CN114232022A - Carbon-supported iridium molybdenum tungsten intermetallic compound and preparation method and application thereof - Google Patents
Carbon-supported iridium molybdenum tungsten intermetallic compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon-supported iridium molybdenum tungsten intermetallic compound and a preparation method and application thereof. The composition of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises a carbon carrier and a supported iridium molybdenum tungsten intermetallic compound, wherein the chemical formula of the iridium molybdenum tungsten intermetallic compound is IrMo1‑xWxX is more than or equal to 0 and less than or equal to 1. The preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises the following steps: mixing the iridium source, molybdenum source or/and tungsten source and carbon carrier in solvent system, removing solvent, and heat treating in reducing atmosphere to obtain carbon-carried iridium molybdenumA tungsten-based intermetallic compound. The carbon-supported iridium molybdenum tungsten intermetallic compound has excellent electrocatalytic hydrogen evolution and oxygen evolution activities in both acid electrolyte and alkaline electrolyte, has a simple preparation method, and is suitable for being used as a cathode/anode catalyst in an acid/alkaline water electrolysis device.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to a carbon-supported iridium molybdenum tungsten intermetallic compound and a preparation method and application thereof.
Background
Hydrogen energy is renewable energy with high energy density and zero emission, and is praised as the most promising energy carrier in the future. At present, the acquisition of hydrogen energy mainly comprises two types of hydrogen production by reforming and hydrogen production by electrolyzing water, and the electrolysis of water by using electric energy generated by intermittent energy power generation is an important way for realizing the sustainable development of hydrogen energy.
Oxygen Evolution Reaction (OER) generated at the anode and Hydrogen Evolution Reaction (HER) generated at the cathode in the process of hydrogen production by water electrolysis are key processes affecting the overall efficiency of hydrogen production by water electrolysis. At present, the development of high performance catalysts for OER and HER still faces a number of problems, specifically as follows: 1) the OER reaction generated at the anode is in an acid electrolytic water system or an alkaline electrolytic water system, the dynamics is very slow due to the multi-electron-proton coupling process, even if noble metals iridium and iridium oxide are used as catalysts, the OER can be catalyzed by a high overpotential, and due to the strong corrosivity (high potential and strong acid) of the acid system, a material capable of stably keeping high OER activity is fresh; 2) the HER reaction in an acidic system has higher reaction kinetics than that of a basic system, the acidic HER catalyst with the best activity is mainly a noble metal platinum catalyst, the platinum reserves are limited, the price is high, and no non-noble metal-based acidic system HER catalyst capable of meeting the practical application exists at present; 3) the HER reaction in basic systems involves a multi-step water dissociation process, the reaction rate is far less than that of an acidic environment, and even noble metal catalysts are relatively low in efficiency, and although most non-noble metal-based catalysts are stable in a basic environment, the activity is far lower than that of noble metal-based catalysts.
Therefore, it is very important to develop a catalyst having excellent electrocatalytic hydrogen and oxygen evolution activities in both acidic and alkaline electrolytes.
Disclosure of Invention
The invention aims to provide a carbon-supported iridium molybdenum tungsten intermetallic compound and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the carbon-supported iridium molybdenum tungsten intermetallic compound comprises a carbon carrier and a supported iridium molybdenum tungsten intermetallic compound, wherein the chemical formula of the iridium molybdenum tungsten intermetallic compound is IrMo1-xWx，0≤x≤1。
Preferably, the carbon support is at least one of a commercial carbon support and a carbon nanotube.
Further preferably, the carbon support is a carbon nanotube.
Preferably, the iridium molybdenum tungsten intermetallic compound is at least one of an iridium molybdenum intermetallic compound, an iridium tungsten intermetallic compound, and an iridium molybdenum tungsten intermetallic compound.
Preferably, the iridium molybdenum tungsten intermetallic compound loading amount in the iridium molybdenum tungsten intermetallic compound on carbon is 10% to 30%.
Preferably, the molar ratio of iridium element, molybdenum element or/and tungsten element in the iridium molybdenum tungsten intermetallic compound is 1: 0.3-1: 3.0.
The preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises the following steps: and uniformly mixing the iridium source, the molybdenum source or/and the tungsten source and the carbon carrier in a solvent system, removing the solvent, and then placing in a reducing atmosphere for heat treatment to obtain the carbon-supported iridium molybdenum tungsten intermetallic compound.
Preferably, the method for preparing the iridium molybdenum tungsten intermetallic compound carried on carbon comprises the following steps: and adding an iridium source, a molybdenum source or/and a tungsten source and a carbon carrier into a solvent system, performing ultrasonic treatment, performing freeze drying or rotary evaporation to remove the solvent, and performing heat treatment in a reducing atmosphere to obtain the carbon-supported iridium molybdenum tungsten intermetallic compound.
Preferably, the iridium source is at least one of iridium trinitrate, iridium trichloride, iridium tetrachloride, chloroiridate and iridium acetate.
Further preferably, the iridium source is iridium trichloride trihydrate.
Preferably, the molybdenum source is at least one of ammonium paramolybdate, sodium paramolybdate, potassium paramolybdate, ammonium molybdate, sodium molybdate, potassium molybdate, molybdenum trichloride, molybdenum pentachloride and molybdenum hexachloride.
Further preferably, the molybdenum source is ammonium molybdate tetrahydrate.
Preferably, the tungsten source is at least one of ammonium metatungstate, sodium metatungstate, potassium metatungstate, ammonium tungstate, sodium tungstate, potassium tungstate, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride and tungsten hexachloride.
Further preferably, the tungsten source is ammonium tungstate tetrahydrate.
Preferably, the carbon support is subjected to hydrophilic treatment.
Preferably, the hydrophilic treatment is performed by the following specific operations: the carbon carrier is dispersed in an oxidizing acid to be subjected to oxidation treatment.
Preferably, the oxidizing acid is one of sulfuric acid, hydrochloric acid, nitric acid, a sulfuric acid-nitric acid mixture, a sulfuric acid-hydrogen peroxide solution mixture and a nitric acid-hydrogen peroxide solution mixture.
Preferably, the oxidation treatment is carried out at 60-160 ℃ for 2-12 h.
Preferably, the time of the ultrasonic treatment is 0.5 h-6.5 h.
Preferably, the freeze drying is carried out by the following specific steps: adding the mixture obtained by ultrasonic treatment into a freeze drying device, freezing and solidifying for 1-12 h at-120 to-20 ℃, and then vacuumizing and drying for 12-48 h.
Preferably, the specific operation of the rotary evaporation is as follows: adding the mixture obtained by ultrasonic treatment into a rotary evaporator, and vacuumizing for 2-24 h at 30-80 ℃.
Preferably, the reducing atmosphere is N2-H2Mixed atmosphere, Ar-H2One of mixed atmospheres.
More preferably, the reducing atmosphere is H2Volume fraction 8% of N2-H2Mixed atmosphere, H2Volume fraction of 8% of Ar-H2One of mixed atmospheres.
Preferably, the specific operation of the heat treatment is as follows: heating from room temperature (25 +/-5 ℃) to 600-900 ℃ at the heating rate of 2-10 ℃/min, and then preserving heat for 1-12 h.
The invention has the beneficial effects that: the carbon-supported iridium molybdenum tungsten intermetallic compound has excellent electrocatalytic hydrogen evolution and oxygen evolution activities in both acid electrolyte and alkaline electrolyte, has a simple preparation method, and is suitable for being used as a cathode/anode catalyst in an acid/alkaline water electrolysis device.
Specifically, the method comprises the following steps:
1) according to the invention, the iridium and the cheap molybdenum or/and tungsten are combined to form the ordered alloy, so that the iridium content in the catalyst is reduced, and the cost is lower than that of catalysts such as platinum and iridium;
2) according to the invention, the molybdenum, the tungsten and the iridium form an intermetallic compound, the electronic structure of active metal iridium can be regulated and controlled, and the coordination environment of iridium is optimized, so that the electrocatalytic activity and stability of the catalyst can be improved;
3) the iridium molybdenum tungsten intermetallic compound can still keep smaller particle size after being subjected to high-temperature heat treatment, and overcomes the problem that the common noble metal catalyst is easy to agglomerate and sinter after being subjected to high-temperature heat treatment, so that the iridium molybdenum tungsten intermetallic compound has higher electrochemical active area and improves the utilization rate of noble metals;
4) the iridium molybdenum tungsten intermetallic compound has an ordered structure, has better electrocatalytic activity and stability compared with common disordered alloy, and particularly has higher stability than common metal catalysts and alloy catalysts in acid electrolysis water cathode/anode reaction;
5) the preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound is simple and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an XRD pattern of the iridium-molybdenum-tungsten intermetallic compound on carbon according to examples 1 to 6.
FIG. 2 is a TEM image of the iridium molybdenum tungsten intermetallic compound on carbon of examples 1 to 3 and a HAAD-STEM image of the iridium molybdenum tungsten intermetallic compound on carbon of examples 4 to 6.
FIG. 3 is a graph of the concentration of H in 0.5mol/L for the carbon-supported Ir-Mo-W intermetallic compound and commercial Ir/C catalyst of examples 1-32SO4Polarization curve of electrocatalytic oxygen evolution in solution.
FIG. 4 is a graph showing the concentration of H in 0.5mol/L for the carbon-supported Ir-Mo-tungsten intermetallic compound, commercial Ir/C catalyst and commercial Pt/C catalyst of examples 1 to 32SO4Polarization curve of electrocatalytic hydrogen evolution in solution.
FIG. 5 is an electrocatalytic oxygen evolution polarization curve of the iridium molybdenum tungsten on carbon intermetallic compounds and commercial Ir/C catalysts of examples 4-5 in KOH solution with a concentration of 1 mol/L.
FIG. 6 is a graph showing the polarization curves of electrocatalytic hydrogen evolution of the iridium molybdenum tungsten intermetallic compound on carbon, the commercial Ir/C catalyst and the commercial Pt/C catalyst of examples 5 to 6 in a KOH solution having a concentration of 1 mol/L.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
the preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises the following steps:
1) adding 4g of commercial carbon nano tube into 400g of nitric acid aqueous solution with the mass fraction of 10%, stirring for 12h at 160 ℃ and the rotating speed of 300r/min, filtering, washing and filtering the obtained solid for 3 times, and transferring the solid into a vacuum drying oven for drying for 6h at 100 ℃ to obtain the hydrophilic modified carbon nano tube;
2) mixing an iridium chloride trihydrate solution with the concentration of 0.055mol/L, an ammonium molybdate tetrahydrate solution with the concentration of 0.055mol/L and 80mg of hydrophilic modified carbon nano tubes to ensure that the mass ratio of the total mass of iridium elements and molybdenum elements to the hydrophilic modified carbon nano tubes is 1:4 and the molar ratio of iridium elements and molybdenum elements is 1:1, carrying out ultrasonic treatment for 3.5H, adding the mixture obtained by ultrasonic treatment into a freeze drying device, freezing and solidifying for 6.5H at-70 ℃, carrying out vacuum drying for 30H, transferring the obtained solid into a tubular furnace, and filling H into the tubular furnace2Volume fraction of 8% Ar-H2The mixed gas is mixed with the water and the air,Ar-H2and (3) the flow rate of the mixed gas is 50mL/min, the temperature is increased from room temperature to 800 ℃ at the temperature increase rate of 5 ℃/min, the temperature is maintained for 6h, and the carbon-supported iridium molybdenum tungsten intermetallic compound (marked as IrMo/CNT) is obtained after cooling to room temperature.
Example 2:
the preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises the following steps:
1) adding 4g of commercial carbon nano tube into 220g of nitric acid aqueous solution with the mass fraction of 40%, stirring for 7h at the temperature of 110 ℃ and the rotating speed of 750r/min, filtering, washing the filtered solid for 3 times, and then transferring the solid to a vacuum drying oven for drying for 6h at the temperature of 100 ℃ to obtain the hydrophilic modified carbon nano tube;
2) mixing an iridium chloride trihydrate solution with the concentration of 0.005mol/L, an ammonium tungstate tetrahydrate solution with the concentration of 0.005mol/L and 80mg of hydrophilic modified carbon nano tubes to ensure that the mass ratio of the total mass of iridium elements and tungsten elements to the hydrophilic modified carbon nano tubes is 1:9 and the molar ratio of the iridium elements and the tungsten elements is 1:1, carrying out ultrasonic treatment for 0.5H, adding the mixture obtained by ultrasonic treatment into a freeze drying device, freezing and solidifying for 1H at-120 ℃, then carrying out vacuum drying for 48H, transferring the obtained solid into a tubular furnace, and filling H into the tubular furnace2Volume fraction of 8% Ar-H2Mixed gas, Ar-H2And (3) heating the mixed gas to 800 ℃ from room temperature at the heating rate of 5 ℃/min, preserving the heat for 6h, and cooling to room temperature to obtain the carbon-supported iridium molybdenum tungsten intermetallic compound (recorded as IrW/CNT).
Example 3:
the preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises the following steps:
1) adding 4g of commercial carbon nano tube into 40g of nitric acid aqueous solution with the mass fraction of 70%, stirring for 2h at the temperature of 60 ℃ and the rotating speed of 1200r/min, filtering, washing and filtering the obtained solid for 3 times, and transferring the solid into a vacuum drying oven to dry for 6h at the temperature of 100 ℃ to obtain the hydrophilic modified carbon nano tube;
2) mixing 0.0225mol/L iridium chloride trihydrate solution, 0.01125mol/L ammonium molybdate tetrahydrate solution, 0.01125mol/L ammonium tungstate tetrahydrate solution and 80mg of hydrophilic modified carbon nano tubeMixing until the mass ratio of the total mass of the iridium element, the molybdenum element and the tungsten element to the hydrophilic modified carbon nano tube is 3:7, the molar ratio of the iridium element, the molybdenum element and the tungsten element is 1:0.5:0.5, performing ultrasonic treatment for 6.5H, adding the mixture obtained by ultrasonic treatment into a freeze drying device, freezing and solidifying at-20 ℃ for 12H, performing vacuum drying for 12H, transferring the obtained solid into a tube furnace, and filling H2Volume fraction of 8% Ar-H2Mixed gas, Ar-H2The flow rate of the mixed gas is 50mL/min, the temperature is raised from room temperature to 800 ℃ at the temperature rise rate of 5 ℃/min, the temperature is maintained for 6h, and the carbon-supported iridium molybdenum intermetallic compound (marked as IrMo) is obtained after cooling to room temperature0.5W0.5/CNT)。
Example 4:
the preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises the following steps:
1) adding 4g of commercial carbon nano tube into 400g of nitric acid aqueous solution with the mass fraction of 10%, stirring for 12h at 160 ℃ and the rotating speed of 300r/min, filtering, washing and filtering the obtained solid for 3 times, and transferring the solid into a vacuum drying oven for drying for 6h at 100 ℃ to obtain the hydrophilic modified carbon nano tube;
2) mixing an iridium chloride trihydrate solution with the concentration of 0.055mol/L, an ammonium molybdate tetrahydrate solution with the concentration of 0.055mol/L and 80mg of hydrophilic modified carbon nano tubes to ensure that the mass ratio of the total mass of iridium elements and molybdenum elements to the hydrophilic modified carbon nano tubes is 1:4 and the molar ratio of iridium elements and molybdenum elements is 1:1, carrying out ultrasonic treatment for 3.5H, adding the mixture obtained by ultrasonic treatment into a rotary evaporator, vacuumizing for 24H at the temperature of 30 ℃, transferring the obtained solid into a tubular furnace, and filling H into the tubular furnace2Volume fraction of 8% Ar-H2Mixed gas, Ar-H2And (3) the flow of the mixed gas is 50mL/min, the temperature is increased from room temperature to 800 ℃ at the temperature increase rate of 5 ℃/min, the temperature is maintained for 6h, and the carbon-supported iridium molybdenum intermetallic compound (marked as IrMo/CNT) is obtained after cooling to room temperature.
Example 5:
the preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises the following steps:
1) adding 4g of commercial carbon nano tube into 400g of nitric acid aqueous solution with the mass fraction of 10%, stirring for 12h at 160 ℃ and the rotating speed of 300r/min, filtering, washing and filtering the obtained solid for 3 times, and transferring the solid into a vacuum drying oven for drying for 6h at 100 ℃ to obtain the hydrophilic modified carbon nano tube;
2) mixing an iridium chloride trihydrate solution with the concentration of 0.055mol/L, an ammonium molybdate tetrahydrate solution with the concentration of 0.055mol/L and 80mg of hydrophilic modified carbon nano tubes to ensure that the mass ratio of the total mass of iridium elements and molybdenum elements to the hydrophilic modified carbon nano tubes is 1:4 and the molar ratio of iridium elements and molybdenum elements is 1:1, carrying out ultrasonic treatment for 3.5H, adding the mixture obtained by ultrasonic treatment into a rotary evaporator, vacuumizing for 13H at 55 ℃, transferring the obtained solid into a tubular furnace, and filling H into the tubular furnace2Volume fraction of 8% Ar-H2Mixed gas, Ar-H2And (3) the flow of the mixed gas is 50mL/min, the temperature is increased from room temperature to 800 ℃ at the temperature increase rate of 5 ℃/min, the temperature is maintained for 6h, and the carbon-supported iridium molybdenum intermetallic compound (marked as IrMo/CNT) is obtained after cooling to room temperature.
Example 6:
the preparation method of the carbon-supported iridium molybdenum tungsten intermetallic compound comprises the following steps:
1) adding 4g of commercial carbon nano tube into 400g of nitric acid aqueous solution with the mass fraction of 10%, stirring for 12h at 160 ℃ and the rotating speed of 300r/min, filtering, washing and filtering the obtained solid for 3 times, and transferring the solid into a vacuum drying oven for drying for 6h at 100 ℃ to obtain the hydrophilic modified carbon nano tube;
2) mixing an iridium chloride trihydrate solution with the concentration of 0.055mol/L, an ammonium molybdate tetrahydrate solution with the concentration of 0.055mol/L and 80mg of hydrophilic modified carbon nano tubes to ensure that the mass ratio of the total mass of iridium elements and molybdenum elements to the hydrophilic modified carbon nano tubes is 1:4 and the molar ratio of iridium elements and molybdenum elements is 1:1, carrying out ultrasonic treatment for 3.5H, adding the mixture obtained by ultrasonic treatment into a rotary evaporator, vacuumizing for 2H at the temperature of 80 ℃, transferring the obtained solid into a tubular furnace, and filling H into the tubular furnace2Volume fraction of 8% Ar-H2Mixed gas, Ar-H2And (3) the flow of the mixed gas is 50mL/min, the temperature is increased from room temperature to 800 ℃ at the temperature increase rate of 5 ℃/min, the temperature is maintained for 6h, and the carbon-supported iridium molybdenum intermetallic compound (marked as IrMo/CNT) is obtained after cooling to room temperature.
And (3) performance testing:
1) according to the X-ray diffraction test method, the phase of the iridium molybdenum tungsten intermetallic compounds on carbon supports of examples 1 to 6 was characterized by using a MiniFlex 600X-ray diffractometer from japan, under the conditions of a test voltage of 35kV and a test current of 30mA, and the obtained X-ray diffraction (XRD) pattern is shown in fig. 1.
As can be seen from fig. 1:
a) the diffraction peak of the IrMo/CNT prepared in example 1 is consistent with the PDF standard card of the IrMo intermetallic compound, which shows that the IrMo intermetallic compound of the ordered phase is successfully prepared;
b) the diffraction peak of IrW/CNT prepared in example 2 is consistent with the PDF standard card of IrW intermetallic compound, which shows that IrW intermetallic compound with ordered phase is successfully prepared;
c) IrMo prepared in example 30.5W0.5The diffraction peak of the/CNT is similar to the PDF standard card of IrW intermetallic compound and IrMo intermetallic compound, which shows that IrMo of ordered phase is successfully prepared0.5W0.5An intermetallic compound;
d) the diffraction peaks of IrMo/CNT prepared in examples 4-6 are consistent with the PDF standard card of IrMo intermetallic compound, which shows that IrMo intermetallic compound with ordered phase is successfully prepared.
2) Morphology characterization of the iridium molybdenum tungsten intermetallic compounds on carbon in examples 1 to 6 was performed by using a Talos F200X transmission electron microscope under a voltage of 200kV, and Transmission Electron Microscope (TEM) images of the iridium molybdenum tungsten intermetallic compounds on carbon in examples 1 to 3 and high-angle annular dark-field scanning transmission electron microscope (HAAD-STEM) images of the iridium molybdenum tungsten intermetallic compounds on carbon in examples 4 to 6 were obtained as shown in fig. 2.
As can be seen from fig. 2:
a) the IrMo/CNT prepared in the embodiment 1 has uniform particle distribution and particle size of 2 nm-4 nm, which indicates that the IrMo intermetallic compound with uniform particle distribution and small size is successfully prepared;
b) the IrW/CNT prepared in example 2 has uniform particle distribution and a particle size of 3 nm-5 nm, which indicates that IrW intermetallic compound with uniform particle distribution and small size is successfully prepared;
c) IrMo prepared in example 30.5W0.5The particles of the/CNT are uniformly distributed, and the particle size is 3-5 nm, which shows that the IrMo with uniform particle distribution and small size is successfully prepared0.5W0.5An intermetallic compound;
d) the IrMo/CNT prepared in the embodiments 4-6 have uniform particle distribution and particle size of 2 nm-4 nm, which shows that the IrMo intermetallic compound with uniform particle distribution and small size is successfully prepared.
3) According to the electrochemical linear volt-ampere test method, under the condition that the scanning speed is 10mV/s, the carbon-supported iridium molybdenum tungsten intermetallic compounds, the commercial Ir/C catalysts and the commercial Pt/C catalysts of the examples 1 to 3 are subjected to N reaction by adopting an Autolab electrochemical workstation of Vantone Switzerland2Saturated concentration of 0.5mol/L H2SO4Performing electrochemical test in the solution, and respectively measuring the activity of the electrocatalytic oxygen evolution reaction and the electrocatalytic hydrogen evolution reaction, wherein the test rotating speed of the rotating disc electrode is 1600r/min, and the load capacity of Ir in the catalyst on the electrode is 5g/cm2The obtained electrocatalytic oxygen evolution polarization curve is shown in fig. 3, and the electrocatalytic hydrogen evolution polarization curve is shown in fig. 4.
As can be seen from fig. 3 and 4:
a) the over potential of electrocatalytic oxygen evolution of the IrMo/CNT prepared in the example 1 is lower than that of a commercial Ir/C catalyst, and the over potential of electrocatalytic hydrogen evolution is lower than that of the commercial Ir/C catalyst and that of the commercial Pt/C catalyst, which indicates that the IrMo/CNT prepared in the example 1 has the electrocatalytic hydrogen evolution and electrocatalytic oxygen evolution activities superior to that of the commercial catalyst in an acid environment and shows good catalytic efficiency of electrolyzed water;
b) the IrW/CNT prepared in example 2 has lower electrocatalytic oxygen evolution overpotential than commercial Ir/C catalyst and lower electrocatalytic hydrogen evolution overpotential than commercial Ir/C catalyst and commercial Pt/C catalyst, which indicates that the IrW/CNT prepared in example 2 has electrocatalytic hydrogen evolution and electrocatalytic oxygen evolution activity superior to that of commercial catalyst in an acidic environment and shows good electrolytic water catalysis efficiency;
c) IrMo prepared in example 30.5W0.5The electrocatalytic oxygen evolution overpotential of the/CNT is lower than that of the commercial Ir/C catalyst, and the electrocatalytic hydrogen evolution overpotential of the/CNT is lower than that of the commercial Ir/C catalyst and the commercial Ir/C catalystCommercial Pt/C catalyst Low, indicating IrMo prepared in example 30.5W0.5the/CNT has electrocatalytic hydrogen and oxygen evolution activities exceeding those of commercial catalysts in an acidic environment and shows good electrolytic water catalysis efficiency.
4) According to the electrochemical linear voltammetry test method, under the condition that the scanning speed is 10mV/s, the carbon-supported iridium molybdenum tungsten intermetallic compound and the commercial Ir/C catalyst of the examples 4 to 5 are subjected to N reaction by adopting an Autolab electrochemical workstation of Vanton, Switzerland2Carrying out electrochemical test in saturated KOH solution with the concentration of 1mol/L, and determining the activity of the solution to the electrocatalytic oxygen evolution reaction, wherein the test rotating speed of a rotating disc electrode is 1600r/min, and the load capacity of Ir in the catalyst on the electrode is 5g/cm2The obtained electrocatalytic oxygen evolution polarization curve is shown in fig. 5.
As can be seen from fig. 5:
a) the electrocatalytic oxygen evolution overpotential of the IrMo/CNT prepared in the example 4 is lower than that of the commercial Ir/C catalyst, which shows that the IrMo/CNT prepared in the example 4 has the electrocatalytic oxygen evolution activity superior to that of the commercial catalyst in an alkaline environment and shows good electrolytic water catalysis efficiency;
b) the electrocatalytic oxygen evolution overpotential of the IrMo/CNT prepared in example 5 is lower than that of the commercial Ir/C catalyst, which shows that the IrMo/CNT prepared in example 5 has electrocatalytic oxygen evolution activity superior to that of the commercial catalyst in an alkaline environment and shows good electrolytic water catalysis efficiency.
5) According to the electrochemical linear volt-ampere test method, under the condition that the scanning speed is 10mV/s, the carbon-supported iridium molybdenum tungsten intermetallic compounds, the commercial Ir/C catalysts and the commercial Pt/C catalysts of the examples 5 to 6 are subjected to N reaction by adopting an Autolab electrochemical workstation of Vantone Switzerland2Carrying out electrochemical test in saturated KOH solution with the concentration of 1mol/L, and determining the activity of the solution to the electrocatalytic hydrogen evolution reaction, wherein the test rotating speed of a rotating disc electrode is 1600r/min, and the load capacity of Ir in the catalyst on the electrode is 5g/cm2The obtained electrocatalytic hydrogen evolution polarization curve is shown in fig. 6.
As can be seen from fig. 6:
a) the electrocatalytic hydrogen evolution overpotential of the IrMo/CNT prepared in example 5 is lower than that of the commercial Ir/C catalyst and the commercial Pt/C catalyst, and the electrocatalytic hydrogen evolution overpotential is lower than that of the commercial Ir/C catalyst and the commercial Pt/C catalyst, which indicates that the IrMo/CNT prepared in example 5 has the electrocatalytic hydrogen evolution activity superior to that of the commercial catalyst in an alkaline environment and shows good electrolyzed water catalytic efficiency;
b) the over potential of electrocatalytic hydrogen evolution of the IrMo/CNT prepared in example 6 is lower than that of the commercial Ir/C catalyst and the commercial Pt/C catalyst, and the over potential of electrocatalytic hydrogen evolution is lower than that of the commercial Ir/C catalyst and the commercial Pt/C catalyst, which indicates that the IrMo/CNT prepared in example 6 has the electrocatalytic hydrogen evolution activity superior to that of the commercial catalyst in an alkaline environment and shows good catalytic efficiency of electrolyzed water.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A carbon-supported iridium molybdenum tungsten intermetallic compound is characterized in that: the carbon-supported iridium molybdenum tungsten intermetallic compound comprises a carbon support and a supported iridium molybdenum tungsten intermetallic compound; the chemical formula of the iridium molybdenum tungsten intermetallic compound is IrMo1-xWx，0≤x≤1。
2. The iridium molybdenum tungsten on carbon intermetallic compound according to claim 1, characterized in that: the carbon carrier is at least one of a commercial carbon carrier and a carbon nano tube.
3. The iridium molybdenum tungsten on carbon intermetallic compound according to claim 1 or 2, characterized in that: the iridium molybdenum tungsten intermetallic compound is at least one of iridium molybdenum intermetallic compound, iridium tungsten intermetallic compound and iridium molybdenum tungsten intermetallic compound.
4. The iridium molybdenum tungsten on carbon intermetallic compound according to claim 1 or 2, characterized in that: the load amount of the iridium molybdenum tungsten intermetallic compound in the carbon-supported iridium molybdenum tungsten intermetallic compound is 10-30%.
5. The iridium molybdenum tungsten on carbon intermetallic compound according to claim 4, characterized in that: the molar ratio of iridium element, molybdenum element or/and tungsten element in the iridium molybdenum tungsten intermetallic compound is 1: 0.3-1: 3.0.
6. The method for producing the iridium-molybdenum-tungsten-on-carbon intermetallic compound according to any one of claims 1 to 5, characterized by comprising the steps of: and uniformly mixing the iridium source, the molybdenum source or/and the tungsten source and the carbon carrier in a solvent system, removing the solvent, and then placing in a reducing atmosphere for heat treatment to obtain the carbon-supported iridium molybdenum tungsten intermetallic compound.
7. The method according to claim 6, wherein the iridium molybdenum tungsten intermetallic compound on carbon comprises: the iridium source is at least one of iridium trinitrate, iridium trichloride, iridium tetrachloride, chloroiridic acid and iridium acetate; the molybdenum source is at least one of ammonium paramolybdate, sodium paramolybdate, potassium paramolybdate, ammonium molybdate, sodium molybdate, potassium molybdate, molybdenum trichloride, molybdenum pentachloride and molybdenum hexachloride; the tungsten source is at least one of ammonium metatungstate, sodium metatungstate, potassium metatungstate, ammonium tungstate, sodium tungstate, potassium tungstate, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride and tungsten hexachloride.
8. The method for producing an iridium molybdenum tungsten intermetallic compound on carbon according to claim 6 or 7, characterized in that: the reducing atmosphere is N2-H2Mixed atmosphere, Ar-H2One of mixed atmospheres.
9. The method for producing an iridium molybdenum tungsten intermetallic compound on carbon according to claim 6 or 7, characterized in that: the specific operation of the heat treatment is as follows: heating from room temperature to 600-900 ℃ at the heating rate of 2-10 ℃/min, and then preserving heat for 1-12 h.
10. Use of the iridium molybdenum tungsten intermetallic compound supported on carbon according to any one of claims 1 to 5 in the preparation of an OER catalyst or an HER catalyst.
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| CN112760677A (en) * | 2020-12-28 | 2021-05-07 | 中国科学技术大学 | Iridium-tungsten alloy nano material, preparation method thereof and application of iridium-tungsten alloy nano material as acidic oxygen evolution reaction electrocatalyst |
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| US4202934A (en) * | 1978-07-03 | 1980-05-13 | United Technologies Corporation | Noble metal/vanadium alloy catalyst and method for making |
| CN103972519A (en) * | 2013-02-01 | 2014-08-06 | 福特全球技术公司 | Catalyst assembly including an intermetallic compound of iridium and tungsten |
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