CN115572988A - Preparation method of CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis - Google Patents

Preparation method of CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis Download PDF

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CN115572988A
CN115572988A CN202211287418.6A CN202211287418A CN115572988A CN 115572988 A CN115572988 A CN 115572988A CN 202211287418 A CN202211287418 A CN 202211287418A CN 115572988 A CN115572988 A CN 115572988A
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fecos
comop
composite catalyst
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蔡晓东
宋群
焦丹花
于化童
陆文娟
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Guizhou Minzu University
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a preparation method of a CoMoP/FeCoS/NF composite catalyst for producing hydrogen by full-pH electrolysis, and belongs to the technical field of new energy materials. The invention aims to solve the problems that the existing noble metal catalyst is high in cost, but the non-noble metal catalyst is only suitable for an alkaline electrolytic cell and has limited reaction activity under the condition of an acidic or neutral medium. The method comprises the following steps: 1. preparing FeCoS/NF precursor; 2. and (3) preparing a CoMoP/FeCoS/NF composite catalyst. The method is used for preparing the CoMoP/FeCoS/NF composite catalyst for the full-pH electrolysis of the water hydrogen.

Description

Preparation method of CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis
Technical Field
The invention belongs to the technical field of new energy materials.
Background
The excessive consumption of non-renewable energy and the consequent environmental pollution problems compel us to find and develop renewable clean energy, of which hydrogen energy is considered to be one of the most promising clean energy of the 21 st century. The hydrogen production (HER) by water electrolysis is considered to be a clean production technology which is environment-friendly, has high selectivity and does not produce secondary pollution. However, since the water decomposition process belongs to a non-spontaneous reaction from the chemical thermodynamic perspective and the reaction rate is slow, it needs to overcome a certain activation potential with the aid of a catalyst, and thus the development of a high-efficiency water electrolysis catalyst is urgent. At present, the high-efficiency electrocatalyst is mainly made of rare and expensive noble metal-based materials, which is not beneficial to the large-scale popularization of hydrogen production by water electrolysis in industry. Most of the reported non-noble metal catalysts are only suitable for alkaline electrolytic cells, and the reaction activity under the condition of acidic or neutral medium is very limited, but in the practical application process, the water electrolysis hydrogen production technology puts diversified requirements on the pH of the electrolyte solution. Therefore, the development of a full-pH hydrogen evolution electrocatalyst which is efficient, stable, low in overpotential and low in price is imperative.
Disclosure of Invention
The invention provides a preparation method of a CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis, aiming at solving the problems that the existing noble metal catalyst is high in cost, but a non-noble metal catalyst is only suitable for an alkaline electrolytic cell and has limited reaction activity under the condition of an acidic or neutral medium.
A preparation method of a CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis is carried out according to the following steps:
1. preparing FeCoS/NF precursor:
uniformly dispersing a cobalt source, an iron source and a sulfur source in ethylene glycol, then carrying out ultrasonic treatment to obtain a uniform and stable mixed solution A, soaking foamed nickel in the uniform and stable mixed solution A, reacting for 8-12 h at the temperature of 150-240 ℃, and finally washing and drying to obtain a FeCoS/NF precursor;
2. preparation of a CoMoP/FeCoS/NF composite catalyst:
uniformly dispersing cobalt nitrate hexahydrate, sodium hypophosphite, sodium molybdate and trisodium citrate in deionized water, stirring to obtain a uniform and stable mixed solution B, taking the uniform and stable mixed solution B as an electrolyte, taking a FeCoS/NF precursor as a working electrode, a carbon rod as a counter electrode and Ag/AgCl as a reference electrode, and depositing for 60-150 s under a constant voltage condition to obtain the CoMoP/FeCoS/NF composite catalyst.
The beneficial effects of the invention are: the invention discloses a preparation method of a CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis. The catalyst has a current density of 10mA/cm 2 Under the condition of (1), the overpotentials tested in alkaline, neutral and acidic environments are respectively 104mV, 171mV and 27mV, the electrolytic water performance with excellent full pH is shown, and the stability of not less than 20h can be maintained. The CoMoP/FeCoS/NF composite catalyst prepared by the invention has the advantages of simple preparation method, low cost, catalytic performance comparable to that of a commercial noble metal catalyst, and good application prospect in the aspect of hydrogen production by water electrolysis.
The invention is used for a preparation method of a CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD), 1 is a CoMoP/FeCoS/NF composite catalyst prepared in example one, 2 is a FeCoS/NF catalyst prepared in comparative experiment one, and 3 is a NF catalyst prepared in comparative experiment three;
FIG. 2 is X-ray photoelectron diffraction (XPS) analysis of a CoMoP/FeCoS/NF composite catalyst prepared in example one;
FIG. 3 is a Scanning Electron Micrograph (SEM), (a) showing FeCoS/NF catalyst prepared in comparative experiment one and (b) showing CoMoP/FeCoS/NF composite catalyst prepared in example one;
FIG. 4 is a Transmission Electron Micrograph (TEM) of a CoMoP/FeCoS/NF composite catalyst prepared in example one, wherein (a) is a scale of 500nm, (b) is a partial magnified view of (a), (c) is a scale of 5nm, and (d) is a partial magnified view of (c);
FIG. 5 is a graph showing the HER linear sweep voltammetric polarization curve (LSV) and stability test of the catalyst under alkaline conditions, (a) is the HER linear sweep voltammetric polarization curve (LSV), 1 is the CoMoP/FeCoS/NF composite catalyst prepared in example one, 2 is the FeCoS/NF catalyst prepared in comparative experiment one, 3 is the CoMoP/NF catalyst prepared in comparative experiment two, 4 is the NF catalyst prepared in comparative experiment three, and (b) is the i-t curve obtained by testing the CoMoP/FeCoS/NF composite catalyst prepared in example one at a potential of 0.101V relative to RHE;
FIG. 6 is a graph showing the HER linear sweep voltammetric polarization curve (LSV) and stability test of the catalyst under neutral conditions, (a) is the HER linear sweep voltammetric polarization curve (LSV), 1 is the CoMoP/FeCoS/NF composite catalyst prepared in the first example, 2 is the FeCoS/NF catalyst prepared in the first comparative experiment, 3 is the CoMoP/NF catalyst prepared in the second comparative experiment, 4 is the NF catalyst prepared in the third comparative experiment, and (b) is the i-t curve obtained by testing the CoMoP/FeCoS/NF composite catalyst prepared in the first example at a potential of 0.171V relative to RHE;
fig. 7 is a graph showing HER linear sweep voltammetric polarization curve (LSV) and stability test of the catalyst under acidic conditions, (a) is a graph showing HER linear sweep voltammetric polarization curve (LSV), 1 is a coop/FeCoS/NF composite catalyst prepared in example one, 2 is a FeCoS/NF catalyst prepared in comparative experiment one, 3 is a coop/NF catalyst prepared in comparative experiment two, 4 is a NF catalyst prepared in comparative experiment three, and (b) is an i-t curve obtained by testing the coop/FeCoS/NF composite catalyst prepared in example one at a potential of 0.027V with respect to RHE.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis in the embodiment is carried out according to the following steps:
1. preparing FeCoS/NF precursor:
uniformly dispersing a cobalt source, an iron source and a sulfur source in ethylene glycol, then carrying out ultrasonic treatment to obtain a uniform and stable mixed solution A, soaking foamed nickel in the uniform and stable mixed solution A, reacting for 8-12 h at the temperature of 150-240 ℃, and finally washing and drying to obtain a FeCoS/NF precursor;
2. preparation of a CoMoP/FeCoS/NF composite catalyst:
uniformly dispersing cobalt nitrate hexahydrate, sodium hypophosphite, sodium molybdate and trisodium citrate in deionized water, stirring to obtain a uniform and stable mixed solution B, taking the uniform and stable mixed solution B as an electrolyte, taking a FeCoS/NF precursor as a working electrode, a carbon rod as a counter electrode and Ag/AgCl as a reference electrode, and depositing for 60-150 s under a constant voltage condition to obtain the CoMoP/FeCoS/NF composite catalyst.
In the embodiment, a cobalt source, an iron source, a sulfur source and ethylene glycol are used as raw materials, foam nickel is used as a conductive substrate, and a FeCoS/NF precursor is prepared by adopting a solvothermal method; and directly taking the FeCoS/NF precursor as a working electrode to prepare the CoMoP/FeCoS/NF composite catalyst by adopting an electrodeposition method.
The beneficial effects of the embodiment are as follows:
the embodiment discloses a preparation method of a CoMoP/FeCoS/NF composite catalyst for producing hydrogen by full-pH electrolysis. The catalyst has a current density of 10mA/cm 2 Under the condition of (1), the overpotentials tested in alkaline, neutral and acidic environments are respectively 104mV, 171mV and 27mV, the electrolytic water performance with excellent full pH is shown, and the stability of not less than 20h can be maintained. The CoMoP/FeCoS/NF composite catalyst prepared by the embodiment has the advantages of simple preparation method, low cost, catalytic performance comparable to that of a commercial noble metal catalyst, and good application prospect in the aspect of hydrogen production by water electrolysis.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the cobalt source in the step one is cobalt chloride hexahydrate; the iron source in the step one is ferrous sulfate heptahydrate; the sulfur source in the step one is thiourea. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the molar ratio of the cobalt source to the iron source in the first step is 1 (0.5-2); the molar ratio of the cobalt source to the sulfur source in the first step is 1 (1-3); the volume ratio of the mole of the cobalt source to the volume of the ethylene glycol in the step one is 1mmol (20-50) mL. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the ultrasonic treatment in the step one is ultrasonic treatment for 0.5 to 2 hours under the condition that the power is 200 to 500W. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the foam nickel in the step one is pretreated foam nickel; the pretreatment is specifically carried out according to the following steps: (1) ultrasonic cleaning is carried out by hydrochloric acid with the concentration of 2 mol/L-4 mol/L, acetone, ethanol and ultrapure water in sequence; (2) repeating the steps (1)2-4 times, and finally drying for 6-10 h at the temperature of 50-60 ℃. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the washing and drying in the step one are specifically washing with deionized water, and then drying for 8-12 h at the temperature of 50-60 ℃. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the purity of the foamed nickel in the step one is 99.99%, the thickness is 1 mm-2 mm, and the pore diameter is 100 PPI-120 PPI. The others are the same as in the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the mass ratio of the cobalt nitrate hexahydrate to the sodium hypophosphite in the step two is 1 (3-4); the mass ratio of the cobalt nitrate hexahydrate to the sodium molybdate in the second step is 1 (0.5-1.5); the mass ratio of the cobalt nitrate hexahydrate to the trisodium citrate in the second step is 1 (0.5-1); the volume ratio of the mass of the cobalt nitrate hexahydrate to the deionized water in the step two is 1g (700-1000) mL. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the stirring in the second step is specifically stirring for 0.5 to 1.5 hours at a rotating speed of 200 to 500 r/min. The others are the same as in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and in the second step, the deposition is carried out for 60 to 150 seconds under the condition that the constant voltage is-0.5 to-3V. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method of a CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis is carried out according to the following steps:
1. preparing FeCoS/NF precursor:
uniformly dispersing 1mmol of cobalt source, 1mmol of iron source and 2mmol of sulfur source in 30mL of ethylene glycol, then carrying out ultrasonic treatment for 1h under the condition that the power is 300W to obtain a uniform and stable mixed solution A, vertically soaking foamed nickel in the uniform and stable mixed solution A, reacting for 12h under the condition that the temperature is 200 ℃, and finally washing and drying to obtain a FeCoS/NF precursor;
2. preparation of a CoMoP/FeCoS/NF composite catalyst:
uniformly dispersing 58mg of cobalt nitrate hexahydrate, 200mg of sodium hypophosphite, 62mg of sodium molybdate and 50mg of trisodium citrate in 50mL of deionized water, stirring for 1h at the rotating speed of 300r/min to obtain a uniform and stable mixed solution B, depositing for 90s under the condition of constant voltage of-1.0V by taking the uniform and stable mixed solution B as an electrolyte, a FeCoS/NF precursor as a working electrode, a carbon rod as a counter electrode and Ag/AgCl as a reference electrode to obtain the CoMoP/FeCoS/NF composite catalyst.
The cobalt source in the first step is cobalt chloride hexahydrate; the iron source in the step one is ferrous sulfate heptahydrate; the sulfur source in the step one is thiourea.
The foam nickel in the step one is pretreated foam nickel; the pretreatment is specifically carried out according to the following steps: (1) sequentially carrying out ultrasonic cleaning by using hydrochloric acid with the concentration of 3mol/L, acetone, ethanol and ultrapure water; (2) the procedure was repeated (1)2 times, finally dried at 50 ℃ for 6h.
The purity of the foamed nickel in the step one is 99.99%, the pore size is 110PPI, and the size is 2cm multiplied by 4cm multiplied by 1.5mm.
The washing and drying in the step one are specifically washing with deionized water, and then drying for 8 hours at the temperature of 50 ℃.
Comparison experiment one: the comparative experiment differs from the first example in that: and step two is eliminated, and FeCoS/NF precursor is used as FeCoS/NF catalyst. The rest is the same as the first embodiment.
Comparative experiment two: the difference between this comparative experiment and the first example is that: and (4) eliminating the step one, and depositing by taking the pretreated foamed nickel as a working electrode to obtain the CoMoP/NF composite catalyst. The rest is the same as the first embodiment.
A third comparative experiment: the comparative experiment differs from the first example in that: and (3) eliminating the first step and the second step, and taking the pretreated foamed nickel as an NF catalyst. The rest is the same as the first embodiment.
FIG. 1 is an X-ray diffraction pattern (XRD), 1 is a CoMoP/FeCoS/NF composite catalyst prepared in example one, 2 is a FeCoS/NF catalyst prepared in comparative experiment one, and 3 is a NF catalyst prepared in comparative experiment three. As can be seen from the figure, the characteristic peaks at 45.0 °, 52.2 ° and 76.7 ° correspond to the (111), (200) and (220) crystal planes of NF (JDPDSNo.04-0850), respectively; the characteristic peaks at 31.6 °, 38.3 °, 47.4 °, 50.5 ° and 55.6 ° correspond to Co 3 S 4 (JDPDSNo.74-0138) crystal planes (311), (400), (422), (511) and (440); characteristic peaks at 29.9 °, 47.8 ° and 73.66 ° correspond to Fe, respectively 3 S 4 (JDPDSNo.23-1122) crystal planes (311), (511) and (731). These results demonstrate the successful preparation of FeCoS/NF composites. Diffraction peaks of related substances of Co, mo and P elements are not detected, which is caused by that the content of a CoMoP sample deposited on the surface of FeCoS/NF by adopting an electrodeposition method is very small and does not reach the detection limit.
FIG. 2 is X-ray photoelectron diffraction (XPS) analysis of a CoMoP/FeCoS/NF composite catalyst prepared in example one; the existence of Co, mo, P, fe, S and Ni elements can be obviously observed from the graph, and the successful preparation of the CoMoP/FeCoS/NF composite catalyst is proved.
FIG. 3 is a Scanning Electron Micrograph (SEM), (a) showing FeCoS/NF catalyst prepared in comparative experiment one and (b) showing CoMoP/FeCoS/NF composite catalyst prepared in example one. As can be seen from the graph (a), feCoS nanoparticles are closely attached to the surface of the three-dimensional foam nickel, after Co-Mo-P is electrodeposited on the surface of the three-dimensional foam nickel, the morphology of the CoMoP/FeCoS/NF composite catalyst is significantly changed, and the three-dimensional nanosheet cluster structure and the large specific surface area can effectively buffer the interaction between gas and the solid surface and promote the discharge of the gas, and can also effectively increase the reactive sites, promote the sufficient contact between the catalyst and the electrolyte, and accelerate the electron transfer rate. This indicates that the CoMoP/FeCoS/NF composite catalyst has good activity of producing hydrogen by electrolyzing water.
FIG. 4 is a Transmission Electron Micrograph (TEM) of the CoMoP/FeCoS/NF composite catalyst prepared in example one, (a) is a scale 500nm, (b) is a partial magnified view of (a), (c) is a scale 5nm, and (d) is a partial magnified view of (c). The core-shell structure of the composite material can be clearly seen from the graphs (a) and (b), a CoMoP shell layer is uniformly coated on the surface of FeCoS nano-particles, and the thickness of the CoMoP shell layer is about 130nm; furthermore, from graph (c), it can be observed that the heterostructure composed of FeCoS and CoMoP, which generates the electron coupling effect, has important influence on accelerating electron migration and enriching the electron migration path. In addition, the graph (d) shows the correspondence to Co 3 S 4 (400) Crystal face, fe 3 S 4 (400) The interplanar spacings of the crystallographic planes and of the CoMoP (020) crystallographic plane were 0.24nm, 0.28nm and 0.18nm, respectively. These results correspond to XRD, XPS and SEM one-to-one, and the accuracy of the characterization results is verified.
And (3) electrochemical performance testing: the operation was carried out in a three-electrode system using an electrochemical workstation (CHI 760E). Using the catalysts prepared in the examples and comparative experiments one to three as working electrodes, carbon rods as counter electrodes, and silver/silver chloride electrodes (Ag/AgCl) as reference electrodes, 0.5mol/L of H was used 2 SO 4 1.0mol/L PBS (pH = 7) and 1mol/L KOH solution as electrolytes under different pH environments.
Alkaline condition hydrogen evolution test: FIG. 5 is a HER Linear sweep voltammetry polarization curve (LSV) and stability test chart of the catalyst under alkaline conditions, (a) is a HER Linear sweep voltammetry polarization curve (LSV), and 1 is prepared in example oneThe catalyst is a CoMoP/FeCoS/NF composite catalyst, 2 is a FeCoS/NF catalyst prepared in the first comparative experiment, 3 is a CoMoP/NF catalyst prepared in the second comparative experiment, 4 is a NF catalyst prepared in the third comparative experiment, and (b) is an i-t curve obtained by testing the CoMoP/FeCoS/NF composite catalyst prepared in the first example at a potential of 0.101V relative to RHE. It can be observed from graph (a) that the overpotential of the CoMoP/FeCoS/NF composite catalyst is minimal at the same current density, which indicates that the CoMoP/FeCoS/NF composite catalyst has better HER performance under alkaline conditions, which can be attributed to the synergy between morphology, composition and dissimilar metal interface effect of the composite material. Specifically, at 10mA/cm 2 The overpotential required for the CoMoP/FeCoS/NF composite catalyst prepared in the example is 104mV, which is the minimum among all catalysts prepared, i.e. the optimal HER reactivity is achieved. As shown in the figure (b), the catalyst can stably maintain high activity for more than 24h without obvious attenuation, which proves the excellent chemical stability of the CoMoP/FeCoS/NF composite catalyst under alkaline conditions. This is attributable to the interaction between the sulfide and the phosphide, so that the bonding ability between chemical bonds is effectively enhanced, thereby promoting the chemical stability and durability of the electrocatalyst.
Neutral condition hydrogen evolution test: fig. 6 is a HER linear sweep voltammetric polarization curve (LSV) and a stability test chart of the catalyst under a neutral condition, (a) is a HER linear sweep voltammetric polarization curve (LSV), 1 is a coop/FeCoS/NF composite catalyst prepared in example one, 2 is a FeCoS/NF catalyst prepared in comparative experiment one, 3 is a coop/NF catalyst prepared in comparative experiment two, 4 is an NF catalyst prepared in comparative experiment three, and (b) is an i-t curve obtained by testing the coop/FeCoS/NF composite catalyst prepared in example one at a potential of 0.171V relative to RHE. As can be seen, the concentration of the metal oxide is 10mA/cm 2 The overpotentials of the individual catalysts are 171mV, 189mV, 298mV and 423mV, respectively, and the overpotentials required for the CoMoP/FeCoS/NF composite catalyst are minimal, i.e., the material still exhibits optimal HER reaction activity under neutral conditions. As shown in the figure (b), the catalyst can stably maintain the catalytic activity for more than 24h, and the excellent chemistry of the CoMoP/FeCoS/NF composite catalyst under the neutral condition is provedAnd (4) stability.
Acid condition hydrogen evolution test: fig. 7 is a graph showing HER linear sweep voltammetric polarization curve (LSV) and stability test of the catalyst under acidic conditions, (a) is a graph showing HER linear sweep voltammetric polarization curve (LSV), 1 is a coop/FeCoS/NF composite catalyst prepared in example one, 2 is a FeCoS/NF catalyst prepared in comparative experiment one, 3 is a coop/NF catalyst prepared in comparative experiment two, 4 is a NF catalyst prepared in comparative experiment three, and (b) is an i-t curve obtained by testing the coop/FeCoS/NF composite catalyst prepared in example one at a potential of 0.027V with respect to RHE. As can be seen, the concentration of the metal oxide is 10mA/cm 2 The overpotential of each catalyst was 27mV, 70mV, 117mV, and 199mV, respectively, at current density of (2). Example one the prepared CoMoP/FeCoS/NF hybrid catalyst requires the least overpotential, i.e. the material exhibits the optimal HER reactivity under acidic conditions. As can be seen from the graph (b), the catalyst can stably maintain the catalytic activity for more than 20 hours, and the CoMoP/FeCoS/NF composite catalyst is proved to have excellent chemical stability under acidic conditions.

Claims (10)

1. A preparation method of a CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis is characterized by comprising the following steps:
1. preparing FeCoS/NF precursor:
uniformly dispersing a cobalt source, an iron source and a sulfur source in ethylene glycol, then carrying out ultrasonic treatment to obtain a uniform and stable mixed solution A, soaking foamed nickel in the uniform and stable mixed solution A, reacting for 8-12 h at the temperature of 150-240 ℃, and finally washing and drying to obtain a FeCoS/NF precursor;
2. preparation of a CoMoP/FeCoS/NF composite catalyst:
uniformly dispersing cobalt nitrate hexahydrate, sodium hypophosphite, sodium molybdate and trisodium citrate in deionized water, stirring to obtain a uniform and stable mixed solution B, taking the uniform and stable mixed solution B as an electrolyte, taking a FeCoS/NF precursor as a working electrode, a carbon rod as a counter electrode and Ag/AgCl as a reference electrode, and depositing for 60-150 s under a constant voltage condition to obtain the CoMoP/FeCoS/NF composite catalyst.
2. The method for preparing a CoMoP/FeCoS/NF composite catalyst for hydrogen production through full-pH electrolysis according to claim 1, wherein the cobalt source in the step one is cobalt chloride hexahydrate; the iron source in the step one is ferrous sulfate heptahydrate; the sulfur source in the step one is thiourea.
3. The preparation method of the CoMoP/FeCoS/NF composite catalyst for hydrogen production through full-pH electrolysis according to claim 1, wherein the molar ratio of the cobalt source to the iron source in the step one is 1 (0.5-2); the molar ratio of the cobalt source to the sulfur source in the first step is 1 (1-3); the volume ratio of the mole of the cobalt source to the volume of the ethylene glycol in the step one is 1mmol (20-50) mL.
4. The preparation method of the CoMoP/FeCoS/NF composite catalyst for full-pH electrolyzed water production according to claim 1, wherein the ultrasonic treatment in the step one is ultrasonic treatment for 0.5-2 h under the condition that the power is 200-500W.
5. The preparation method of the CoMoP/FeCoS/NF composite catalyst for full-pH electrolysis of hydrogen production according to claim 1, wherein the foamed nickel in the first step is pretreated foamed nickel; the pretreatment is specifically carried out according to the following steps: (1) ultrasonic cleaning is carried out by hydrochloric acid with the concentration of 2 mol/L-4 mol/L, acetone, ethanol and ultrapure water in sequence; (2) repeating the steps (1)2-4 times, and finally drying for 6-10 h at the temperature of 50-60 ℃.
6. The preparation method of the CoMoP/FeCoS/NF composite catalyst for full-pH electrolysis of hydrogen production according to claim 1, wherein the washing and drying in the step one is specifically washing with deionized water, and then drying for 8-12 h at a temperature of 50-60 ℃.
7. The method for preparing a CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis according to claim 5, wherein the purity of the nickel foam in the step one is 99.99%, the thickness is 1 mm-2 mm, and the pore size is 100 PPI-120 PPI.
8. The preparation method of the CoMoP/FeCoS/NF composite catalyst for hydrogen production through full-pH electrolysis according to claim 1, wherein the mass ratio of cobalt nitrate hexahydrate to sodium hypophosphite in the step two is 1 (3-4); the mass ratio of the cobalt nitrate hexahydrate to the sodium molybdate in the second step is 1 (0.5-1.5); the mass ratio of the cobalt nitrate hexahydrate to the trisodium citrate in the second step is 1 (0.5-1); the volume ratio of the mass of the cobalt nitrate hexahydrate in the step two to the deionized water is 1g (700-1000) mL.
9. The preparation method of the CoMoP/FeCoS/NF composite catalyst for full-pH electrolyzed water production according to claim 1, wherein the stirring in the step two is specifically stirring for 0.5-1.5 h at a rotation speed of 200-500 r/min.
10. The preparation method of the CoMoP/FeCoS/NF composite catalyst for full-pH electrolysis hydrogen production according to claim 1, wherein in the second step, the deposition is carried out for 60 s-150 s under the condition that the constant voltage is-0.5V-3V.
CN202211287418.6A 2022-10-20 2022-10-20 Preparation method of CoMoP/FeCoS/NF composite catalyst for hydrogen production by full-pH electrolysis Pending CN115572988A (en)

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