Oxygen-dominated supra-nano dual-phase catalytic reaction material on a substrate

Abstract

The invention provides an oxygen-dominated ultra-nano dual-phase catalytic reaction material. The oxygen-dominated ultra-nano dual-phase catalytic reaction material comprises a uniform oxygen-enriched amorphous shell and a core encapsulated in the uniform oxygen-enriched amorphous shell. The catalyst shows ultrahigh HER performance which is a key reaction in a water decomposition process, so that the catalyst is suitable for being applied to hydrogen production industries, battery companies, new energy vehicle enterprises and large power stations.

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Patent Application No. 18 / 764,418, filed July 5, 2024, which is incorporated herein by reference in its entirety. Technical Field

[0002] This invention generally relates to the field of electrochemical catalytic materials. More specifically, this invention relates to oxygen-dominant ultrananostructures, which provide a pathway for developing electrocatalysts with exceptionally high hydrogen evolution activity. Background Technology

[0003] Electrochemical water splitting to produce hydrogen is widely considered an ideal strategy for reducing the consumption of traditional fossil fuels and contributing to carbon neutrality. In particular, the hydrogen evolution reaction (HER) is a key reaction involving electrochemical splitting. In recent years, researchers have focused on developing high-performance electrocatalytic materials for HER by carefully manipulating their structure or morphology.

[0004] Currently, commercial HER catalysts for water splitting are based on Pt nanoparticles dispersed on a carbon substrate, such as 20% Pt / C. Furthermore, the current manufacturing methods for commercial Pt / C are complex and very costly. Although the HER performance of commercial Pt / C is sufficient for water splitting, further development of novel catalysts with low overpotential, high conductivity, and high stability is desired to further reduce energy consumption.

[0005] Crystalline-amorphous ultranano dual-phase (SNDP) materials are a novel type of nanostructure characterized by a uniform and continuous distribution of both crystalline and amorphous regions, with both crystal size and amorphous region thickness less than 10 nm. SNDP materials inherit the advantages of both crystalline and amorphous phases and, due to their multi-component synergistic effects and extremely large active catalytic interfaces, represent a promising alternative to commercial Pt / C HER catalysts. Furthermore, SNDP materials with closely contacted coexisting phases that differ in their chemical properties exhibit unique interfacial interactions. These characteristics of SNDP materials fulfill the requirements for excellent electrocatalysts.

[0006] Oxygen is an essential component of many materials, and its presence or absence affects material properties. Highly electronegative oxygen influences the local coordination environment of active sites, thus transferring these sites to higher oxidation states and affecting water absorption capacity and the Gibbs free energy (ΔG) of hydrogen adsorption (H*). H* ).

[0007] In the catalytic reduction of hydrogen evolution (HER), it is undesirable for the active site to directly coordinate with oxygen. Therefore, how to utilize oxygen to modulate the electronic structure to enhance hydrogen evolution performance has become a major challenge. Summary of the Invention

[0008] Therefore, this invention proposes to utilize high-entropy amorphous alloys (HEAA) and Al... 0.5 A series of SNDP materials have been industrially prepared by magnetron sputtering of ZnTiZrSiCuNi with transition metals (e.g., palladium, iridium, platinum, ruthenium, gold, silver, vanadium, and tungsten). The composition of the SNDP structure can be precisely controlled over a wide range by varying the oxygen content.

[0009] Specifically, in a first aspect, the present invention provides an oxygen-dominant ultra-nano dual-phase catalytic reaction material on a substrate, the oxygen-dominant ultra-nano dual-phase catalytic reaction material comprising a uniform oxygen-rich amorphous shell and a core encapsulated within the uniform oxygen-rich amorphous shell. The oxygen-dominant ultra-nano dual-phase catalytic reaction material has an intrinsic crystalline-amorphous dual-phase structure. At 10 mA cm⁻¹ -2 Under these conditions, the oxygen-dominant ultra-nano biphase catalytic reaction material exhibits an overpotential of 10 mV to 25 mV relative to the reversible hydrogen electrode (RHE).

[0010] Crystalline phases have a face-centered cubic structure, while amorphous phases have a typical disordered and random arrangement.

[0011] In one embodiment, the uniform oxygen-rich amorphous shell is made of a high-entropy amorphous alloy, the high-entropy amorphous alloy comprising Al 0.5 Alloys of ZnTiZrSiCuNi and alloys containing FeCoNiMoPB. The thickness of the uniform oxygen-rich amorphous shell ranges from approximately 1-5 nm.

[0012] In one embodiment, the core is made of at least one transition metal, a non-precious metal, or a NiMo / NiW binary alloy. The transition metal includes palladium, platinum, iridium, ruthenium, rhodium, gold, and silver, and the non-precious metal includes vanadium, molybdenum, and tungsten. The diameter of the core is 1-10 nm.

[0013] In one embodiment, the oxygen-dominant ultranano biphase catalytic reaction material contains 20-30 at% palladium, 10-50 at% oxygen, 1-5 at% aluminum, 5-20 at% silicon, 5-20 at% titanium, 5-20 at% nickel, 5-20 at% copper, 1-15 at% zinc, and 5-20 at% zirconium.

[0014] In another embodiment, the oxygen-dominant ultranano biphase catalytic reaction material contains 10-30 at% platinum, 10-40 at% oxygen, 5-20 at% iron, 5-20 at% cobalt, 5-20 at% nickel, 1-15 at% molybdenum, 1-10 at% phosphorus, and 1-10 at% boron.

[0015] In one embodiment, the substrate includes nickel foam, carbon cloth, carbon paper, silicon wafer, porous titanium sheet, titanium foam, or platinum foil.

[0016] In one embodiment, at 20 mA cm in a three-electrode system -2 At a current density of 500 mA cm⁻¹, the oxygen-dominant ultranano dual-phase catalytic reactive material exhibited stability during a 100-hour long-term test and could be used in a flow-type membrane exchange assembly alkaline water electrocatalytic cell unit at 500 mA cm⁻¹. -2 It operates stably for 1000 hours at the specified current density.

[0017] On the other hand, the oxygen-dominant ultra-nano biphase catalytic reaction material can be used to fabricate water splitting electrodes, including HER electrodes and / or oxygen evolution reaction (OER) electrodes.

[0018] On the other hand, the present invention provides a method for manufacturing oxygen-dominant ultra-nano biphase catalytic reactive materials, the method comprising co-sputtering a crystalline metal and a high-entropy amorphous alloy onto a substrate by industrial magnetron sputtering, wherein oxygen is introduced during the magnetron sputtering process.

[0019] In one embodiment, the oxygen flow rate is in the range of approximately 0.01 sccm to 50 sccm.

[0020] In one embodiment, the high-entropy amorphous alloy is a multi-component alloy containing Al 0.5 Alloys of ZnTiZrSiCuNi, and alloys containing FeCoNiMoPB.

[0021] In one embodiment, the industrial magnetron sputtering employs a sputtering temperature of approximately 0.1°C to 200°C.

[0022] In one embodiment, the substrate rotates at a speed ranging from 0.1 rpm to 20 rpm during sputtering.

[0023] This invention provides a novel transition metal-based SNDP material with a high-entropy amorphous alloy by employing an oxygen-dominant strategy and industrial magnetron sputtering at ambient temperature. The SNDP palladium / high-entropy amorphous alloy (SNDP-Pd@HEAA) of this invention comprises a Pd-rich nanocrystalline core and an oxygen-rich amorphous glassy shell, rich in numerous active Pd sites coordinated with near-nearest neighbor oxygen, which effectively accelerates hydrogen proton adsorption / desorption at 10 mA cm⁻¹. -2It exhibits a near-zero overpotential (10.16 mV, significantly lower than the 34.01 mV overpotential of commercial 20% Pt / C) and excellent hydrogen evolution stability under alkaline conditions. The preparation and compositional manipulation techniques of this SNPD nanostructure, along with the active site mechanism of near-nearest neighbor oxygen coordination, establish a new paradigm for hydrogen evolution reaction catalysts.

[0024] The catalyst of the present invention offers the following advantages: (1) compared with existing commercial 20 wt% Pt / C catalysts, the catalyst of the present invention exhibits lower overpotential and higher hydrogen evolution reaction stability; (2) by changing the oxygen concentration, the composition of the SNDP structure can be precisely tuned over a wide range, thereby overcoming the limited diversity and limited range of composition tuning of conventional SNDP structures; and (3) the present invention utilizes room temperature industrial magnetron sputtering technology, which has greater potential for large-scale production compared with the technology used in existing catalysts. Attached Figure Description

[0025] Embodiments of the invention are described in more detail below with reference to the accompanying drawings, in which:

[0026] Figure 1A XRD patterns of ultra-nano biphase palladium / high-entropy amorphous alloys were depicted, including SNDP-Pd@HEAA, As-SNDP-Pd@HEAA, o-HEAA, As-HEAA, o-Pd, and As-Pd. Figure 1B A scanning electron microscope image of SNDP-Pd@HEAA on carbon cloth is shown. Figure 1C An atomic force microscope of SNDP-Pd@HEAA is shown. Figure 1D The SEM energy-dispersive spectroscopy (EDS) plot of SNDP-Pd@HEAA is shown;

[0027] Figure 2A A low-magnification transmission electron microscope of SNDP-Pd@HEAA is shown. Figure 2B A high-resolution transmission electron microscope (TEM) image of the cross-section of SNDP-Pd@HEAA is shown. The fast Fourier transform image in the inset reveals that the crystalline phase has a face-centered cubic structure and the amorphous phase has a typically disordered and randomized structure. Figure 2C It shows Figure 2A The corresponding selected region electron diffraction pattern of SNDP-Pd@HEAA;

[0028] Figure 3A The three-dimensional reconstructed TEM image of SNDP-Pd@HEAA is shown. Figure 3BThe grain size distribution obtained from multiple TEM images is depicted. Planar plots are used for the xz plane, and cross-sections 1 and 2 correspond to the xy and yz planes, respectively. Figure 3C This image shows a typical high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) image. The arrows indicate the direction of the line scan in energy-dispersive spectroscopy. Figure 3D Depicting the journey Figure 3C The arrows in the diagram indicate the line scan intensity of elements in energy-dispersive spectroscopy. Figure 3E Three-dimensional atomic probe tomography images showing elemental distribution and multi-component properties are presented;

[0029] Figure 4A TEM images of SNDP-Pd@HEAA with different oxygen contents are shown. Figure 4B XRD patterns of SNDP-Pd@HEAA with different oxygen contents were depicted;

[0030] Figure 5A The Pd 3d X-ray photoelectron spectroscopy of SNDP-Pd@HEAA was depicted. Figure 5B The O 1s X-ray photoelectron spectroscopy of SNDP-Pd@HEAA was depicted. Figure 5C X-ray photoelectron microscopy depicts SNDP-Pd@HEAA with detailed fitted peaks;

[0031] Figure 6A The near-edge structure spectra of Pd K-edge X-ray absorption in SNDP-Pd@HEAA were depicted. Figure 6B The corresponding k values ​​for X-ray absorption fine structure (EXAFS) spectra are shown. 2 Weighted Fourier Transform. Figure 6C The k-values ​​of the EXAFS spectra at the Pd K-edge of SNDP-Pd@HEAA and As-SNDP-Pd@HEAA were plotted. 2 Fitting the weighted Fourier transform;

[0032] Figure 7 The k- at the Pd K- edge of SNDP-Pd@HEAA, As-SNDP-Pd@HEAA, Pd foil, and PdO is depicted. 2 Wavelet transform of weighted EXAFS signals;

[0033] Figure 8A The XRD patterns of the SNDP-M@HEAA samples (M = Au, Ag, W, Pt, Ru, Ir, Pd) were depicted. Figure 8B TEM images of the SNDP-M@HEAA sample are shown.

[0034] Figure 9AThe figure depicts the effect at 5 mV s under iR correction. -1 The polarization curves of the sample deposited on glassy carbon were obtained at a scanning rate of [missing information]. Figure 9B Polarization curves of SNDP-Pd@HEAA samples with different oxygen contents in 1M KOH under iR correction;

[0035] Figure 10A Depicting Figure 9A The corresponding Tafel plot. Figure 10B Depicting Figure 9B The corresponding Tafel diagram;

[0036] Figure 11 Electrochemical impedance spectroscopy of SNDP-Pd@HEAA, As-SNDP-Pd@HEAA, o-Pd, As-Pd, o-HEAA, As-HEAA and 20% Pt / C at room temperature in 1M KOH solution at an overpotential of 100 mV was depicted.

[0037] Figure 12A Cyclic voltammetry was plotted for SNDP-Pd@HEAA, As-SNDP-Pd@HEAA, o-Pd, As-Pd, o-HEAA, As-HEAA, 20% Pt / C in the region relative to RHE 0-0.1V at various scan rates. Figure 12B The calculated electrochemical double-layer capacitance of the material prepared in this way is described;

[0038] Figure 13A The structural configurations of the SNDP model with and without oxygen are shown. Figure 13B The DFT calculations for ΔE of H2O molecules at various sites in interface models with and without oxygen are depicted. H2O For reference, ΔE of the Pt(111) surface H2O Marked with a gray dashed line. Figure 13C The ΔE of H2O molecules at Pd sites is depicted in crystalline, amorphous, and interface models with and without elemental oxygen. H2O The DFT calculation. For reference, the ΔE of the Pt(111) surface. H2O Marked with a gray dashed line;

[0039] Figure 14 DFT simulations depict the atomic configurations and corresponding electron density differences after H₂O adsorption at Pd, Ti, Zr, and Al sites in interface models with and without elemental oxygen. X-O This indicates the bonding distance between the oxygen atom at H2O and the Pd, Ti, Zr, and Al sites;

[0040] Figure 15 The p-PDOS of oxygen atoms in H2O molecules after adsorption onto Pd, Ti, Zr, and Al sites is depicted in interfacial models with and without elemental oxygen. The black dashed line at zero energy represents the Fermi level (E0). F );

[0041] Figure 16A Representative local chemical environments following H* adsorption at the top site of Pd are depicted in crystalline / amorphous interface models with no oxygen coordination, with neighboring oxygen coordination, and with sub-nearest neighboring oxygen coordination. Figure 16B The ΔG values ​​of Pd sites in crystalline, amorphous, and crystalline / amorphous interface models with no oxygen coordination, near-near oxygen coordination, and second-nearest ... H* distributed. Figure 16C The local chemical environment after H* adsorption at the top site of Pd is depicted in crystalline and amorphous models with no oxygen coordination, with neighboring oxygen coordination, and with sub-nearest neighbor oxygen coordination.

[0042] Figure 17A DFT simulation results depicting the two-dimensional electron density difference and equilibrium distance of Pd-Ti, Pd-O and Pd-Ti(O) are presented. Figure 17B The d-orbital partial density of states (d-PDOS) of Pd catalytic sites at interfaces with no oxygen coordination, with nearest-neighbor oxygen coordination, and with second-nearest-neighbor oxygen coordination are depicted. The black dashed line represents the Fermi level. The solid line represents the corresponding d-band center.

[0043] Figure 18A The Gibbs free energy (ΔG) of various bridges and hollow sites in crystalline / amorphous interface models with and without elemental oxygen was depicted. H* )distributed. Figure 18B The local chemical environments of various H* adsorption sites (bridges and hollows) in crystalline / amorphous interface models with and without elemental oxygen are depicted.

[0044] Figure 19A The relationship between the catalytic performance of SNDP-Pd@HEAA and oxygen content was depicted, showing that the hydrogen evolution reaction performance improved with increasing oxygen content. Figure 19B Electrochemical impedance spectroscopy was depicted for SNDP-Pd@HEAA samples with different oxygen contents in 1M KOH solution at an overpotential of 100 mV and at room temperature. Figure 19C Cyclic voltammetry was plotted for SNDP-Pd@HEAA samples with different oxygen atom contents in the region relative to RHE 0-0.1V at various scan rates;

[0045] Figure 20 The catalyst in alkaline solution at 10 mA cm⁻¹ was described.-2 Performance comparison at current densities;

[0046] Figure 21A The performance of SNDP-Pd@HEAA and As-SNDP-Pd@HEAA in alkaline solution at 20 mA cm⁻¹ was described. -2 Long-term performance under constant current density. Figure 21B X-ray photoelectron microscopy depicts As-SNDP-Pd@HEAA after 100 hours in 1M KOH;

[0047] Figure 22A The polarization curves of SNDP-Pt@HEAA and As-SNDP-Pt@HEAA in 1MKOH under iR correction were plotted. Figure 22B The polarization curves of SNDP-Au@HEAA and As-SNDP-Au@HEAA in 1M KOH under iR correction were plotted. Figure 22C The polarization curves of SNDP-Ag@HEAA and As-SNDP-Ag@HEAA in 1M KOH under iR correction were plotted. Figure 22D The polarization curves of SNDP-W@HEAA and As-SNDP-W@HEAA in 1M KOH under iR correction were plotted. Figure 22E The polarization curves of SNDP-Ir@HEAA, As-SNDP-Ir@HEAA and IrO2 in 1M KOH were plotted under iR correction. Figure 22F The polarization curves of SNDP-Ru@HEAA and As-SNDP-Ru@HEAA in 1M KOH under iR correction were plotted; and

[0048] Figure 23 The SNDP-Pd@HEAA / SNDP-Ir@HEAA battery cell was depicted at 0.5 A cm⁻¹. -2 Long-term durability under constant current density. Detailed Implementation

[0049] Large-scale fabrication of excellent hydrogen evolution reaction catalysts with near-zero overpotentials is challenging. Supernano-biphase (SNDP) structures are a promising commercial alternative to platinum-supported carbon (Pt / C) catalysts, combining the best of both crystalline and amorphous phases with multi-component synergistic effects and highly active catalytic interphases. However, the types of elements available for fabrication of SNDP structures are limited, and the range of compositional tuning is also relatively narrow.

[0050] Therefore, this invention provides an oxygen-dominant ultra-nano biphase catalytic reaction material on a substrate, the oxygen-dominant ultra-nano biphase catalytic reaction material comprising a uniform oxygen-rich amorphous shell and a core encapsulated within the uniform oxygen-rich amorphous shell. The oxygen-dominant ultra-nano biphase catalytic reaction material possesses an intrinsic crystalline-amorphous biphase structure. At 10 mA cm⁻¹ -2 Under these conditions, the oxygen-dominant ultra-nano dual-phase catalytic reaction material exhibits an overpotential of 10 mV to 25 mV relative to RHE.

[0051] Preferably, the oxygen-dominant ultra-nano dual-phase catalytic reaction material is used at 10 mA / cm². -2 The overpotential exhibited by the lower RHE is 10.16 mV.

[0052] In one embodiment, the uniform oxygen-rich amorphous shell is made of a high-entropy amorphous alloy, the high-entropy amorphous alloy comprising Al-containing... 0.5 Alloys of ZnTiZrSiCuNi and alloys containing FeCoNiMoPB. The thickness of the uniform oxygen-rich amorphous shell is approximately 1-5 nm.

[0053] In one embodiment, the core is made of at least one transition metal, a non-precious metal, or a NiMo / NiW binary alloy. The transition metal includes palladium, platinum, iridium, ruthenium, rhodium, gold, and silver, and the non-precious metal includes vanadium, molybdenum, and tungsten. The diameter of the core is 1-10 nm.

[0054] In one embodiment, the oxygen-dominant ultranano dual-phase catalytic reaction material contains 20-30 at% Pd, 10-50 at% O, 1-5 at% Al, 5-20 at% Si, 5-20 at% Ti, 5-20 at% Ni, 5-20 at% Cu, 1-15 at% Zn, and 5-20 at% Zr.

[0055] Preferably, an O concentration of 42.24 at.% exhibits the best electrocatalytic performance. The oxygen-dominant ultranano dual-phase catalytic reactive material contains 25.12 at% Pd, 42.24 at% O, 2.74 at% Al, 3.35 at% Si, 2.9 at% Ti, 3.99 at% Ni, 4.62 at% Cu, 8.62 at% Zn, and 6.41 at% Zr.

[0056] In another embodiment, the oxygen-dominant ultranano biphase catalytic reaction material contains 10-30 at% Pt, 10-40 at% O, 5-20 at% Fe, 5-20 at% Co, 5-20 at% Ni, 1-15 at% Mo, 1-10 at% P and 1-10 at% B.

[0057] In one embodiment, the substrate includes nickel foam, carbon cloth, carbon paper, silicon wafer, porous titanium sheet, titanium foam, or platinum foil.

[0058] In one embodiment, at 20 mA cm in a three-electrode system -2 At a current density of 500 mA cm⁻¹, the oxygen-dominant ultranano dual-phase catalytic reactive material exhibited stability during a 100-hour long-term test and could be used in a flow-type membrane exchange assembly alkaline water electrocatalytic cell unit at 500 mA cm⁻¹. -2 It operates stably for 1000 hours at the specified current density.

[0059] The interesting crystalline / amorphous dual-phase structure and the numerous active sites for second-nearest neighbor oxygen coordination at the interface produce a near-zero ΔG value. H* It has a strong H2O adsorption capacity that promotes H2O adsorption and hydrogen / proton adsorption, and thus contributes to the excellent HER performance of SNDP-Pd@HEAA.

[0060] The crystalline regions are rich in elements found in crystalline materials, while the amorphous regions are highly rich in oxygen. All elements from the crystalline materials are uniformly distributed within the material. The content of crystalline elements is higher in the crystalline regions than in the amorphous regions. The atomic ratio of elements from the crystalline materials ranges from approximately 20 at% to 80 at% in the crystalline regions and from approximately 0 at% to 40 at% in the amorphous regions. The atomic ratio of oxygen ranges from approximately 0.01 at% to 30 at% in the crystalline regions and from approximately 10 at% to 70 at% in the amorphous regions. The atomic ratio of all elements from the crystalline materials ranges from approximately 0.01 at% to 30 at%.

[0061] In one embodiment, the oxygen content in the crystalline region is much lower than that in the amorphous region.

[0062] SNDP-Pd@HEAA has a uniformly distributed three-dimensional structure comprising Pd-rich crystalline nuclei with a diameter of approximately 1-10 nm and a uniform amorphous shell rich in HEAA with a thickness of approximately 1-5 nm.

[0063] In one embodiment, the SNDP material is an SNDP-Pd / high-entropy amorphous alloy (SNDP-Pd@HEAA). SNDP-Pd@HEAA, with Pd-rich grains (4.76 nm in diameter) and a uniform oxygen-rich amorphous shell (approximately 1.2 nm thick), exhibits a near-zero overpotential (at 10 mA cm⁻¹). -2 (10.16 mV), and therefore a promising alternative to commercial Pt / C HER catalysts under alkaline conditions.

[0064] During magnetron sputtering, the size of nanocrystals and the thickness of amorphous layers in a catalyst can be easily tuned by simply applying different power to the target and rotating the receiving substrate. For example, the power applied to metals is a radio frequency (RF) power supply. The power applied to high-entropy amorphous alloys is a direct current (DC) power supply. RF power supplies range from 30W to 200W, and DC power supplies range from 35W to 225W.

[0065] When used directly as a HER electrocatalyst without further post-treatment, SNDP-Pd@HEAA exhibits a near-zero overpotential under alkaline conditions (at 10 mA cm⁻¹). -2 (The value below is 10.16 mV). The long-term durability of SNDP-Pd@HEAA in alkaline media can be attributed to the limited oxidation tendency of oxygen-dominant HEAA.

[0066] In one embodiment, the SNDP structure can be deposited on a variety of substrates depending on its application. For example, the substrate may include nickel foam, carbon cloth, carbon paper, silicon wafer, titanium sheet, or platinum foil.

[0067] All SNDP samples uniformly deposited on conductive substrates by magnetron sputtering exhibited similarly smooth surfaces. However, the electrochemically active surface area of ​​SNDP-Pd@HEAA with a flat and smooth surface was 2.75 times that of the commercial 20wt% Pt / C containing ultrasmall nanoparticles.

[0068] On the other hand, oxygen-dominant ultra-nano biphase catalytic reaction materials can be used to fabricate water splitting electrodes.

[0069] On the other hand, the present invention also provides an industrial method for developing SNDP nanostructures with near-zero potentials for a wide range of electrocatalytic applications, and provides new insights into the next nearest-neighbor oxygen coordination active site.

[0070] Specifically, this invention provides a method for manufacturing oxygen-dominant ultra-nano dual-phase catalytic reactive materials. The method includes co-sputtering a crystalline metal and a high-entropy amorphous alloy onto a substrate using industrial magnetron sputtering. Oxygen is introduced during the magnetron sputtering process.

[0071] Crystalline metals and high-entropy amorphous alloys can be combined arbitrarily according to the final application scenario and operating conditions. Application scenarios include hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, hydrogen oxidation reaction, carbon dioxide reduction reaction, water splitting, proton exchange membrane fuel cell unit materials, and metal-air batteries. Operating conditions can be within a wide pH range.

[0072] High-entropy amorphous alloys are multi-component alloys that readily form amorphous structures during sputtering processes. They require some easily oxidizable elements and some non-metallic elements, such as alloys containing Al, Zn, Ti, Zr, Si, Cu, and Ni.

[0073] Industrial magnetron sputtering uses sputtering temperatures ranging from approximately 0.1°C to 200°C.

[0074] Example

[0075] Example 1 - Materials and Methods

[0076] Material

[0077] China Material Technology Co., Ltd. mixes elemental particles of aluminum (Al), zinc (Zn), titanium (Ti), zirconium (Zr), silicon (Si), copper (Cu), and nickel (Ni) with a purity higher than 99.95% to obtain a theoretical atomic composition (at%) of Al. 0.5 High-entropy amorphous alloy (HEAA) sputterings of ZnTiZrSiCuNi. Pure palladium (Pd) with a purity greater than 99.99% was purchased from Angstrom Engineering Inc.Co., Ltd. Analytical grade potassium hydroxide (KOH) and anhydrous ethanol were supplied by Sigma Aldrich. All solutions were prepared using Milli-Q water (18.2 MΩ cm).

[0078] Material characterization

[0079] Samples were characterized using scanning electron microscopy (SEM, Philips XL-30FESEM), atomic force microscopy (AFM, Bruker Icon), and high-resolution transmission electron microscopy (TEM, JEOL TEM 2100F FEG, operating at an accelerating voltage of 200 kV). Atomic resolution scanning transmission electron microscopy (STEM) images and energy-dispersive spectroscopy (EDS) plots were obtained on a Titan FEI Themis G60-300 S / TEM (equipped with a high-brightness field emission gun (X-FEG), a probe CS corrector, and an ultra-X EDS with four windowless silicon drift detectors). Cu Kα radiation was used. X-ray diffraction (XRD) patterns were collected using an X-ray diffractometer (Rigaku SmartLab). Three-dimensional atomic probe tomography (APT) characterization was performed using a local electrode atomic probe (CAMECALEAP 5000XR). APT experiments were conducted in 60K laser mode with a laser energy of 50 pJ, a pulse rate of 125 kHz, and a detection rate of 0.3%. Corresponding three-dimensional reconstructions and data analysis were performed using Imago visualization and analysis software (IVAS, version 3.8.2). Both TEM and APT samples were prepared using a raised and ring-thinning method on a FEI focused ion beam / scanning electron microscope (FIB / SEM). For the preparation of TEM and APT samples for stability testing, SNDP-Pd@HEAA was sputtered onto nickel foam. The leached metal ions in the stability test were measured using inductively coupled plasma-optical emission spectrometry (ICP-OES) (Optima ICP-OES spectrometer, PerkinElmer) with a 10-fold dilution. (Results corrected with dilution factor.) X-ray photoelectron microscopy was performed on an ESCALAB 250 photoelectron spectrometer (Thermo Fisher Scientific), with Al Ka ​​(1486.6 eV) as the X-ray source set at 150 W and a flux of 30 eV for high-resolution scanning. The baseline pressure was 3 × 10⁻⁶. -9 mbar, and combined with a reference C1s line at 284.8 eV from uncertain carbon. X-ray absorption near-edge structure and extended X-ray absorption fine structure experiments of the SNDP-Pd@HEAA catalyst were performed on the BL14W1 beamline of the Shanghai Synchrotron Radiation Facility. Data were collected using a Lytle detector in fluorescence mode, while the corresponding reference sample was measured in transmission mode. The incident beam was monochromated using a dual-crystal monochromator with a fixed Si(111) exit, and a harmonic suppression mirror was applied to cut off higher harmonics. The obtained X-ray absorption fine structure data were processed in Athena (version 0.9.26) for background, front-edge, and back-edge calibration. Fourier transform fitting was then performed in Artemis (version 0.9.26). k 3 Weighted scheme, The range of k and 1 to approximately The R range is used in the fitting of Pd foil, and will The range of k and 1 to approximately The R-range is used for fitting SNDP-Pd@HEAA samples. The following three parameters can be freely fitted with a set of Debye-Woller factors σ. 2Coordination number, bond length, and E0 offset (CN, R, ΔE0). In wavelet transform analysis, χ(k) derived from Athena was imported into the HamaFortran code. The parameters are... The R range for Pd The range of k and the weight of k are 3. The Morlet function with κ=10 and σ=1 is used as the mother wavelet to give the overall distribution.

[0080] Electrochemical Measurement

[0081] An SNDP-Pd@HEAA film was deposited on a carbon cloth with a thickness of approximately 350 nm and a glassy carbon electrode (Φ4 mm) for electrochemical studies. Electrochemical measurements were performed at room temperature in 1.0 M KOH solution on a CH1660e electrochemical station with a three-electrode cell system. SNDP-Pd@HEAA, a Hg / HgO electrode, and a graphite rod were used as the working electrode, reference electrode, and counter electrode, respectively.

[0082] To more accurately measure the intrinsic overpotential of the deposited film, at 5 mV s -1 Polarization curves were obtained by linear sweep voltammetry (LSV) of the sample deposited on a glassy carbon electrode at a scan rate of [missing value]. Electrochemical impedance spectroscopy (EIS) was performed from 100 kHz to 0.1 Hz. Within a potential range of 0–0.1 V (relative to RHE), [missing value] was obtained at 10 mV s [missing value]. -1 Up to 80mV s -1 A series of cyclic voltammograms were obtained at non-Radiladian overpotentials within a scan rate range to demonstrate the effectiveness in estimating the double-layer capacitance (C0). dl The current in the capacitor is used for charging and discharging. The electrochemical surface area is expressed in terms of C. dl / C s Obtain, where C dl It is the measured double-layer capacitance and C s It is specific capacitance. In this invention, due to the flat surface of SNDP-Pd@HEAA, it is assumed that C s The value is 0.04 mF cm -2 Without iR loss correction, chronocurrent analysis was employed, by continuously applying 20 mA cm⁻¹ to the working electrode. -2 and 200mAcm 2 The current density was used to test the long-term stability of the samples on the carbon cloth. The current density was calculated from the geometric surface area. All presented data were corrected for iR loss and background current, and the potential was later converted to the reversible hydrogen electrode (RHE) scale.

[0083] RHE calibration

[0084] All potentials in this invention were calibrated and converted to the RHE scale. In a high-purity hydrogen-saturated electrolyte, Pt wire and carbon rod were used as the working and counter electrodes, respectively. In 1M KOH, a Hg / HgO electrode was used as the reference electrode. At 1 mV s -1 CV was measured at a scan rate of [value missing]. The average of the two potentials at which the current reaches zero was taken as the thermodynamic potential of the hydrogen electrode reaction. In 1M KOH, E [value missing]. RHE =E Hg / HgO +0.9280.

[0085] DFT calculation

[0086] Density functional theory (DFT) calculations were performed using the Cambridge Sequential Total Energy Package (CASTEP) module in Materials Studio. The exchange and correction of atomic interactions were described using the general gradient approximation method of the Perdew-Burke-Emzerh function (GGA-PBE), and the interaction between valence electrons and ion nuclei was described using an ultrasoft pseudopotential method. A plane-wave basis set with a cutoff energy of 400 eV was specified. The Brillouin zone was sampled using a Monkhorst-Pack lattice for the crystal model and Γ points for the amorphous and crystalline / amorphous interface models. The tolerances for energy, force, and displacement used for structure optimization were 1.0 × 10⁻⁶. -6 eV / atom, and Set the self-consistent field to 1.0 × 10 -5 eV / atom. Calculate the H2O adsorption energy (ΔE) at the catalyst surface according to the following formula. H2O ): Where E surf and It is the total surface energy before and after H2O adsorption. This represents the energy of a free water molecule.

[0087] The Gibbs free energy (ΔG) used for hydrogen adsorption is calculated according to the following formula. H* ): in ΔZPE, T, and ΔS represent the binding energy, zero-point energy change, temperature, and entropy change of the H* adsorption system, respectively.

[0088] The vibrational entropy of H* in the adsorbed state is usually negligible. Therefore, ΔS is calculated as: in It is the entropy of gaseous H2 under standard conditions.

[0089] Furthermore, ΔZPE is calculated as follows:

[0090] Therefore, the Gibbs free energy of the adsorbed state of H* is calculated using a simplified equation:

[0091] A series of atomic models were established to study the H2O adsorption energy and Gibbs free energy of H* at various active sites in different regions of HEAA samples with and without elemental oxygen. The modeling results are consistent with experimental results. Specifically, three representative models with crystalline, amorphous, and crystalline / amorphous dual-phase structures (referred to as crystalline, MG, and interface, respectively) were constructed.

[0092] To reveal the effect of oxygen addition on the hydrogen evolution reaction performance, three additional models with crystalline, amorphous, and bicrystalline / amorphous phase structures were constructed under oxygen addition conditions. To obtain a reliable configuration for the amorphous model, all atoms were first randomly assigned to a cubic supercell, and periodic boundary conditions were applied in three directions. Then, the amorphous model was thoroughly relaxed and optimized to remove artificial influences. The crystalline / amorphous interface model was established by combining the crystalline and amorphous models, followed by further relaxation and optimization. Using the optimized crystalline, amorphous, and interface models established above, approximately... A wide vacuum gap was used to study the hydrogen evolution reaction performance of various active sites on the surface of these models. Therefore, the H₂O adsorption energy and H* Gibbs free energy of six representative models (crystalline, amorphous, and interface models with and without added oxygen) could be studied to reveal the atomic mechanisms explaining the improved hydrogen evolution reaction performance of the catalyst of the present invention.

[0093] Example 2 - Preparation of SNDP-Pd@HEAA catalyst

[0094] A catalyst with a novel ultra-nano dual-phase structure was synthesized by innovatively introducing a large amount of oxygen. In this example, the SNDP-Pd@HEAA catalyst was synthesized using dual-target magnetron sputtering (a bottom-up industrial method capable of large-scale production of various nanomaterials). The manufacturing method used in this invention is magnetron co-sputtering (Estrom Engineering Ltd.). The background vacuum was 4 × 10⁻⁶. -7 HEAA and Pd targets were used for co-sputtering. Then, SNDP-Pd@HEAA was simultaneously deposited on different substrates (Si(001), carbon cloth and nickel foam, Pt foil) for different purposes.

[0095] The film thickness is easily controlled by sputtering time, and the film composition is controlled by adjusting the distance difference between the substrate and the target. During the co-sputtering process, the power supplied to the HEAA target using a DC source was set to 135W; the power supplied to the Pd target using an RF source was set to 105W; the Ar flow rate was 20 sccm and the O2 flow rate was 1 sccm; the chamber pressure was 3 mTorr; and the deposition rate was approximately 6 nm / min. -1 Furthermore, the temperature of the substrate is below 50°C.

[0096] In addition, a series of SNDP-M@HEAA materials (M = Ir, Pt, Ru, Au, Ag or W) were prepared using the same method.

[0097] Example 3 - Characterization of SNDP-Pd@HEAA catalyst

[0098] refer to Figure 1A The X-ray diffraction patterns of the SNDP-Pd@HEAA and As-SNDP-Pd@HEAA catalysts exhibit broad diffraction peaks without strong Bragg crystalline diffraction. These peaks are much narrower than those of amorphous HEAA, indicating the amorphous and ultra-small nanocrystalline nature of the catalysts. SEM images of SNDP-Pd@HEAA deposited on carbon cloth reveal a smooth surface. Figure 1B Furthermore, atomic force microscopy revealed an ultrasmooth surface of SNDP-Pd@HEAA, exhibiting a roughness of only approximately 1.36 nm. Figure 1C ).

[0099] The components of SNDP-Pd@HEAA were identified using EDS plotting. (Reference) Figure 1D SNDP-Pd@HEAA contains 25.12 at% Pd, 42.24 at% O, 2.74 at% Al, 3.35 at% Si, 2.9 at% Ti, 3.99 at% Ni, 4.62 at% Cu, 8.62 at% Zn and 6.41 at% Zr.

[0100] Figure 2A The TEM images show a uniform distribution of nanoparticles surrounded by a thin amorphous layer. Figure 2B The high-resolution STEM images further reveal the amorphous / nanocrystalline SNDP structure, characterized by uniformly dispersed nanocrystals with a diameter of approximately 4.5 nm and a face-centered cubic crystalline structure. Surrounding the nanocrystals is an amorphous layer with a thickness of approximately 1.2 nm. (Reference) Figure 2CThe findings are consistent with the selected region electron diffraction (SAED) pattern, which shows amorphous rings and several crystalline rings. These crystalline rings can be indexed to a polycrystalline face-centered cubic Pd with random orientation.

[0101] The 3D reconstructed TEM image shows the same SNDP structure from the horizontal region to the cross-sectional region. Figure 3A This indicates that SNDP-Pd@HEAA possesses a uniform SNDP structure in three dimensions, which differs significantly from the particle / columnar structure of conventional sputtered films. Statistical analysis of the grain size distribution of over 300 nanocrystals showed that the average grain size was approximately 4.76 nm, and over 94.47% of the nanocrystals were in the size range of 3–6 nm. Figure 3B Cross-sectional high-angle annular dark-field STEM (HAADF-STEM) images provide additional evidence for the nanocrystalline nature of SNDP-Pd@HEAA. Figure 3C The corresponding associated EDS line scan composition distribution (). Figure 3D The study revealed a sharp compositional transition between Pd and oxygen across the amorphous and crystalline regions. Specifically, the Pd content was higher in the nanocrystalline regions compared to the amorphous regions, while the oxygen content showed an inverse distribution relative to Pd. Other elements (e.g., Al, Zn, Ti, Zr, Si, Cu, and Ni) were uniformly distributed in the SNDP film.

[0102] Figure 3E Two-dimensional tomographic reconstructions from a typical three-dimensional atom probe tomography dataset are presented, revealing the content variations of all elements across the truncated plane. Specifically, the crystalline and amorphous phases are enriched in Pd and O, respectively, while Al, Zn, Ti, Zr, Si, Cu, and Ni are uniformly distributed in both phases as conventional solutes.

[0103] For comparison, samples obtained under identical conditions, except for the introduction of oxygen during the synthesis process, are designated As-SNDP-Pd@HEAA. Pure HEAA and pure Pd films were prepared by single-target sputtering under the same conditions. For comparison, samples with different oxygen contents were prepared at different O2 flow rates. The As-SNDP-Pd@HEAA sample exhibits a crystalline-amorphous SNDP structure similar to that of SNDP-Pd@HEAA. The o-Pd and o-HEAA samples exhibit pure PdO crystalline and pure amorphous properties, respectively. Similarly, the As-Pd and As-HEAA samples exhibit pure Pd crystalline and pure amorphous properties, respectively.

[0104] SNDP-Pd@HEAA samples with varying oxygen contents were generated by adjusting the oxygen flow rate. The elemental composition of these samples was determined using SEM-EDS and is summarized in Table 1. Oxygen content was positively correlated with oxygen flow rate.

[0105] Table 1 - Elemental composition of SNDP-Pd@HEAA samples with different oxygen contents obtained by SEM-EDS

[0106] refer to Figure 4A Detailed TEM analysis revealed a consistent SNDP structure across the entire range of oxygen contents studied. SNDP-Pd@HEAA samples with different oxygen contents exhibited similar broad diffraction peaks, with peak positions shifting. Figure 4B ).

[0107] To determine the chemical states of elements in SNDP-Pd@HEAA, XPS was performed, such as... Figures 5A-5C As shown in the figure. The Pd3d spectrum has a value at 340.64 eV (Pd3d 3 / 2 ) and 335.32eV (Pd 3d 5 / 2 The two peaks are those of metallic Pd (Pd). 0 ) 10 The characteristics of the SNDP are as follows. Additionally, a slight shift towards higher energies is observed compared to pure Pd metal, likely due to the surrounding amorphous structure. Introducing oxygen into SNDP causes a downshift in the Pd 3d signal, indicating that the d-band electronic structure of SNDP-Pd@HEAA can be readily modulated by oxygen atoms. Similarly, binding energies at 951.67 eV and 931.85 eV reveal a single metallic state for Cu. Ni 2p XPS spectra show that most Ni is in a metallic state with only a small amount oxidized. Conversely, Si 2p XPS spectra reveal that most silicon is in an oxidized state, with only a small amount remaining in a zero-valence state. Al 2p, Ti 2p, Ti 2p, and Zr 3d XPS spectra indicate that all these elements are in an oxidized state. O 1s spectra can be deconvoluted into multiple peaks, indicating a complex coordination state of oxygen with other atoms in SNDP-Pd@HEAA. These results further illustrate that the introduced oxygen preferentially reacts with the elements of HEAA, and that HEAA protects Pd from oxidation, leading to oxygen enrichment in the amorphous region.

[0108] Furthermore, X-ray absorption fine structure (XAFS) measurements were performed to elucidate the electronic and atomic structures of SNDP-Pd@HEAA and As-SNDP-Pd@HEAA. (Reference) Figure 6AThe X-ray absorption near-edge structure spectra at the Pd K-edge indicate that in both SNDP-Pd@HEAA and As-SNDP-Pd@HEAA, elemental Pd is primarily in the Pd0 metallic state. The significant increase in oxygen content does not affect the valence state of Pd, which is consistent with the previously mentioned XPS results. The corresponding X-ray absorption fine structure (EXAFS) of the extended Pd K-edge is shown below. Figure 6B ) and its fitting analysis ( Figure 6C Tables 2 and 3 reveal the presence of Pd-Pd and Pd-M (M = Ni, Cu, Zn) coordination in both SNDP-Pd@HEAA and As-SNDP-Pd@HEAA.

[0109] Table 2 - EXAFS fitting parameters (S0) at the Pd K-edge for SNDP-Pd@HEAA 2 =0.82) CN: Coordination number; R: Bonding distance; σ 2 Debye-Woller factor; ΔE0: internal potential correction; R factor: goodness of fit; M = Cu, Ni, Zn.

[0110] Table 3 - EXAFS fitting parameters (S0) at the Pd K-edge for As-SNDP-Pd@HEAA 2 =0.84) CN: Coordination number; R: Bonding distance; σ 2 Debye-Woller factor; ΔE0: internal potential correction; R factor: goodness of fit; M = Cu, Ni, Zn.

[0111] In Tables 2 and 3, unlike As-SNDP-Pd@HEAA, the presence of Pd-O coordination and the lack of Pd-Zr coordination in SNDP-Pd@HEAA indicate that the coordination environment is affected by the introduction of oxygen during the preparation process. Figure 7 As shown, such differences are related to k 2 The wavelet transform of the weighted EXAFS signal can distinguish them more clearly.

[0112] The limited presence of Pd-O coordination in SNDP-Pd@HEAA, compared to the significant oxidation observed in o-Pd (Table 4), and the simultaneous reduction in the intensity of the white line in the near-edge structure X-ray absorption spectrum compared to the PdO standard, further illustrate the minimal oxidation of Pd due to a high degree of Pd-M coordination, which reduces the likelihood of Pd oxidation.

[0113] The interatomic distance between Pd atoms in SNDP-Pd@HEAA is approximately This is greater than As-SNDP-Pd@HEAA (approximately) ) and Pd foil (approximately The interatomic distance between Pd atoms in SNDP-Pd@HEAA is slightly shorter. Furthermore, both SNDP-Pd@HEAA and As-SNDP-Pd@HEAA exhibit lower total coordination numbers compared to Pd foil, indicating that crystalline Pd exists as small nanoparticles prominently present on the surface. This observation further suggests the presence of numerous interfaces within the unique SNDP structure.

[0114] Table 4 - EXAFS fitting parameters (S0) at the edge of o-Pd and Pd K-. 2 =0.82) CN: Coordination number; R: Bonding distance; σ 2 Debye-Woller factor; ΔE0: internal potential correction; R factor: goodness of fit.

[0115] Furthermore, all of the aforementioned SNDP-M@HEAA materials (M = Ir, Pt, Ru, Au, Ag, or W) exhibit similar X-ray diffraction patterns. Figure 8A ) and crystalline-amorphous dual-phase structure ( Figure 8B This demonstrates the universality of the method of the present invention.

[0116] Example 4 - Mechanism of the HER process

[0117] Further research was conducted using SNDP-Pd@HEAA as the model material to elucidate the structural advantages and mechanisms involved in the HER process.

[0118] Figures 9A-9B The electrocatalytic HER properties of the SNDP-Pd@HEAA sample are shown. Linear sweep voltammograms reveal that SNDP-Pd@HEAA exhibits the highest HER performance at 10 mA cm⁻¹. -2 It exhibits a low overpotential of 10.16 mV relative to RHE, which is significantly better than the overpotential of commercial 20 wt% Pt / C (34.01 mV relative to RHE) and other samples (i.e., As-SNDP-Pd@HEAA, o-Pd, As-Pd, o-HEAA and As-HEAA).

[0119] Furthermore, the HER mechanism of these catalysts was analyzed using the corresponding Tafel diagrams. (Reference) Figures 10A-10B In the linear region, the SNDP-Pd@HEAA catalyst exhibits a tenfold increase in V0.4. -1The minimum Tafel slope indicates the fastest Heyrovsky-dominated Volmer-Tafel reaction mechanism during hydrogen evolution. SNDP-Pd@HEAA samples with different oxygen contents also showed a similar trend.

[0120] It is well known that low charge transfer resistance indicates excellent electrocatalysts. Therefore, electrochemical impedance spectroscopy was performed at an overpotential of 100 mV to collect data and confirm the occurrence of HER. Figure 11 As shown, compared to the control sample, SNDP-Pd@HEAA has a much smaller semicircular trend diameter, which is comparable to that of a carbon-containing 20wt% Pt / C sample, indicating that the unique SNDP structure in SNDP-Pd@HEAA has great potential for optimizing the corresponding electronic structure.

[0121] Since changes in surface area can affect HER performance, the electrochemical surface area of ​​the catalyst is estimated by measuring the electrochemical double-layer capacitance (Cd1) using cyclic voltammetry. This electrochemical surface area represents the electrochemically active surface area. Figure 12A ).like Figure 12B As shown, the calculation C of SNDP-Pd@HEAA d1 It is 126.7 mF cm -2 And it is far higher than the commercial 20wt% Pt / C (46.0mF cm⁻¹) -2 ), As-SNDP-Pd@HEAA(40.0mF cm -2 ) and other samples (all less than 8 mF cm) -2 Calculation of C) d1 .

[0122] like Figure 13A As shown, the SNDP-Pd@HEAA electrocatalyst exhibits an inherent biphase structure containing both crystalline and amorphous regions, both with and without the addition of O. Initially, three types of models were constructed—crystalline interface, amorphous interface, and crystalline / amorphous interface, with and without oxygen. The structural integrity of these models was then optimized.

[0123] First, for the initial water adsorption step, the adsorption energy (ΔE) of H2O molecules at different catalytic sites in the three models was calculated. H2O ). Figure 13B-13C The Ti, Zr, and Al sites exhibited strong H2O adsorption in all three models, thus highlighting the ΔE of HEAA on the catalyst of this invention. H2O The main contribution is noteworthy. It is worth noting that the increase in H2O adsorption caused by the addition of elemental oxygen is most pronounced at the crystal / amorphous interface.

[0124] Figure 14 This diagram illustrates the atomic configurations, corresponding electron density differences, and bonding distances between O atoms in the H₂O molecule and the associated active sites at representative Pd, Ti, Zr, and Al sites, in interface models with and without element O. It also shows the shortening of the bonding distance between the active sites and O atoms in the H₂O molecule, and the departure of the O atom from the Fermi level (E) in the p-orbital partial wave density of states (p-PDOS) of the O atom in the H₂O molecule. F left shift () Figure 15 This reveals the ΔE caused by element O. H2O Increased physical origins.

[0125] As is well known, the Gibbs free energy of H* (ΔG) H* H* is a key descriptor for HER performance. A value close to zero is preferred because the HER process involves reversible adsorption and desorption of H*, requiring the interaction between the catalytic site and H* to be neither too strong nor too weak. It also facilitates the introduction of oxygen into the amorphous region, allowing less oxygen to directly coordinate with the active Pd centers in the crystalline region.

[0126] To specify the effect of oxygen coordination, the ΔG at the Pd site was compared under three conditions. H* Values: 1) No oxygen coordination, 2) With the nearest oxygen coordination, and 3) With the second nearest neighbor oxygen coordination. Observations revealed that the nearest oxygen coordination negatively affects ΔG. H* The second nearest neighbor oxygen coordination has been shown to be beneficial for optimizing ΔG. H* .

[0127] Density functional theory (DFT)-based calculations were performed to explore the atomic physical origins of the superior HER performance of the SNDP-Pd@HEAA of this invention. Analysis was conducted after H protons were adsorbed onto Pd sites located on catalyst surfaces in crystalline, amorphous, and crystalline / amorphous interface models. Figure 16A The ΔG described in H* Changes and Figure 16B-16C The corresponding atomic arrangement is shown in the figure. The results show that the Pd sites at the crystalline / amorphous interface have a higher ΔG value than those in the crystalline and amorphous models. H* A more favorable value for ΔG H* Value. Specifically, Pd sites with second-nearest neighbor oxygen coordination have near-zero ΔG. H* The value of 0.062 eV indicates that the second nearest neighbor oxygen coordination has a positive impact on HER performance. The high O content in the amorphous phase and the high Pd content in the crystalline phase may generate a high proportion of Pd sites with second nearest neighbor oxygen coordination.

[0128] Furthermore, by analyzing the two-dimensional electron density difference (in Figure 17AThe diagram shows that Ti coordination was selected as a representative of the 'interface' and 'interface-O-NN' models) and d-orbit partial density of states (d-PDOS). Figure 17B The effects of nearest and second nearest neighbor oxygen coordination at Pd sites in the crystalline / amorphous interface model were examined. Observations revealed that Pd sites experienced the most significant electron losses and a leftward shift of the d-band center away from the Fermi level due to nearest-nearest oxygen coordination, thus exacerbating HER performance. Simultaneously, electron losses in Pd were reduced, and when the Pd site was adjacent to the second nearest neighbor oxygen atom, the d-band center shifted rightward toward the Fermi level. This effectively promoted electron transfer and increased the strength of the interaction between H* and Pd sites, thus optimizing ΔG. H* .

[0129] In addition to Pd sites, ΔG was also observed at single-atom catalytic sites (such as Pd-Al and Pd-Cu sites). H* The observation indicates that the synergistic effect between the Pd site and HEAA significantly contributes to the outstanding HER performance of the developed electrocatalyst. Figures 18A-18B This allows the HER performance of crystalline / amorphous biphase catalysts without elemental oxygen to be comparable to that of commercial Pt / C catalysts.

[0130] In summary, experiments and DFT reveal that a large number of second-nearest neighbor oxygen coordination active sites at the interface generate a near-zero ΔG value. H* Strong H2O and hydrogen / proton adsorption are also observed. The enhanced H2O and hydrogen / proton adsorption contribute to the excellent HER performance of SNDP-Pd@HEAA. The near-nearest neighbor oxygen coordination with the Pd site effectively promotes electron transfer and increases the strength of the interaction between H* and the Pd site, thus optimizing the electron transfer efficiency. It also produced excellent HER performance.

[0131] Example 5 - The role of introducing oxygen

[0132] The introduction of oxygen can reduce the overpotential and accelerate the reaction kinetics. Figures 19A-19CThe relationship between oxygen content and electrocatalytic performance was summarized. All SNDP-Pd@HEAA samples with different oxygen contents exhibited significantly higher electrochemically active surface areas than or equivalent to those at 20 wt% Pt / C. This highlights the importance of the crystalline-amorphous dual-phase structure and the addition of oxygen. The results showed that SNDP-Pd@HEAA with an O concentration of 42.24 at.% exhibited the best electrocatalytic performance. This can be attributed to the introduction of oxygen, which weakens the adsorption energy of OH* due to the downward shift of the d-band center of Pd, resulting in lower impedance and a larger electrochemical surface area. However, excessively high oxygen concentrations led to severe oxidation of the metal component, as indicated by the upward shift of the d-band center of Pd, higher impedance, and smaller electrochemical surface area. Therefore, the enhanced HER performance caused by the addition of oxygen can be mainly attributed to the optimized electronic coupling and increased surface area within the SNDP-Pd@HEAA samples.

[0133] exist Figure 20 In this study, previously reported HER electrocatalysts tested in alkaline media at 10 mA cm⁻¹ were compared. -2 The overpotential at the current density is shown. This demonstrates that the SNDP-Pd@HEAA catalyst is competitive with existing HER catalysts. Specifically, Table 5 lists the hydrogen evolution reaction performance of SNDP-Pd@HEAA in 1M KOH and previously reported crystalline-amorphous biphase catalysts.

[0134] Table 5

[0135] In addition to enhancing catalytic efficiency, the effect of introducing oxygen on stability was also examined. (Reference) Figure 21A SNDP-Pd@HEAA performed at 20 mAcm during a 100-hour long-term test. -2 It exhibits good stability at current densities, with the overpotential of SNDP-Pd@HEAA decreasing by only about 17.3 mV, which is much smaller than that of As-SNDP-Pd@HEAA. After a long-term test of 100 hours, SNDP-Pd@HEAA maintained its SNDP structure and valence state, confirming the robust stability of SNDP-Pd@HEAA during HER operation. Nevertheless, at the end of the stability test, the elements Al, Zn, Ti, Zr, and Si in As-SNDP-Pd@HEAA were significantly oxidized ( Figure 21B This indicates that the introduction of oxygen effectively enhances the structural stability of SNDP-Pd@HEAA.

[0136] The concentrations of the elements Pd, Al, Zn, Ti, Zr, Si, Cu, and Ni dissolved in the solution are at 200 mA / cm² under alkaline conditions. -2The 200-hour durability test conducted at the current density was completed using inductively coupled plasma-optical emission spectroscopy, as shown in Table 6.

[0137] Table 6 - At 200mA cm -2 ICP-OES results of SNDP-Pd@HEAA after 200 hours at a current density of [value missing]. *Reliable measurement of the lowest concentration of a substance via ICP-OES

[0138] The concentrations of all detected elements were close to the instrument's detection limit, consistent with the slight variations observed in XPS elemental composition analysis of SNDP-Pd@HEAA. This further highlights the superior stability of SNDP-Pd@HEAA.

[0139] In addition, such as Figures 22A-22F As shown, introducing oxygen into the SNDP catalyst resulted in electrocatalytic HER and / or OER performance exceeding that of other samples. This further underscores the universality of oxygen addition as an effective strategy for enhancing electrocatalytic performance.

[0140] Example 6 - Preparation of a flow-type membrane exchange assembly alkaline water electrocatalytic cell unit

[0141] SNDP-Pd@HEAA deposited on carbon felt and SNDP-Ir@HEAA deposited on porous titanium sheet were used as cathode and anode, respectively.

[0142] refer to Figure 23 It was observed that the SNDP-Pd@HEAA‖SNDP-Ir@HEAA electrolyzer operated at 500 mA cm⁻¹ -2 After 1000 hours of stable operation, the voltage did not decrease significantly relative to the initial state.

[0143] The above description of the present invention is for illustrative purposes only and is not intended to be exhaustive or to limit the invention to the specific forms disclosed. Many modifications and variations will be apparent to those skilled in the art.

[0144] The embodiments have been selected and described in order to best explain the principles of the invention and its practical application, thereby enabling those skilled in the art to understand the invention with respect to the various embodiments and its various modifications for particular purposes.

[0145] definition

[0146] Throughout this specification, unless the context otherwise requires, the word “comprise” or variations thereof, such as “comprises” or “comprising”, should be understood to imply inclusion of the stated whole or group of wholes, but not to exclude any other whole or group of wholes. It should also be noted that in this disclosure and particularly in the claims and / or paragraphs, terms such as “comprise,” “comprised,” and “comprising” may have the meaning attributed to them under U.S. patent law, for example, allowing elements not expressly listed but excluding elements found in the prior art or elements affecting the essential or novel features of the invention.

[0147] Furthermore, throughout this specification and claims, unless the context otherwise requires, the word "include" or variations such as "includes" or "including" shall be understood to imply inclusion of the stated whole or group of wholes, but not to exclude any other whole or group of wholes.

[0148] As used herein and unless otherwise defined, the terms “substantially,” “basically,” “approximately,” and “about” are used to describe and explain small variations. When used in conjunction with an event or situation, the terms may cover instances where the event or situation occurred precisely or instances where the event or situation was close to occurring. For example, when used in conjunction with a numerical value, the terms may cover a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%.

[0149] References to "an embodiment," "an example embodiment," "exemplary embodiment," etc., in this specification indicate that the described embodiment may include specific features, structures, or characteristics, but not every embodiment necessarily includes specific features, structures, or characteristics. Furthermore, such phrases do not necessarily refer to the same embodiment. Additionally, when a specific feature, structure, or characteristic is described in connection with an embodiment, it is assumed that the effect of such feature, structure, or characteristic in conjunction with other embodiments is within the knowledge of those skilled in the art, whether explicitly described or not.

[0150] In the preparation methods described herein, steps may be performed in any order without departing from the principles of the invention, except where the timing or order of operations is explicitly stated. A statement in a claim that a step is performed first, followed by several other steps, should be interpreted as meaning that the first step is performed before any of the other steps, but the other steps may be performed in any suitable order unless the order is further stated in the other steps. For example, a claim element stating "step A, step B, step C, step D, and step E" should be interpreted as meaning that step A is performed first and step E is performed last, and steps B, C, and D may be performed in any order between steps A and E, and such order still falls within the literal scope of the claimed process. A given step or subset of steps may also be repeated. Furthermore, unless the claim language explicitly states that the specified steps are performed separately, they may be performed simultaneously.

[0151] The term "double-layer capacitance" refers to the capacitive effect formed between an electrode surface and an electrolyte solution, where the adsorbed charges on the electrode surface and the corresponding ions in the electrolyte create a charge barrier. This charge barrier can store charge and produce a capacitive effect under the influence of an electric field.

[0152] The term "at.%" indicates an atomic percentage. This term is a unit of concentration used in chemistry and materials science to express the proportion of one type of atom relative to the total number of atoms in a mixture, compound, or alloy. For example, in a sample having 10 at.% of element A and 90 at.% of element B, this means that out of every 100 atoms in the sample, 10 are atoms of element A and 90 are atoms of element B.

[0153] Other definitions of the selected terms used herein can be found in the detailed description of the invention and apply throughout. Unless otherwise defined, all other technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

Claims

1. An oxygen dominated ultra-nanobiphase catalytic reaction material on a substrate, characterized by, The oxygen-dominated ultra-nano dual-phase catalytic reaction material comprises a uniform oxygen-rich amorphous shell and a core encapsulated in the uniform oxygen-rich amorphous shell, wherein the oxygen-dominated ultra-nano dual-phase catalytic reaction material has an intrinsic crystal-amorphous dual-phase structure, and wherein the oxygen-dominated ultra-nano dual-phase catalytic reaction material has an overpotential of 10 mV to 25 mV relative to a reversible hydrogen electrode. -2 The overpotential relative to a reversible hydrogen electrode is 10 mV to 25 mV.

2. The oxygen-dominated ultra-nanophasic catalytic reaction material of claim 1, wherein the uniform oxygen-rich amorphous shell is made of high-entropy amorphous alloy comprising Al 0.5 AlTiCrZrSiCuNi, alloys with FeCoNiMoPB.

3. The oxygen-dominant ultra-nano dual-phase catalytic reaction material of claim 1, wherein the core is made of at least one transition metal or non-noble metal or NiMo, NiW binary alloy, the transition metal comprising palladium, platinum, iridium, ruthenium, rhodium, gold, silver, the non-noble metal comprising vanadium, molybdenum, tungsten.

4. The oxygen-dominant ultra-nano dual-phase catalytic reaction material of claim 1, wherein the core has a diameter ranging from 1 to 10 nm, and the uniform oxygen-rich amorphous shell has a thickness ranging from 1 to 5 nm.

5. The oxygen-dominant ultra-nano dual-phase catalytic reaction material of claim 1, wherein the oxygen-dominant ultra-nano dual-phase catalytic reaction material contains 20-30 at% of palladium, 10-50 at% of oxygen, 1-5 at% of aluminum, 5-20 at% of silicon, 5-20 at% of titanium, 5-20 at% of nickel, 5-20 at% of copper, 1-15 at% of zinc, and 5-20 at% of zirconium.

6. The oxygen-dominant ultra-nano dual-phase catalytic reaction material of claim 1, wherein the oxygen-dominant ultra-nano dual-phase catalytic reaction material contains 10-30 at% of platinum, 10-40 at% of oxygen, 5-20 at% of iron, 5-20 at% of cobalt, 5-20 at% of nickel, 1-15 at% of molybdenum, 1-10 at% of phosphorus, and 1-10 at% of boron.

7. The oxygen-dominant ultra-nano dual-phase catalytic reaction material of claim 1, wherein the substrate comprises a nickel foam, a carbon cloth, a carbon paper, a silicon wafer, a titanium sheet, or a platinum foil.

8. The oxygen-dominant ultra-nano dual-phase catalytic reaction material of claim 1, wherein the crystalline phase has a face-centered cubic structure and the amorphous phase has a typical disordered and random arrangement structure.

9. The oxygen-dominant ultra-nano bi-phase catalytic reaction material of claim 1, wherein the oxygen-dominant ultra-nano bi-phase catalytic reaction material exhibits stability in a 100-hour long-term test at a current density of 20 mA cm-2 in a three-electrode system and is capable of stable operation for 1000 hours at a current density of 500 mA cm-2 in a flow-type membrane exchange assembly alkaline water electrolysis catalytic cell. 2 2 ​​ 10. A water-splitting electrode made of the oxygen-dominant ultra-nano dual-phase catalytic reaction material of claim 1.

11. A method for manufacturing an oxygen-dominant ultra-nano dual-phase catalytic reaction material, the method comprising co-sputtering a crystalline metal species and a high-entropy amorphous alloy species on a substrate by industrial magnetron sputtering, and wherein oxygen gas is introduced during the magnetron sputtering process.

12. The method of claim 11, wherein the crystalline metal species is selected from one or more of the following: noble metals palladium, platinum, iridium, ruthenium, rhodium, gold, silver; non-noble metals vanadium, molybdenum, tungsten; and NiMo, NiW binary alloy.

13. The method of claim 11, wherein the oxygen gas has a flow rate ranging from 0.01 seem to 50 seem.

14. The method of claim 11, wherein the high-entropy amorphous alloy species is a multi-component alloy comprising an alloy with AlZnTiZrSiCuNi, an alloy with FeCoNiMoPB.

15. The method of claim 14, wherein the oxygen-dominated ultra-nano dual-phase catalytic reaction material contains 20-30 at% of palladium, 10-50 at% of oxygen, 1-5 at% of aluminum, 5-20 at% of silicon, 5-20 at% of titanium, 5-20 at% of nickel, 5-20 at% of copper, 1-15 at% of zinc, and 5-20 at% of zirconium.

16. The method of claim 14, wherein the oxygen-dominated ultra-nano dual-phase catalytic reaction material contains 10-30 at% of platinum, 10-40 at% of oxygen, 5-20 at% of iron, 5-20 at% of cobalt, 5-20 at% of nickel, 1-15 at% of molybdenum, 1-10 at% of phosphorus, and 1-10 at% of boron.

17. The method of claim 11, wherein the industrial magnetron sputtering employs a sputtering temperature of 0.1 °C to 200 °C.

18. The method of claim 11, further comprising applying different powers to the crystalline metal object and the high-entropy amorphous alloy object.

19. The method of claim 12, wherein a rotation speed of the substrate during sputtering is in a range of 0.1 rpm to 20 rpm.

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