Supported metal catalyst as well as synthesis method and application thereof

Abstract

The invention discloses a supported metal catalyst as well as a synthesis method and application thereof. The catalyst comprises a modified resin-based carbon carrier, elemental metal and a cerium-containing compound. The synthesis method of the catalyst comprises the following steps: 1) dispersing chloromethyl resin in a first solvent, adding a modifier nitrogen-containing organic compound under a first heating and stirring condition, reacting to obtain a solid, and drying the solid to obtain a modified intermediate; and 2) under a second heating and stirring condition, mixing the modified intermediate with a cerium precursor, an elemental metal precursor and a second solvent, reacting to obtain a solid, drying the solid, and roasting in an inert gas atmosphere to obtain the catalyst. The catalyst disclosed by the invention is applied to oxygen evolution reaction and shows good catalytic performance.

Description

Technical Field

[0001] This invention belongs to the field of catalysis technology, and specifically relates to a supported metal catalyst for the oxygen evolution reaction, its synthesis method, and its application. Background Technology

[0002] Hydrogen energy is a widely available, safe, efficient, and renewable green and low-carbon new energy source with high energy density and conversion efficiency, and has become a key pathway for global energy transition. Electrolysis of water to produce hydrogen is one of the important methods for achieving hydrogen production from renewable energy sources, and it has broad development prospects. To further develop low-cost hydrogen production processes, electrolysis catalysts are one of the most important components. Although precious metals such as palladium, platinum, ruthenium, and rhodium have shown good catalytic performance, their high price and low yield limit their large-scale application. Transition metals, with their low price and good performance, have become very promising electrocatalytic materials.

[0003] CN 116905018A reports a nickel-iron-cerium ternary metal catalyst and its preparation method, wherein the catalytic electrode is formed by depositing iron and cerium metal elements on the surface of nickel foam. CN117248219A reports a nickel-iron-cerium ternary catalyst, which is prepared by first activating a nickel substrate material in a hydrogen atmosphere at high temperature and then impregnating it in an iron and cerium precursor solution. CN116876027A reports a Ni3Fe@carbon nanotube / cerium oxide / foam metal electrolytic catalyst, which is obtained by calcining NiFeCe-LDH / foam metal with melamine. It is evident that the above methods are relatively cumbersome, the preparation process is complex, and the catalyst quality is difficult to control. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a supported metal catalyst, its synthesis method, and its applications. The catalyst of this invention exhibits excellent catalytic performance in the oxygen evolution reaction (OER).

[0005] The first aspect of the present invention provides a supported metal catalyst comprising a modified resin-based carbon support, a elemental metal, and a cerium-containing compound.

[0006] In this invention, the elemental metal is selected from one or more of nickel, iron, cobalt, and copper, more preferably one or more of nickel, iron, and copper. Preferably, the elemental metal is nickel and iron, wherein the mass ratio of nickel to iron is 0.3-10:1.

[0007] In this invention, the modified resin-based carbon support refers to a carbon support derived from the carbonization of chloromethyl resin.

[0008] In this invention, the mass ratio of the elemental metal to the modified resin-based carbon support is 0.01-10:100, preferably 0.03-10:100.

[0009] In this invention, the cerium-containing compound is cerium chloride. The molecular formula of cerium chloride is CeNCl.

[0010] In this invention, the mass ratio of the cerium-containing compound to the modified resin-based carbon support is 0.01-10:100, preferably 0.02-10:100.

[0011] In this invention, the total mass content of nitrogen in the catalyst is 1%-10%.

[0012] In this invention, the catalyst has an average pore size of 50-500 nm and a specific surface area of ​​5-50 m². 2 / g.

[0013] A second aspect of the present invention provides a method for synthesizing the above-mentioned catalyst, comprising:

[0014] 1) Disperse chloromethyl resin in a first solvent, add a nitrogen-containing organic modifier under first heating and stirring conditions, and dry the solid obtained after the reaction to obtain a modified intermediate;

[0015] 2) Under the second heating and stirring conditions, the modified intermediate, cerium precursor, elemental metal precursor, and second solvent are mixed. The solid obtained after the reaction is dried and then calcined in an inactive gas atmosphere to obtain the catalyst.

[0016] In the synthesis method of this invention, the chloromethyl resin is one or more of chloromethyl polystyrene, chloromethyl polyethylene, chloromethyl carboxylic acid resin and chloromethyl phenolic resin; preferably chloromethyl polystyrene.

[0017] In the synthesis method of this invention, the chloromethyl resin contains more than 1% chlorine by mass, preferably 10%-25%.

[0018] In the synthesis method of the present invention, the first solvent is one or more of toluene, methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, dichloromethane, chloroform, amide and ether, preferably N,N-dimethylformamide.

[0019] In the synthesis method of this invention, the mass ratio of the chloromethyl resin to the first solvent is 1:1 to 1:10.

[0020] In the synthesis method of the present invention, the nitrogen-containing organic compound is selected from one or more of piperazine, amine, pyridine, imidazole, quinoline, pyrrole, indole, and carbazole, preferably one or more of piperazine, imidazole, and pyridine.

[0021] In the synthesis method of the present invention, the mass ratio of the nitrogen-containing organic compound to the chloromethyl resin is 0.5-5.0, preferably 0.8-2.0.

[0022] In the synthesis method of the present invention, the conditions for the first heating and stirring include: a heating temperature of 50-150℃, preferably 70-90℃; a stirring rate of 50-1000 rpm, preferably 400-600 rpm; and a stirring time of 1-24h, preferably 10-14h.

[0023] In the synthesis method of the present invention, step 1) involves solid-liquid separation of the obtained reaction materials, and the obtained solid is washed and then dried.

[0024] In the synthesis method of this invention, the drying conditions in step 1) include a temperature of 70-150℃ and a time of 2-48h.

[0025] In the synthesis method of the present invention, the second solvent is water and / or alcohol, preferably one or more of water, methanol, ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, and pentanol, and more preferably one or more of water, ethylene glycol, and glycerol.

[0026] In the synthesis method of the present invention, the mass ratio of the modified intermediate to the second solvent is 1:1 to 1:10.

[0027] In the synthesis method of the present invention, the conditions for the second heating and stirring include: a heating temperature of 20-150℃, preferably 30-100℃; a stirring rate of 50-1000 rpm, preferably 400-600 rpm; and a stirring time of 1-24 h, preferably 2-6 h.

[0028] In the synthesis method of the present invention, the inactive gas is one or more of nitrogen, carbon dioxide, and argon, preferably nitrogen and / or argon; the calcination temperature is 300-1200℃, and the calcination time is 1-48h, preferably the calcination temperature is 400-900℃, and the calcination time is 2-36h.

[0029] In the synthesis method of this invention, the cerium precursor is selected from cerium nitrate and / or cerium chloride.

[0030] In the synthesis method of this invention, the elemental metal precursor is selected from metal nitrates and / or metal chlorides.

[0031] In the synthesis method of this invention, the cerium precursor and the elemental metal precursor can be added to the system in solid form or in solution form.

[0032] In the synthesis method of the present invention, the molar ratio of the cerium precursor to the elemental metal precursor is 0.01-10, preferably 0.05-8.

[0033] In the synthesis method of the present invention, the mass ratio of the elemental metal precursor to the modified intermediate is 0.001-0.5, preferably 0.005-0.2.

[0034] In the synthesis method of the present invention, step 2) involves solid-liquid separation of the obtained reaction materials, and the obtained solid is washed and then dried.

[0035] In the synthesis method of this invention, the drying conditions in step 2) include a temperature of 70-150℃ and a time of 2-48h.

[0036] A third aspect of the present invention provides the application of the above-described catalyst in the oxygen evolution reaction.

[0037] In this invention, the application refers to the use of the catalyst in the anodic oxygen evolution reaction of water electrolysis.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The catalyst of this invention uses a modified resin-based carbon support and also includes elemental metal and cerium compound, namely cerium chloride. The catalyst has a well-organized three-dimensional network pore structure with good mass transfer channels, exhibiting good catalytic performance in the reaction. At the same time, it has good mechanical strength and can adapt to harsh industrial environments, and is expected to have good applications in the field of electrochemistry. Attached Figure Description

[0040] Figure 1 The XRD patterns are those of catalyst C1 obtained in Example 1, catalyst C2 obtained in Example 2, and standard CeNCl.

[0041] Figure 2 Here is a SEM image of catalyst C1 obtained in Example 1;

[0042] Figure 3 The image shows the XRD pattern of catalyst S2 obtained in Comparative Example 2. Detailed Implementation

[0043] The technical solution of the present invention will be further described below through embodiments, but the scope of protection of the present invention is not limited by the embodiments.

[0044] In this specification, including the following examples and comparative examples, XRD was performed on a Bruker D8 AdvanceSS with CuKα radiation, 40 kV, 300 mA, a scan rate of 2° / min, and a 2θ scan range of 5–70°.

[0045] In this specification, including the examples and comparative examples below, the catalysts were SEMed using a scanning electron microscope (SEM, Merlin) from ZEISS GmbH, Germany, at a scanning voltage of 1 kV.

[0046] In this invention, the mass content of nitrogen, sulfur, and phosphorus in the sample was measured using a Therm2000 elemental analyzer, and the testing method was elemental analysis.

[0047] In this invention, the average pore size and specific surface area of ​​the sample are measured by the nitrogen physical adsorption-desorption method (BET method): the nitrogen physical adsorption-desorption isotherm of the sample is measured using a physical adsorption instrument (Micromeretic ASAP2020M physical adsorption instrument), and then calculated using the BET equation and t-plot equation.

[0048] Example 1

[0049] In a 500ml three-necked flask, 50g of chloromethylstyrene resin (chlorine content 17wt%) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 70℃. 50g of imidazole was then added, and the reaction was allowed to proceed for 12 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain the modified intermediate. Then, in another 500ml three-necked flask, 10g of the modified intermediate, 0.327g of nickel nitrate, 0.454g of ferric nitrate, and 0.4882g of cerium nitrate were added and diluted with water to a 40g solution. The mixture was stirred at 600 rpm for 2 hours at 50℃, dried in an oven at 100℃ for 24 hours, and then calcined in a muffle furnace at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst C1. The XRD pattern of catalyst C1 is shown below. Figure 1 As shown, its characteristic peaks are consistent with those of cerium chloride.

[0050] Catalyst C1 contains 2.0% iron, 2.1% nickel, and 4.5% cerium chloride (NCH), with the remainder being a modified resin-based carbon support. Catalyst C1 has a total nitrogen content of 3.7% by mass, an average pore size of 200 nm, and a specific surface area of ​​20.1 m². 2 / g.

[0051] Example 2

[0052] In a 500ml three-necked flask, 50g of chloromethylstyrene resin (chlorine content 17wt%) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 70℃. 50g of imidazole was then added, and the reaction was allowed to proceed for 12 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain the modified intermediate. Then, in another 500ml three-necked flask, 10g of the modified intermediate, 0.327g of nickel nitrate, 0.454g of ferric nitrate, and 0.9764g of cerium nitrate were added and diluted with water to a 40g solution. The mixture was stirred at 600 rpm for 2 hours at 50℃, dried in an oven at 100℃ for 24 hours, and then calcined in a muffle furnace at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst C2. The XRD pattern of sample C2 is similar to... Figure 1 .

[0053] Catalyst C2 contains 1.8% iron, 1.9% nickel, and 9.1% cerium chloride (NCH), with the remainder being a modified resin-based carbon support. Catalyst C2 has a total nitrogen content of 3.9% by mass, an average pore size of 300 nm, and a specific surface area of ​​12.4 m². 2 / g.

[0054] Example 3

[0055] In a 500ml three-necked flask, 50g of chloromethylstyrene resin (chlorine content 17wt%) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 70℃. 50g of imidazole was added, and the reaction was allowed to proceed for 12 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain the modified intermediate. Then, in another 500ml three-necked flask, 10g of the modified intermediate, 0.327g of nickel nitrate, 0.227g of ferric nitrate, and 0.4882g of cerium nitrate were added and diluted with water to a 40g solution. The mixture was stirred at 600 rpm for 2 hours at 50℃, dried in an oven at 100℃ for 24 hours, and then calcined in a muffle furnace at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst C3. The XRD pattern of sample C3 is similar to... Figure 1 .

[0056] Catalyst C3 contains 1% iron, 2.0% nickel, and 4.9% cerium chloride (NCH), with the remainder being a modified resin-based carbon support. Catalyst C3 has a total nitrogen content of 3.3% by mass, an average pore size of 100 nm, and a specific surface area of ​​32.4 m². 2 / g.

[0057] Example 4

[0058] In a 500ml three-necked flask, 50g of chloromethylstyrene resin (chlorine content 17wt%) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 70℃. 50g of imidazole was then added, and the reaction was allowed to proceed for 12 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain the modified intermediate. Then, in another 500ml three-necked flask, 10g of the modified intermediate, 0.327g of nickel nitrate, 0.227g of ferric nitrate, and 0.9764g of cerium nitrate were added and diluted with water to a 40g solution. The mixture was stirred at 600 rpm for 2 hours at 50℃, dried in an oven at 100℃ for 24 hours, and then calcined in a muffle furnace at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst C4. The XRD pattern of sample C4 is similar to... Figure 1 .

[0059] Catalyst C4 contains 1% iron, 3.9% nickel, and 8.8% cerium chloride (NCH), with the remainder being a modified resin-based carbon support. Catalyst C4 has a total nitrogen content of 3.1% by mass, an average pore size of 50 nm, and a specific surface area of ​​43.1 m². 2 / g.

[0060] Example 5

[0061] In a 500ml three-necked flask, 50g of chloromethylstyrene resin (chlorine content 17wt%) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 70℃. 50g of imidazole was then added, and the reaction was allowed to proceed for 12 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain the modified intermediate. Then, in another 500ml three-necked flask, 10g of the modified intermediate, 0.154g of nickel nitrate, 0.454g of ferric nitrate, and 0.4882g of cerium nitrate were added and diluted with water to a 40g solution. The mixture was stirred at 600 rpm for 2 hours at 50℃, dried in an oven at 100℃ for 24 hours, and then calcined in a muffle furnace at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst C5. The XRD pattern of sample C5 is similar to... Figure 1 .

[0062] Catalyst C5 contains 1.9% iron, 1.0% nickel, and 4.8% cerium chloride (NCH), with the remainder being a modified resin-based carbon support. Catalyst C5 has a total nitrogen content of 3.1% by mass, an average pore size of 200 nm, and a specific surface area of ​​19.8 m². 2 / g.

[0063] Example 6

[0064] In a 500ml three-necked flask, 50g of chloromethylstyrene resin (chlorine content 17wt%) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 70℃. 50g of imidazole was then added, and the reaction was allowed to proceed for 12 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain the modified intermediate. Then, in another 500ml three-necked flask, 10g of the modified intermediate, 0.985g of nickel nitrate, 0.454g of ferric nitrate, and 0.4882g of cerium nitrate were added and diluted with water to a 40g solution. The mixture was stirred at 600 rpm for 2 hours at 50℃, dried in an oven at 100℃ for 24 hours, and then calcined in a muffle furnace at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst C6. The XRD pattern of sample C6 is similar to... Figure 1 .

[0065] Catalyst C6 contains 1.8% iron, 5.8% nickel, and 4.8% cerium chloride (NCH), with the remainder being a modified resin-based carbon support. Catalyst C6 has a total nitrogen content of 2.9% by mass, an average pore size of 100 nm, and a specific surface area of ​​29.1 m². 2 / g.

[0066] Example 7

[0067] In a 500ml three-necked flask, 50g of chloromethylstyrene resin (chlorine content 17wt%) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 70℃. 50g of imidazole was then added, and the reaction was allowed to proceed for 12 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain the modified intermediate. Then, in another 500ml three-necked flask, 10g of the modified intermediate, 0.327g of nickel nitrate, 0.454g of ferric nitrate, and 0.1221g of cerium nitrate were added and diluted with water to a 40g solution. The mixture was stirred at 600 rpm for 2 hours at 50℃, dried in an oven at 100℃ for 24 hours, and then calcined in a muffle furnace at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst C7. The XRD pattern of sample C7 is similar to... Figure 1 .

[0068] Catalyst C7 contains 2.0% iron, 2.1% nickel, and 1.2% cerium chloride (NCH), with the remainder being a modified resin-based carbon support. Catalyst C7 also contains 2.4% nitrogen by mass, has an average pore size of 200 nm, and a specific surface area of ​​17.1 m². 2 / g.

[0069] Comparative Example 1

[0070] In a 500ml three-necked flask, 50g of chloromethylstyrene resin (chlorine content 17wt%) was added, followed by 200ml of N,N-dimethylformamide. The mixture was stirred at 500 rpm and heated to 70℃. 50g of imidazole was then added, and the reaction was carried out for 12 hours. After cooling, the mixture was separated, washed with deionized water, and dried overnight at 100℃ to obtain the modified intermediate. Then, in another 500ml three-necked flask, 10g of the modified intermediate, 0.327g of nickel nitrate, and 0.454g of ferric nitrate were added and diluted with water to prepare a 40g solution. The mixture was stirred at 600 rpm for 2 hours at 50℃, dried in an oven at 100℃ for 24 hours, and then calcined in a muffle furnace at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst S1.

[0071] Catalyst S1 contains 2.1% iron, 2.2% nickel, and the remainder is a modified resin-based carbon support. Catalyst S1 also contains 2.0% nitrogen by mass, has an average pore size of 200 nm, and a specific surface area of ​​20.1 m². 2 / g.

[0072] Comparative Example 2

[0073] In a 500ml three-necked flask, 10g of chloromethylstyrene resin (chlorine content 17wt%), 0.327g of nickel nitrate, 0.454g of ferric nitrate, and 0.4882g of cerium nitrate were added, and water was added to prepare a 40g solution. The solution was stirred at 600 rpm for 2 hours at 50℃, then dried in an oven at 100℃ for 24 hours. Finally, it was transferred to a muffle furnace and calcined at 700℃ for 4 hours under a nitrogen atmosphere to obtain catalyst S2. The XRD pattern of catalyst S2 is shown below. Figure 3 As shown, there are no characteristic peaks of cerium chloride, only characteristic peaks of cerium dioxide.

[0074] Catalyst S2 contains 2.1% iron, 2.2% nickel, 4.5% cerium dioxide, and 0% nitrogen by mass. It has an average pore size of 200 nm and a specific surface area of ​​20.1 m². 2 / g.

[0075] Example 8

[0076] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2The corresponding electric potential at that time is the voltage condition. When catalyst C1 is used as the catalyst, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 227mV.

[0077] Example 9

[0078] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2 The corresponding electric potential at that time is the voltage condition. When catalyst C2 is used as the catalyst, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 215mV.

[0079] Example 10

[0080] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2 The corresponding electric potential at that time is the voltage condition. When catalyst C3 is used, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 219mV.

[0081] Example 11

[0082] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2 The corresponding electric potential at that time is the voltage condition. When catalyst C4 is used, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 202mV.

[0083] Example 12

[0084] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2 The corresponding electric potential at that time is the voltage condition. When catalyst C5 is used, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 233mV.

[0085] Example 13

[0086] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2 The corresponding electric potential at that time is the voltage condition. When catalyst C6 is used, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 207mV.

[0087] Example 14

[0088] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2 The corresponding electric potential at that time is the voltage condition. When catalyst C7 is used, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 235mV.

[0089] Comparative Example 3

[0090] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2The corresponding electric potential at that time is the voltage condition. When catalyst S1 is used as the catalyst, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 279mV.

[0091] Comparative Example 4

[0092] Electrocatalytic reactions were performed using a three-electrode system. A glassy carbon electrode coated with a catalyst layer was used as the working electrode, an Hg / HgO electrode as the reference electrode, and a carbon rod as the counter electrode. A 1M KOH solution was used as the electrolyte, and a CHI 660E electrochemical workstation was used as the power source. Activity was evaluated using linear sweep voltammetry at a scan rate of 5 mV / s. Stability was tested using a galvanostatic method at a current density of 10 mA / cm². 2 The corresponding electric potential at that time is the voltage condition. When catalyst S2 is used as the catalyst, the catalyst reaches 10 mA·cm⁻¹. -2 The corresponding overpotential is 377mV.

Claims

1. A supported metal catalyst comprising a modified resin-based carbon support, a elemental metal, and a cerium-containing compound.

2. The catalyst according to claim 1, characterized in that, The elemental metal is at least one of nickel, iron, cobalt, and copper, preferably nickel and iron, wherein the mass ratio of nickel to iron is 0.3-10:

1.

3. The catalyst of claim 1, wherein The mass ratio of the elemental metal to the modified resin-based carbon support is 0.01-10:

100.

4. The catalyst of claim 1, wherein The cerium-containing compound is cerium chloride.

5. The catalyst according to claim 1 or 4, characterized in that, The mass ratio of the cerium-containing compound to the modified resin-based carbon support is 0.01-10:100; And / or, the total mass content of nitrogen in the catalyst is 1-10%; and / or the average pore diameter of the catalyst is 50-500 nm and the specific surface area is 5-50 m 2 / g.

6. A method for synthesizing the catalyst according to any one of claims 1-5, comprising: 1) Disperse chloromethyl resin in a first solvent, add a nitrogen-containing organic modifier under first heating and stirring conditions, and dry the solid obtained after the reaction to obtain a modified intermediate; 2) Under the second heating and stirring conditions, the modified intermediate, the added cerium precursor, the elemental metal precursor, and the second solvent are mixed. The solid obtained after the reaction is dried and then calcined in an inactive gas atmosphere to obtain the catalyst.

7. The method of claim 6, wherein, In step 1), the chloromethyl resin is one or more of chloromethyl polystyrene, chloromethyl polyethylene, chloromethyl carboxylic acid resin and chloromethyl phenolic resin, preferably chloromethyl polystyrene; And / or, in step 1), the chloromethyl resin contains more than 1% chlorine by mass, preferably 10%-25%.

8. The method of claim 6, wherein, In step 1), the first solvent is one or more of toluene, methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, dichloromethane, chloroform, amide, and ether; And / or, in step 1), the mass ratio of the chloromethyl resin to the first solvent is 1:1 to 1:10; And / or, in step 1), the nitrogen-containing organic compound is selected from one or more of piperazine, amine, pyridine, imidazole, quinoline, pyrrole, indole, and carbazole; And / or, in step 1), the mass ratio of the nitrogen-containing organic compound to the chloromethyl resin is 0.5-5.0; And / or, in step 1), the conditions for the first heating and stirring include: a heating temperature of 50-150°C; a stirring rate of 50-1000 rpm; and a stirring time of 1-24 h.

9. The method according to any of claims 6-8, characterized by, In step 2), the second solvent is water and / or alcohol, preferably one or more of water, methanol, ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, and pentanol; And / or, in step 2), the mass ratio of the modified intermediate to the second solvent is 1:1 to 1:10; And / or, in step 2), the conditions for the second heating and stirring include: a heating temperature of 20-150°C; a stirring rate of 50-1000 rpm; and a stirring time of 1-24 h. And / or, in step 2), the inactive gas is one or more of nitrogen, carbon dioxide, and argon; the calcination temperature is 300-1200℃, and the calcination time is 1-48h; And / or, in step 2), the cerium precursor is selected from cerium nitrate and / or cerium chloride; the elemental metal precursor is selected from metal nitrates and / or metal chlorides; And / or, in step 2), the molar ratio of the cerium precursor to the elemental metal precursor is 0.01-10, preferably 0.05-8; And / or, in step 2), the mass ratio of the elemental metal precursor to the modified intermediate is 0.001-0.5, preferably 0.005-0.

2.

10. The catalytic application of the catalyst according to any one of claims 1-5 or the catalyst synthesized by any one of claims 6-9 in the anodic oxygen evolution reaction of water electrolysis.

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