transition metal disulfide in the present application in the electrolytic cell electrocatalytically reduces CO2 to C1 products, such as HCOOH and CH4;

[0046] 3. Experimentally, tetragonal FeS and CoS have been successfully prepared by topological chemical deintercalation. Therefore, the functionalized tetragonal transition metal disulfide in this application is expected to be used as cathode material for electrocatalytic carbon dioxide reduction;

[0047] 4. The present invention provides a method and system for producing hydrogen at ambient temperature and pressure. In view of the environmental friendliness of hydrogen, especially in new energy industries such as new energy vehicles, and the energy-intensive and environmentally unfavorable conditions commonly used during their manufacture, the present invention has important applicability in various industries;

[0048] 5. Compared with tetragonal selenides, the sulfides doped with transition metal elements in the present application can reduce protons to hydrogen under strong adsorption at ambient temperature and pressure. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 Schematic diagram of the structure of the functionalized tetragonal transition metal disulfide of this application;

[0050] Figure 2 ΔG of functionalized tetragonal transition metal dichalcogenides for this application *CO2 With ΔG *H ;

[0051] Figure 3 The Gibbs free energy diagrams for two-electron processes of Ni-Fe, Cu-FeS, and Ni-CoS;

[0052] Figure 4 This is the Gibbs free energy diagram of the eight-electron process of Fe-CoS, Co-FeS, and Co-CoS. DETAILED DESCRIPTION

[0053] Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings. These examples are provided to further understand the present invention rather than to limit its scope.

[0054] In the following description, a series of steps are described. Those skilled in the art will appreciate that the order of the steps is not critical to the resulting construction and its effects unless the context requires. Furthermore, it will be apparent to those skilled in the art that, regardless of the order of the steps, the presence or absence of a time delay between steps may exist between some or all of the steps.

[0055] As used herein, including in the claims, unless the context indicates otherwise, terms in the singular should be construed to include the plural forms as well, and vice versa. Thus, it should be noted that, as used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly indicates otherwise.

[0056] Throughout the specification and claims, the terms “comprises,” “comprising,” “having,” and “containing” and variations thereof should be understood to mean “including but not limited to,” and are not intended to exclude other components / ingredients.

[0057] When these terms, features, values ​​and ranges are used in conjunction with terms such as "about", "around", "generally", "substantially", "essentially", "at least", etc., the present invention also covers the precise terms, features, values ​​and ranges, etc. (i.e., "about 3" should also precisely cover 3, or "substantially constant" should also precisely cover constant).

[0058] The term "at least one" should be understood to mean "one or more", and thus includes embodiments containing one or more components / ingredients. In addition, dependent claims referring to independent claims that use "at least one" to describe features have the same meaning when the features are referred to as "the" and "at least one".

[0059] It should be understood that the foregoing embodiments of the present invention may be modified while still falling within the scope of the present invention. Unless otherwise specified, the features disclosed in the specification may be replaced by alternative features for the same, equivalent or similar purposes. Therefore, unless otherwise specified, the disclosed model is only an example of a series of equivalent or similar features.

[0060] The use of exemplary language (e.g., "such as", "for example", "such as") is only intended to better illustrate the present invention, and does not limit the scope of the present invention, unless otherwise specified. Any steps described in the specification can be implemented in any order or simultaneously, unless the context clearly indicates otherwise.

[0061] All features and / or steps disclosed in the specification can be combined in any combination, except combinations in which at least some features and / or steps are mutually exclusive. Specifically, the preferred features of the present invention are applicable to all aspects of the present invention and can be used in any combination.

[0062] The present invention provides methods and systems for producing hydrogen at ambient temperature and pressure, in which the electrolytic cell used can be any of a range of conventional commercially available suitable and feasible electrolytic cell designs that can accommodate the cathode for the special purpose of the present invention. Therefore, in some embodiments, the electrolytic cell and system have one or more cathode units and one or more anode units.

[0063] The electrolytic cell in the present application is an electrochemical cell that undergoes a redox reaction when electrical energy is applied to the cell. The electrolytic cell for electrocatalytic carbon dioxide reduction is composed of a cell compartment of an anode and a cell compartment of a cathode. The electrolyte solution is a liquid electrolyte, specifically an aqueous electrolyte solution and / or an electrolyte containing an organic solvent; the aqueous electrolyte solution is composed of one or more of a soluble salt, an alkali metal, an alkaline earth metal oxide and one or more of an organic acid, an inorganic acid, an organic solvent, and an organic solvent miscible with water.

[0064] The electrolytic cell for electrocatalytic carbon dioxide reduction includes a cathode, an anode, an electrolyte solution and at least one proton source; the cathode reaction can be expressed as:

[0065] CO2+8H + +8e – →CH4+2H2O.

[0066] The proton source can be any suitable substance capable of providing protons in the electrolytic cell; the proton source can be an acid, for example, any suitable organic acid or inorganic acid; the proton donor can be provided in an acidic, neutral or alkaline aqueous solution. The protons of the proton source are protons in an acidic medium and protons from water decomposition in a neutral or alkaline environment.

[0067] The temperature for electrocatalytic CO2 reduction is between 0°C and 50°C. Functionalized tetragonal transition metal dichalcogenide surfaces can be hydrogenated by adding one hydrogen atom at a time, representing a proton from the solution and an electron from the electrode surface; the reaction mechanism can be described by the following equation, where the asterisk * indicates a surface site:

[0068] CO2+(H + +e - )+*→*HCO2

[0069] *HCO2+(H + +e - ) → *HCOOH

[0070] *HCOOH+(H + +e - ) → *CHO + H2O

[0071] *CHO+(H + +e - ) → *HCHO

[0072] *HCHO+(H + +e - ) → *H3CO

[0073] *H3CO+(H + +e - ) → *CH3OH

[0074] *CH3OH+(H + +e - ) → *CH3 + H2O

[0075] *CH3+(H + +e - ) → *CH4

[0076] Different parts / portions or components / ingredients may be provided in separate containers, or they may be provided in a single container. Thus, the anode and cathode may be placed in the same compartment of the electrolytic cell of the present invention, but in other embodiments, the anode is in one compartment and the cathode is in another compartment. The electrolyte solution is an acidic, neutral or alkaline aqueous electrolyte solution that conducts current and maintains ion flow. The aqueous electrolyte solution is composed of one or more of a soluble salt, an alkali metal, an alkaline earth metal oxide and one or more of an organic acid, an inorganic acid, an organic solvent, and an organic solvent miscible with water. Soluble salts such as sodium chloride salts.

[0077] In some embodiments, the functionalized tetragonal transition metal disulfide of the present application is one or more of chemically stable Ni-FeS, Cu-FeS, Ni-CoS, Fe-CoS, Co-FeS, Co-CoS, which will not be oxidized or otherwise consumed during the electrolysis process, promotes the formation of hydrogen, especially Co-FeS has the best catalytic activity.

[0078] The functionalized tetragonal transition metal disulfide in the cathode catalyst layer of the electrolytic cell should be able to promote the CRR reaction, have good electrical conductivity, have a large specific surface area, be chemically stable and resistant to poisoning.

[0079] In addition, in order to increase the stability and conductivity of the cathode material, a cathode support is usually coated on the surface of the cathode material. The cathode support can be a porous material, such as carbon fiber cloth, carbon fiber paper, graphite, etc., which is used to increase the surface area of ​​the cathode material and provide an electron conduction channel. In addition, a metal mesh, conductive paper or conductive support rod is required as a cathode current collector, which is tightly connected to the cathode material and the cathode support to collect electrons and conduct them to the conductive element of the external circuit.

[0080] The anode material of the electrolytic cell of the present application is composed of a substrate composed of stainless steel, titanium or aluminum, a catalytic layer and a reaction layer. The present application can use a functionalized tetragonal transition metal disulfide material as the catalyst layer. The reaction layer is also called an adsorption layer, which is often used to enhance gas adsorption or improve the efficiency of the electrolytic reaction.

[0081] The above descriptions are embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structural or equivalent process changes made using the specification of the present invention, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

[0082] Example 1

[0083] A functionalized tetragonal transition metal disulfide, wherein the functionalized tetragonal transition metal disulfide is a tetragonal crystal structure, the functionalized tetragonal transition metal disulfide comprises at least one surface having a (001) crystal plane, the structural space group of the functionalized tetragonal transition metal disulfide is a P4 / nmm configuration, the P4 / nmm configuration has a high degree of symmetry, the substrate of the functionalized tetragonal transition metal disulfide is iron sulfide FeS or cobalt sulfide CoS, and transition metal atoms iron, cobalt, nickel or copper are adsorbed on the hollow sites on the surface of the tetragonal transition metal disulfide;

[0084] Stability analysis of functionalized tetragonal transition metal disulfides, such as Figure 1 As shown, Fe, Co, Ni or Cu is adsorbed on the hollow site of the functionalized tetragonal transition metal disulfide. The more negative the binding energy, the stronger the interaction between the metal single atom and the tetragonal sulfide substrate, while the more negative the formation energy, the higher the feasibility of the experimental synthesis process. According to the calculation results of the binding energy, the binding energies of Fe-FeS, Co-FeS, Ni-FeS, and Cu-FeS are -3.60, -2.95, -3.68, and -2.48 eV, respectively; the binding energies of Fe-CoS, Co-CoS, Ni-CoS, and Cu-CoS are -3.78, -3.25, -3.79, and -2.40 eV, respectively. Calculations show that the functionalized tetragonal transition metal disulfide can effectively anchor the above four metal single atoms and has good structural stability.

[0085] Example 2

[0086] Analysis of adsorption and activation of CO2 molecules by functionalized tetragonal transition metal disulfide in Example 1:

[0087] In order to quantitatively analyze the adsorption of CO2 molecules, this application calculated the Gibbs free energy ΔG of CO2 adsorption *CO2 . Among them, ΔG *CO2 The more negative the adsorption, the stronger the adsorption, and vice versa. According to the calculation results of Gibbs free energy, the ΔG of Fe-FeS, Co-FeS, Ni-FeS, and Cu-FeS *CO2 The ΔG of Fe-CoS, Co-CoS, Ni-CoS and Cu-CoS are 0.17, -0.01, -0.08 and -0.21 eV respectively; *CO2 They are -0.13, -0.11, -0.06, and 0.22 eV respectively. It is not difficult to find that only Co-FeS, Ni-FeS, Cu-FeS, Fe-CoS, Co-CoS, and Ni-CoS have ΔG *CO2 Less than zero means that only the above six materials are feasible for adsorbing CO2 molecules.

[0088] Since the CRR process of the present application occurs in an acidic medium, the adsorption of H will compete in the adsorption process of CO2 molecules, so it is necessary to study the selectivity of the functionalized tetragonal transition metal disulfide of the present application. The hydrogen adsorption Gibbs free energy of Co-FeS, Ni-FeS, Cu-FeS, Fe-CoS, Co-CoS, and Ni-CoS is 0.20, 0.46, 0.33, 0.17, -0.04, and 0.12 eV. Therefore, the functionalized tetragonal transition metal disulfide catalyst designed in the present application has good selectivity and can effectively inhibit the Volmer reaction to ensure the effective adsorption of CO2 molecules.

[0089] Example 3

[0090] Two-electron reduction of functionalized tetragonal transition metal disulfide in Example 1:

[0091] For a two-electron process, Figure 3 As shown, the optimal reaction pathway can be summarized as *CO2(g)→*HCO2→*HCOOH. For Ni-FeS, the corresponding Gibbs free energy ΔG i is 0.01, -0.24eV. ​​For Cu-FeS, ΔG i is 0.12, -0.30eV. For Ni-CoS, the corresponding ΔG i The protonation process *CO2(g)→*HCO2 requires additional energy input, and the corresponding theoretical limiting potentials are -0.01, -0.12, and -0.10 V. In addition, the desorption process of HCOOH *HCOOH→*+HCOOH is also an energy-requiring process, and its desorption Gibbs free energy ΔG des They are 0.68, 0.76, and 0.52 eV respectively. Therefore, Ni-FeS, Cu-FeS, and Ni-CoS can reduce CO2 to HCOOH.

[0092] Example 4

[0093] Eight-electron reduction of functionalized tetragonal transition metal disulfide in Example 1:

[0094] For the eight-electron process, Figure 4 The reaction intermediates of CO2 electroreduction to CH4 are shown in Figure 1. The optimal reaction pathway can be summarized as *CO2(g)→*HCO2→*HCOOH→*CHO→*HCHO→*H3CO→*CH3OH→*CH3→*CH4. For Co-FeS, the Gibbs free energy ΔG i are -0.12, -0.20, 0.06, 0.41, -0.22, -0.54, 0.19, and -0.42 eV. Similarly, for Fe-CoS, ΔGi are -0.15, -0.13, 0.77, -0.07, -0.59, -0.14, 0.03, and -0.61 eV. For Co-CoS, the reaction path is *CO2(g)→*COOH→*CO→*CHO→*HCOH→*CH2OH→*CH3OH→*CH3→*CH4, and the corresponding ΔG i The data show that the potential determining step for Co-FeS is *CHO→*HCHO, while the potential determining step for Fe-CoS and Co-CoS is *HCOOH→*CHO. The theoretical limiting potentials of the above materials are -0.41, -0.77, and -0.91 V. Therefore, Co-FeS, Fe-CoS, and Co-CoS can reduce CO2 to CH4.

[0095] The present invention and its embodiments are described schematically above, and the description is not restrictive. The drawings show only one embodiment of the present invention, and the actual structure is not limited thereto. Therefore, if a person skilled in the art is inspired by it and designs a structural method and an embodiment similar to the technical solution without creativity without departing from the purpose of the invention, they shall all fall within the protection scope of the present invention.

Claims

1. A functionalized tetragonal transition metal disulfide, characterized in that: The functionalized tetragonal transition metal disulfide has a tetragonal crystal structure, comprises at least one surface with a (001) crystal plane, has a structural space group of P4 / nmm configuration, and has transition metal atoms adsorbed at hollow sites.

2. A functionalized tetragonal transition metal disulfide according to claim 1, characterized in that: The substrate of the functionalized tetragonal transition metal disulfide is iron sulfide or cobalt sulfide, and the transition metal atom is iron, cobalt, nickel or copper.

3. A functionalized tetragonal transition metal disulfide according to claim 1, characterized in that: The functionalized tetragonal transition metal disulfide is one or more of Ni-FeS, Cu-FeS, Ni-CoS, Fe-CoS, Co-FeS, and Co-CoS.

4. Use of the functionalized tetragonal transition metal disulfide according to any one of claims 1 to 3 in electrocatalytic carbon dioxide reduction, characterized in that: The electrolytic cell for electrocatalytic carbon dioxide reduction is composed of an anode cell compartment and a cathode cell compartment. The electrolytic cell for electrocatalytic carbon dioxide reduction specifically includes a cathode, an anode, an electrolyte solution and at least one proton source. The anode and the cathode are located in two different compartments of the anode cell compartment and the cathode cell compartment or in the same compartment.

5. The use of the functionalized tetragonal transition metal disulfide in electrocatalytic carbon dioxide reduction according to claim 4, characterized in that: The electrolyte solution is a liquid electrolyte, specifically an aqueous electrolyte solution and / or an electrolyte containing an organic solvent.

6. The use of the functionalized tetragonal transition metal disulfide in electrocatalytic carbon dioxide reduction according to claim 5, characterized in that: The electrolyte solution is an acidic, neutral or alkaline aqueous electrolyte solution.

7. The use of the functionalized tetragonal transition metal disulfide in electrocatalytic carbon dioxide reduction according to claim 6, characterized in that: The aqueous electrolyte solution is composed of one or more of soluble salts, alkali metals, alkaline earth metal oxides and one or more of organic acids, inorganic acids, organic solvents, and organic solvents miscible with water.

8. The use of the functionalized tetragonal transition metal disulfide in electrocatalytic carbon dioxide reduction according to claim 4, characterized in that: The protons of the proton source are protons in an acidic medium and protons from water decomposition in a neutral or alkaline environment.

9. The use of the functionalized tetragonal transition metal disulfide in electrocatalytic carbon dioxide reduction according to claim 4, characterized in that: The temperature of the electrocatalytic carbon dioxide reduction is 0°C to 50°C.

10. The use of the functionalized tetragonal transition metal disulfide in electrocatalytic carbon dioxide reduction according to claim 4, characterized in that: The reaction at the cathode in the electrolytic cell can be expressed as: CO2+8H + +8e – →CH4+2H2O.

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