CN116377502A - Self-supporting multicomponent high-dispersion noble metal film electrocatalyst and preparation method thereof - Google Patents

Self-supporting multicomponent high-dispersion noble metal film electrocatalyst and preparation method thereof Download PDF

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CN116377502A
CN116377502A CN202310429449.9A CN202310429449A CN116377502A CN 116377502 A CN116377502 A CN 116377502A CN 202310429449 A CN202310429449 A CN 202310429449A CN 116377502 A CN116377502 A CN 116377502A
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noble metal
acid
solution
conductive substrate
film
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唐平贵
冯拥军
李殿卿
孙建红
杜冬冬
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Beijing University of Chemical Technology
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • 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
    • C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide

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Abstract

The invention provides a self-supporting multicomponent high-dispersion noble metal film electrocatalyst and a preparation method thereof, wherein an acid etching and in-situ deposition method is adopted to prepare a noble metal coordination compound film precursor M on a conductive substrate in situ 1 M 2 DCl/F, and calcining in a set atmosphere to obtain the self-supporting multicomponent high-dispersion noble metal film electrocatalyst M 1 M 2 OAC/F. Wherein M is 1 、M 2 O, A, C, F represent noble metals, non-noble metals, oxygen, non-metals, carbon and conductive substrates, respectively. Because the noble metal and the non-noble metal in the coordination compound precursor are dispersed in atomic scale, the noble metal is effectively isolated, the noble metal is not easy to agglomerate during calcination treatment, nano particles with extremely small size are formed and embedded into non-noble metal substances, and the noble metal is optimizedBelongs to electronic structure and geometry. And the catalyst layer is tightly combined with the substrate, and reactants and electrons are rapidly transferred and transferred in the electrocatalytic reaction process, so that the catalyst has excellent hydrogen evolution catalytic activity and extremely high stability.

Description

Self-supporting multicomponent high-dispersion noble metal film electrocatalyst and preparation method thereof
Belonging to the field of
The invention relates to the field of catalytic materials, in particular to a self-supporting multicomponent high-dispersion noble metal thin film electrocatalyst and a preparation method thereof.
Background
The widespread use of fossil fuels has led to increasingly severe problems of environmental pollution, climate change, exhaustion of fossil resources, etc., and development of renewable clean energy sources that can replace fossil energy sources is urgent. Hydrogen energy is considered one of the most promising green energy sources as an environmentally friendly, renewable, clean energy source. The traditional hydrogen production method cannot realize green and sustainable production due to the defects of greenhouse gas emission, low production efficiency and the like. In contrast, electrolysis of water is an environmentally friendly method of producing hydrogen.
H in an electrolytic water Hydrogen Evolution Reaction (HER) of noble metal electrocatalysts (e.g., pd, pt, au, ir, rh and Ru, etc.) ads The binding energy intensity is moderate, and the HER catalytic activity is excellent. Electrocatalysts are largely divided into two types, powder-type and self-supporting. Conventional powder-type electrocatalysts are prepared by coating a powder sample onto an electrode with a binder (e.g., nafion) that is added to the electrode to the extent that the electrocatalyst is not in sufficient contact with the electrolyte and causes an increase in contact resistance. In addition, since a large amount of hydrogen is released during HER, the powder sample coated on the electrode is easily detached due to weak adhesion, resulting in a rapid decrease in catalytic performance, which has a great influence on the stability of the electrocatalyst.
The self-supporting electrocatalyst is an integral catalyst prepared by in-situ growth of active substances on conductive substrates such as nickel foam, copper foam, iron foam, carbon cloth, stainless steel mesh and the like. The active substances grown in situ are tightly combined with the conductive substrate, and are not easy to fall off and lose in the HER process. Meanwhile, the electrocatalyst can be highly dispersed on the conductive substrate and is not easy to agglomerate, exposing more active sites. Documents Li K, xu J, chen C, xie Z, liu D, qu D, tang H, wei Q, deng Q, li J, hu N.journal of Colloid and Interface Science,2021,582:591-597 firstly prepare a layer of NiO on Carbon Cloth (CC) by electrochemical deposition, and then vulcanize under Ar atmosphere by taking sulfur powder as a sulfur source to obtain NiS 2 @ CC, re-impregnating H 2 PtCl 6 NiS of solution 2 Heat treatment is carried out on the @ CC electrode to obtain Pt-NiS 2 @ CC catalyst at 0.5M H 2 SO 4 The solution reaches 50mA cm -2 The overpotential is 139mV, and the catalyst has the defects of complex preparation method, low activity, poor stability and the like. Literature Yang S, zhu J-Y, chen X-N, huang M-J, cai S-H, han J-Y, li J-S.applied Catalysis B: environmental,2022,304:120914 prepared NiRu-LDH/NF on Nickel Foam (NF) by hydrothermal method, and then phosphating it to obtain Ni 2 P-Ru 2 P/NF catalyst, 10, 100, 200mA cm in 1M KOH solution -2 The overpotential of the current density of (1) is 101 mV, 185 mV and 228mV, and the defects of high overpotential, low energy utilization efficiency, poor stability and the like caused by overlarge Ru addition amount and low activity exist. Therefore, the catalysts reported in the prior literature have the defects of low activity, poor stability, complex preparation process, large noble metal usage amount and the like, and cannot meet the requirements of industrial production. Therefore, it is important to develop a novel catalyst with high activity (low overpotential), good stability, low noble metal addition amount and low preparation cost.
Aiming at a plurality of defects of the existing catalyst, the invention provides the idea of reducing the consumption of noble metal, optimizing the preparation process and the catalyst structure of the catalyst to reduce the cost of the catalyst and improve the activity and stability of the catalyst, a layer of noble metal coordination compound film precursor is constructed on a conductive substrate in situ by adopting an acid etching and in-situ deposition method, the noble metal is highly dispersed in a non-noble metal material by forming a coordination compound, the noble metal film self-supporting catalyst with strong binding force with the substrate is prepared by calcining, the consumption of the noble metal is greatly reduced, and the electronic structure and the geometric structure of the noble metal are optimized by the non-noble metal, so that the activity and stability of the catalyst on HER reaction are obviously improved.
Disclosure of Invention
The invention aims to provide a self-supporting multicomponent high-dispersion noble metal thin film electrocatalyst and a preparation method thereof, wherein the self-supporting multicomponent high-dispersion noble metal thin film electrocatalyst has excellent electrolytic water hydrogen evolution activity and extremely high stability.
The self-supporting multicomponent high-dispersion noble metal film electrocatalyst provided by the invention is expressed as M 1 M 2 OAC/F, where M 1 Is noble metal, M 2 Is non-noble metal, O is oxygen, A is non-metallic element, C is carbon, and F is conductive substrate. The catalyst has the characteristics of compact film, small particle size of noble metal and non-noble metal compound, high noble metal dispersity, firm combination of the catalyst film and a conductive substrate, and difficult falling off.
Said M 1 One or two of Pd, pt, au, rh, ru, ir, preferably any one or two of Pt, ru and Ir; said M 2 One or two of Ni, co, fe, sc, ti, V, cr, W, cu, nb, mo, ta, la, ce, preferably one or two of Ni, co and Mo; the A is one or two of N, P, S, se, B, preferably one or two of P, se and B; the F is nickel, copper, iron, cobalt and alloy metal sheets, screens or metal foams, preferably nickel foam, iron foam and nickel-iron foam.
The method adopts acid etching and in-situ deposition to prepare the noble metal coordination compound film precursor on the conductive substrate in situ, and carries out calcination treatment at a certain temperature and under a certain atmosphere to obtain the corresponding noble metal film electrocatalyst, wherein noble metal and non-noble metal ions in the noble metal coordination compound precursor are dispersed in atomic scale, the noble metal is not easy to agglomerate in the calcination treatment process, nano particles with extremely small size can be formed and embedded into non-noble metal substances, the electronic structure and the geometric structure of the noble metal are greatly optimized, and the noble metal keeps high activity and stability; because the catalyst layer is tightly combined with the substrate, the rapid transfer and transfer of reactants and electrons can be realized in the electrocatalytic reaction process, so that the catalyst shows excellent HER activity and extremely high stability. Meanwhile, the use amount of noble metal is greatly reduced in the preparation process, and the cost of the catalyst is obviously reduced.
The preparation method of the self-supporting multicomponent high-dispersion noble metal film electrocatalyst provided by the invention comprises the following specific steps:
A. will be solubleM 1 Dissolving salt into acid solution to obtain uniform solution, wherein M 1 And [ H ] + ]The molar ratio is 0.1-5:1, preferably 0.4-2:1, and then the slow release agent and the acid ligand are sequentially added to obtain M 1 Solution, wherein the slow release agent and M 1 The molar ratio of the acidic ligand to M is 2-20:1, preferably 5-10:1 1 The molar ratio of (2) is 1-15:1, preferably 3-8:1.
The soluble M 1 The salt is one or two of chlorate, chloride, nitrate, sulfate and acetate of Pd, pt, au, rh, ru, ir, preferably one or two of chloropalladate, chloroplatinic acid, chloroauric acid, chloroiridic acid and ruthenium trichloride.
The acid solution is any one of hydrochloric acid, sulfuric acid and nitric acid, and the concentration is 0.5-3 mol/L.
The slow release agent is urea or hexamethylenetetramine.
The acid ligand is abbreviated as D and is any one of ethylenediamine tetraacetic acid, citric acid, oxalic acid, lactic acid, salicylic acid, aminosalicylic acid and glycine, preferably salicylic acid and aminosalicylic acid.
B. Will M 2 Adding salt solution into the reactor, vertically placing the pretreated conductive substrate F into M 2 Heating in salt solution at 50-100 deg.c for 0.2-2 hr to activate the conducting substrate; adding M again 1 Solution into a reactor, M 2 And M is as follows 1 The molar ratio of (C) is 0.2-10:1, preferably 1-4:1, and M in the reaction solution 1 The ratio of the mass of the polymer to the area of the conductive substrate is 0.05-2 mg/cm 2 Preferably 0.3 to 1mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Continuing to react for 3-9 hours at 60-100 ℃, wherein the substrate is etched by weak acidity of the solution, and M 1 、M 2 With D and Cl - Formation of complex M 1 M 2 DCl, gradually forming a layer of noble metal M on the surface of the F substrate 1 Non-noble metal M 2 A thin film that is atomically dispersed; taking out the conductive substrate after the reaction is finished, washing the conductive substrate with deionized water and absolute ethyl alcohol for 6 to 9 times, and drying the conductive substrate to obtain compact M 1 M 2 DCl/F precursor film.
The M is 2 The salt solution being soluble M 2 Solution of salt and deionized water, wherein M 2 The concentration of (2) is 0.1-50 mmol/L; the preferable concentration is 1-10 mmol/L; soluble M 2 The salt is one or two of Ni, co, fe, sc, ti, V, cr, W, cu, nb, mo, ta, la, ce chloride, preferably Ni, co, cr, mo chloride.
The conductive substrate F is nickel, copper, iron, cobalt and alloy metal sheets, silk screens or metal foams with the thickness of 0.02-3 mm, preferably nickel foam, iron foam and nickel foam. The pretreatment method of the conductive substrate comprises the following steps: the conductive substrate is ultrasonically treated in 1-10 mol/L hydrochloric acid or sulfuric acid for 5-15 minutes to remove the oxide layer on the surface, and then respectively ultrasonically treated in absolute ethyl alcohol and deionized water for 3-5 minutes, and washed to be neutral by deionized water.
C. M prepared in step B 1 M 2 The DCl/F precursor film and the source A are simultaneously placed in a reaction furnace, wherein the molar ratio of the source A to the noble metal is 2-40:1, and preferably 10-20:1; sealing the reaction furnace, introducing gas at a flow rate of 10-1000 mL/min at a temperature of 1-10 ℃ for min -1 Heating to 250-600 ℃ at the heating rate, calcining for 1-5 hours, cooling, and taking out a sample to obtain the self-supporting multicomponent high-dispersion noble metal thin film electrocatalyst M 1 M 2 OAC/F. The catalyst has the characteristics of compact film, small particle size of noble metal and non-noble metal compound, high noble metal dispersity, firm combination of the catalyst film and a conductive substrate, and difficult falling off.
During calcination, M 1 M 2 The DCl precursor is decomposed and reacts with gas generated by decomposing/volatilizing the non-metal element doping raw material to be converted into M loaded by carbon 1 M 2 OA, doping of element A into M 1 M 2 Optimization of M in O 1 Electronic structure and geometry of (a) are provided.
The source A is a nonmetallic element raw material and is one of a phosphorus source, a sulfur source, a selenium source, a boron source and a nitrogen source, wherein the phosphorus source is any one of sodium hypophosphite and red phosphorus. The sulfur source is any one of sulfur powder, thiourea and thioacetamide. The selenium source is any one of selenium powder, sodium selenite and ammonium selenide. The boron source is any one of sodium borohydride, boron powder and sodium hypoborate. The nitrogen source is any one of urea, dicyandiamide and melamine.
The gas is any one of nitrogen, ammonia, hydrogen-nitrogen mixed gas and hydrogen-argon mixed gas, wherein the volume of hydrogen in the hydrogen-nitrogen mixed gas and the hydrogen-argon mixed gas is less than 20%; the gas is used to prevent oxidation of the conductive substrate during calcination.
The invention constructs a layer of M with noble metal and non-noble metal dispersed in atomic scale on the surface of the conductive substrate by adopting acid etching and in-situ deposition methods 1 M 2 Calcining the DCl coordination compound film in a set atmosphere to obtain a nonmetallic A-doped multicomponent high-dispersion noble metal film electrocatalyst; the noble metal film is connected with the conductive substrate through chemical bonds, so that the combination is very tight, and the catalyst has good conductivity and small electron transfer resistance; due to M 1 M 2 Noble metal and non-noble metal in DCl precursor are dispersed in atomic level, and after calcination, the noble metal and non-noble metal in the catalyst can be dispersed uniformly, more active sites are exposed, and the synergistic effect of the noble metal and the non-noble metal is brought into play, so that the multicomponent high-dispersion noble metal thin film electrocatalyst has excellent catalytic activity and extremely high stability.
The obtained catalyst was characterized and tested for performance, with the following results:
FIG. 1 is a FT-IR spectrum of RuNi (SA) Cl/N prepared in step C of example 1 showing the characteristic absorption peaks of Salicylate (SA) indicating the formation of a salicylic acid-based complex.
Fig. 2 is an SEM photograph of a precursor film, from which it can be seen that the NF surface is covered with a film, and that almost no large gaps are visible, indicating that the precursor film prepared is very dense.
FIG. 3 is an EDS-Mapping photograph of a precursor film, wherein four elements of Ni, ru, O and C are uniformly distributed on NF, indicating that the distribution of Ni, ru metal and ligand in the precursor is very uniform.
Fig. 4 is a HRTEM photograph of the precursor, on which little lattice fringes are seen and the diffraction ring strength is also very weak, indicating that the precursor has a low crystallinity and is almost an amorphous structure.
FIG. 5 is an SEM photograph of the RuNiOPC/NF catalyst obtained in example 1, from which it can be seen that the prepared RuNiOPC/NF electrocatalyst film is very dense and has a rough surface.
FIG. 6 is an EDS-Mapping photograph of the RuNiOPC/NF catalyst obtained in example 1, in which Ni, ru, O, C and P elements are uniformly distributed on NF, showing that Ni, ru, O, C and P elements in the RuNiOPC/NF catalyst are uniformly distributed.
FIG. 7 is a HRTEM photograph of the RuNiOPC/NF catalyst obtained in example 1, wherein the amorphous component is a carbon substance, and a high-resolution photograph shows the presence of RuO 2 NiO and Ni 2 O 3 Crystalline phase and RuO 2 Embedded in NiO and Ni 2 O 3 In (1), description of RuO 2 NiO and Ni 2 O 3 The average is dispersed on amorphous carbon.
FIG. 8 is a graph showing the results of performance testing of the RuNiOPC/NF catalyst obtained in example 1 in 1M KOH solution, showing that the RuNiOPC/NF catalyst has excellent HER performance, significantly higher activity than commercial Pt/C catalyst, reaching 100, 300 and 700mA cm -2 The overpotential required for the current density was as low as 75, 101 and 128mV, respectively, and had a low Tafel slope (41.84 mV. Dec -1 ) Low impedance and high faraday efficiency (96%).
FIG. 9 shows the results of stability test of the RuNiOPC/NF catalyst obtained in example 1, in which LSV curves of the catalyst almost coincide after 5000 cycles at 300 mA.cm -2 The current density is almost not attenuated when the current is operated for 500 hours, which shows that the RuNiOPC/NF has excellent working stability.
The invention has the beneficial effects that: the invention constructs M with noble metal and non-noble metal ion in atomic scale dispersion on the conductive substrate by acid etching and in-situ deposition 1 M 2 Calcining the DCl complex precursor film in a set atmosphere to obtain the self-supporting multicomponent high-dispersion noble metal film electrocatalyst M 1 M 2 OAC/F. Because the noble metal and the non-noble metal in the precursor are dispersed in an atomic level, noble metal ions are effectively isolated, noble metal substances are embedded in the non-noble metal substances and the amorphous carbon during calcination treatment, the noble metal is not easy to agglomerate, and the high-dispersion noble metal thin film electrocatalyst which has small particle size, high dispersity, is compact and is firmly combined with a substrate is obtained, and active sites of the catalyst are fully exposed; the P, S, se, B and N elements introduced into the catalyst can optimize the electronic structure and the geometric structure of noble metal, and improve the activity and the stability of the noble metal; the conductive substrate has high conductivity and small electron transfer resistance, so that the catalyst has rapid electron transfer capability; under the combined action of the factors, the prepared self-supporting noble metal thin film electrocatalyst has extremely high electrocatalytic hydrogen evolution activity and long-term working stability. In addition, the method has the advantages of simple preparation method, mild reaction conditions, high noble metal conversion rate, easily obtained raw materials and the like, and has wide application prospect in the catalytic fields of industrial electrolyzed water and the like.
Description of the drawings:
FIG. 1 is a FT-IR spectrum of a RuNi (SA) Cl/NF precursor obtained in example 1.
FIG. 2 is a SEM photograph of a RuNi (SA) Cl/NF precursor obtained in example 1 at (a) 10K, (b) 20K and (c) 50K magnification.
FIG. 3 is an EDS-Mapping photograph of RuNi (SA) Cl/NF precursor obtained in example 1, which is in turn an SEM photograph, and a Ni, ru, O, C element Mapping photograph.
FIG. 4 is a photograph of HRTEM (a) and SAED (b) of RuNi (SA) Cl/NF precursor obtained in example 1.
FIG. 5 is an SEM photograph of the RuNiOPC/NF catalyst obtained in example 1 at (a) 10K, (b) 20K and (c) 50K magnification.
FIG. 6 is an EDS-Mapping photograph of the RuNiOPC/NF catalyst obtained in example 1, which is in turn an SEM photograph, a Ni, ru, O, C, P element Mapping photograph.
FIG. 7 is a photograph of the HRTEM of the RuNiOPC/NF catalyst obtained in example 1 at (a) 100K and (b) 400K magnification.
FIG. 8 shows (a) LSV curve, (b) Tafel slope, (c) impedance, and (d) Faraday efficiency of the RuNiOPC/NF catalyst obtained in example 1 in 1M KOH solution.
FIG. 9 shows the results of 5000CV cycles (a) and potentiostatic (b) tests of the RuNiOPC/NF catalyst obtained in example 1 in 1M KOH solution.
The specific embodiment is as follows:
example 1:
A. 1mL of hydrochloric acid solution with the concentration of 0.5mol/L is taken, 10mg of ruthenium trichloride is added into the hydrochloric acid solution, and after uniform mixing, 0.29g of urea and 1g of Salicylic Acid (SA) are sequentially added to obtain solution A.
B. Preparing 50mL of nickel chloride solution with the concentration of 0.1 mmol/L; nickel Foam (NF) (3X 5 cm) 2 ) Ultrasonic treatment is carried out in 3mol/L hydrochloric acid for 10 minutes to remove an oxide layer on the surface, ultrasonic treatment is carried out in absolute ethyl alcohol and deionized water for 3 minutes respectively, deionized water is used for washing for 5 times, the treated NF is vertically placed into a prepared nickel chloride solution, and the NF is activated by treatment for 1 hour at 65 ℃. Then adding the solution A, mixing uniformly, continuing to react for 3 hours at 80 ℃, taking out NF after the reaction is finished, washing for 5 times by deionized water and absolute ethyl alcohol, and drying to obtain salicylic acid and Cl - The ion is ligand, ru and Ni are atomically dispersed and compact film electrocatalyst precursor RuNi (SA) Cl/NF. Characterization of the obtained electrocatalyst precursor RuNi (SA) Cl/NF, the results are shown in figures 1-4, which show that SA ligand exists in the film precursor, the crystallinity of the precursor is very low, the precursor is almost of an amorphous structure, and the formed film is uniform and compact.
C. Placing the RuNi (SA) Cl/NF film electrocatalyst precursor prepared in the step B and 0.5g sodium hypophosphite in a tube furnace at the same time, sealing the tube furnace, introducing nitrogen at a flow rate of 40mL/min, and introducing nitrogen at a temperature of 5 ℃ for min -1 Heating to 350 ℃ at the heating rate, calcining for 2 hours, cooling and taking out a sample to obtain the P doped RuO 2 The catalyst layer of the base film electrocatalyst contains Ru, ni, O, P, C elements, so that the catalyst is abbreviated as RuNiOPC/NF.
Characterization of the resulting electrocatalyst RuNiOPC/NF gave the results shown in FIGS. 5-7, which revealed that the catalyst film was very dense, very rough, and very dense in the distribution of Ru, ni, O, P, C elementsUniform, presence of RuO 2 、NiO、Ni 2 O 3 And amorphous carbon, P is the same as RuO 2 NiO and Ni 2 O 3 Doped, and RuO 2 Embedded in NiO and Ni 2 O 3 And uniformly dispersed on amorphous carbon.
SEM and HRTEM characterization results (figures 5-7) show that the catalyst has small particle size, high dispersity and very dense film, and the film cannot fall off from the NF substrate after ultrasonic treatment for 2 hours.
The HER performance of the catalyst was tested in a standard three electrode system using a CHI660E electrochemical workstation, the electrolyte was a 1mol/L KOH solution, hg/HgO and graphite electrodes were used as reference and counter electrodes, the potential value was corrected using 90% IR compensation, and 5mV s -1 Linear Sweep Voltammetric (LSV) curve and catalyst stability. The test results are shown in the accompanying figures 8-9, and the results show that the catalyst has excellent HER performance in 1M KOH solution, reaching 700mA cm -2 The overpotential required for the current density of (2) is as low as 128mV, significantly better than commercial Pt/C catalysts, and exhibits low Tafil slope and impedance, and high Faraday efficiency; the performance of the catalyst is unchanged after 5000CV circulation, and the catalyst is 300mA cm -2 The operation is carried out for 500 hours under the current density which is still kept at 298 mA.cm -2 Is superior to the catalysts reported in the literature. In addition, the catalyst was used in 1M PBS and 0.5. 0.5M H 2 SO 4 The solution reaches 700mA cm -2 The overpotential required for the current density is as low as 243 and 137mV, respectively.
Example 2:
A. 1mL of hydrochloric acid solution with the concentration of 2mol/L is taken, 36mg of palladium chloride is added into the hydrochloric acid solution, and after uniform mixing, 0.7g of urea and 0.8g of aminosalicylic acid (SAN) are sequentially added to obtain solution A.
B. Preparing 30mL of ferric chloride solution with the concentration of 3 mmol/L; NF (3X 6 cm) 2 ) Ultrasonic treatment in 5mol/L hydrochloric acid for 10 min to remove surface oxide layer, ultrasonic treatment in absolute ethanol and deionized water for 5 min, washing with deionized water for 5 times, placing the treated NF vertically into solution, treating at 70deg.C for 0.5 hr to activate NF, and treatingAdding the solution A into a reaction system, mixing uniformly, continuing to react for 4 hours at 80 ℃, taking out the conductive substrate after the reaction is finished, washing the conductive substrate for 4 times by deionized water and absolute ethyl alcohol, and drying to obtain the dense PdFe (SAN) Cl/NF film precursor with Pd and Fe in an atomic level dispersed mode.
C. Placing the PdNi (SAN) Cl/NF precursor prepared in the step B and 1g of sulfur powder into a tube furnace at the same time, sealing the tube furnace, introducing argon at a flow rate of 50mL/min, and introducing argon at a temperature of 2 ℃ for min -1 Heating to 500 ℃, calcining for 4 hours, cooling and taking out a sample to obtain the noble metal Pd-based thin film electrocatalyst with small and compact particle size, which is expressed as PdNIOSC/NF,
the catalysts were tested for HER performance in 1M KOH, 1M PBS, and 0.5. 0.5M H as in example 1 2 SO 4 The solution has excellent HER performance reaching 700mA cm -2 The overpotential required for the current density is as low as 80, 222 and 103mV, respectively.
Example 3:
A. 1mL of a sulfuric acid solution with a concentration of 1mol/L is taken, 30mg of chloroiridic acid is added into the sulfuric acid solution, and after uniform mixing, 0.79g of hexamethylenetetramine and 0.4g of ethylenediamine tetraacetic acid (EDTA) are sequentially added to obtain a solution A.
B. Preparing 50mL of mixed solution with cobalt chloride concentration of 3mmol/L and nickel chloride concentration of 3 mmol/L; NF (5X 6 cm) 2 ) Ultrasonic treatment in 5mol/L sulfuric acid for 10 min to eliminate surface oxide layer, ultrasonic treatment in absolute ethanol and deionized water for 3 min and washing with deionized water for 5 times, vertical NF placing into solution, and treating at 75deg.C for 0.7 hr to activate NF; adding the solution A into a reaction system, uniformly mixing, continuously reacting for 5 hours at 90 ℃, taking out NF after the reaction is finished, washing for 6 times by deionized water and absolute ethyl alcohol, and drying to obtain a compact IrNiCo (EDTA) Cl/NF precursor with Ir and Ni and Co in atomic-scale dispersion.
C. Placing the IrNiCo (EDTA) Cl/NF precursor prepared in the step B and 0.5g dicyandiamide in a tube furnace simultaneously, introducing 10% hydrogen-argon mixed gas at a flow rate of 25mL/min, and controlling the temperature at 5 ℃ for min -1 Heating to 250 ℃ at the heating rate, calcining for 2 hours, cooling and taking out the sample to obtainTo a small particle size, dense noble metal Ir-based thin film electrocatalyst, denoted IrNiCoONC/NF.
The catalysts were tested for HER performance in 1M KOH, 1M PBS, and 0.5. 0.5M H as in example 1 2 SO 4 The solution has excellent HER performance reaching 700mA cm -2 The overpotential required for the current density is as low as 97, 290 and 114mV, respectively.
Example 4:
A. taking 2mL of nitric acid solution with the concentration of 0.3mol/L, adding 20mg of ruthenium acetate and 10mg of chloroplatinic acid into the nitric acid solution, uniformly mixing, and sequentially adding 0.3g of urea and 0.4g of Citric Acid (CA) to obtain a solution A
B. Preparing 25mL of nickel chloride solution with the concentration of 20 mmol/L; copper foam CF (3X 5 cm) 2 ) Ultrasonic treatment in 5mol/L hydrochloric acid for 3 min to remove oxide layer on the surface, ultrasonic treatment in absolute ethanol and deionized water for 3 min respectively, washing with deionized water for 6 times, vertically placing CF into solution, and treating at 60deg.C for 30 min to activate CF; adding the solution A into a reaction system, mixing uniformly, continuing to react for 6 hours at 85 ℃, taking out the conductive substrate after the reaction is finished, washing the conductive substrate with deionized water and absolute ethyl alcohol for 5 times, and drying to obtain a RuPtNi (CA) Cl/CF precursor with Ru, pt and Cu being atomically dispersed and compact.
C. Placing the RuPtNi (CA) Cl/CF precursor prepared in the step B and 0.5g selenium powder into a tube furnace at the same time, sealing the tube furnace, introducing nitrogen at a flow rate of 80mL/min, and heating at 10 ℃ for min -1 The temperature rise rate of (2) is heated to 600 ℃, the calcination treatment is carried out for 4 hours, and after cooling, a sample is taken out to obtain the noble metal RuPt-based thin film electrocatalyst with small particle size and high dispersion and compactness, which is expressed as RuPtNiOSEC/CF.
The catalysts were tested for HER performance in 1M KOH, 1M PBS, and 0.5. 0.5M H as in example 1 2 SO 4 The solution has excellent HER performance reaching 700mA cm -2 The overpotential required for the current density is as low as 95, 232 and 85mV, respectively.
Example 5:
A. 1mL of sulfuric acid solution with the concentration of 0.5mol/L is taken, 10mg of rhodium chloride is added into the sulfuric acid solution, and 0.36g of urea and 0.2g of citric acid are sequentially added after uniform mixing to obtain solution A.
B. Preparing 30mL of mixed solution with cobalt chloride concentration of 20mmol/L and nickel chloride concentration of 10mmol/L, vertically placing CF treated in example 4 into the solution, and treating at 90 ℃ for 0.5 hour to activate the CF; adding the solution A into a reaction system, mixing uniformly, continuing to react for 4 hours at 90 ℃, taking out CF after the reaction is finished, washing the CF with deionized water and absolute ethyl alcohol for 6 times, and drying to obtain a dense RhCo (CA) Cl/CF precursor in which Rh and Co are dispersed in an atomic scale.
C. Placing the RhCu (CA) Cl/CF precursor prepared in the step B and 0.5g melamine in a tube furnace at the same time, sealing the tube furnace, introducing ammonia gas at a flow rate of 60mL/min, and introducing ammonia gas at a temperature of 1 ℃ for min -1 The temperature rise rate of (2) is heated to 300 ℃, the calcination treatment is carried out for 3 hours, and after cooling, a sample is taken out to obtain the noble metal Rh-based thin film electrocatalyst with small particle size and high dispersion, which is expressed as RhCuONC/CF.
The catalysts were tested for HER performance in 1M KOH, 1M PBS, and 0.5. 0.5M H as in example 1 2 SO 4 The solution has higher HER performance, reaching 700mA cm -2 The overpotential required for the current density is as low as 101, 228 and 106mV, respectively.
Example 6:
A. 2mL of a sulfuric acid solution of 0.5mol/L was taken, 20mg of chloroauric acid was added to the sulfuric acid solution, and after mixing uniformly, 0.62g of hexamethylenetetramine and 0.51g of Glycine (GA) were sequentially added to obtain solution A.
B. 35mL of 10mmol/L molybdenum chloride solution is prepared; cobalt sheet (CoF) (3X 6 cm) with a thickness of 0.1mm 2 ) Ultrasonic treatment in 6mol/L hydrochloric acid for 5 min to remove the oxide layer on the surface, ultrasonic treatment in absolute ethanol and deionized water for 3 min respectively, washing with deionized water for 6 times, vertically placing cobalt sheet into solution, and treating at 80deg.C for 0.6 hr to activate cobalt sheet; adding the solution A into a reaction system, uniformly mixing, continuously reacting for 4 hours at 90 ℃, taking out a cobalt sheet after the reaction is finished, washing with deionized water and absolute ethyl alcohol for 5 times, and drying to obtain a compact AuMo (GA) Cl/CoF precursor in which Au and Mo are dispersed in an atomic level.
C. Placing the AuMo (GA) Cl/CoF precursor prepared in the step B and 0.2g urea in a tube furnace at the same time, sealing the tube furnace, introducing nitrogen at a flow rate of 80mL/min, and introducing nitrogen at a temperature of 5 ℃ for min -1 The temperature rise rate of (2) is heated to 400 ℃, the calcination treatment is carried out for 2 hours, and after cooling, a sample is taken out to obtain the noble metal Au-based thin film electrocatalyst with small particle size, high dispersion, compactness and firm combination, which is expressed as AuMoONC/CoF.
The catalysts were tested for HER performance in 1M KOH, 1M PBS, and 0.5. 0.5M H as in example 1 2 SO 4 The solution has excellent HER performance reaching 700mA cm -2 The overpotential required for the current density is as low as 104, 230 and 109mV, respectively.
Example 7:
A. 3mL of a 0.5mol/L nitric acid solution was taken, 35mg of chloroplatinic acid was added to the nitric acid solution, and after uniform mixing, 0.36g urea and 0.566g glycine were added in sequence to obtain solution A.
B. 40mL of 30mmol/L cerium chloride solution was prepared, and NF treated in example 1 was placed vertically in the solution and treated at 80℃for 0.5 hour to activate NF; adding the solution A into a reaction system, mixing uniformly, continuing to react for 5 hours at 85 ℃, taking out NF after the reaction is finished, washing the NF with deionized water and absolute ethyl alcohol for 4 times, and drying to obtain a PtCe (GA) Cl/NF precursor with Pt and Ce being dispersed in an atomic level and compact.
C. Placing PtCe (GA) Cl/NF precursor prepared in the step B and 0.4g boron powder into a tube furnace at the same time, sealing the tube furnace, introducing argon at a flow rate of 60mL/min, and introducing argon at a temperature of 2 ℃ for min -1 The temperature rise rate of (2) is heated to 350 ℃, the calcination treatment is carried out for 3 hours, and after cooling, a sample is taken out to obtain the noble metal Pt-based thin film electrocatalyst with small particle size and firm combination, which is expressed as PtCeONC/NF.
The catalysts were tested for HER performance in 1M KOH, 1M PBS, and 0.5. 0.5M H as in example 1 2 SO 4 The solution has higher HER performance, reaching 700mA cm -2 The overpotential required for the current density is as low as 91, 243 and 83mV, respectively.
Example 8:
A. 5mL of a sulfuric acid solution (0.1 mol/L) was taken, 20mg of palladium chloride and 15mg of chloroplatinic acid were added to the sulfuric acid solution, and after mixing uniformly, 0.14g of urea and 0.17g of ethylenediamine tetraacetic acid (EDTA) were added in this order to obtain a solution A.
B. Preparing 50mL of 40mmol/L cobalt chloride solution; foam Iron (IF) (4X 6 cm) 2 ) Ultrasonic treatment in 1mol/L hydrochloric acid for 5 min to remove oxide layer on the surface, ultrasonic treatment in absolute ethanol and deionized water for 3 min respectively, washing with deionized water for 4 times, vertically placing IF into solution, and treating at 55deg.C for 0.5 hr to activate IF; adding the solution A into a reaction system, uniformly mixing, continuously reacting for 4 hours at 80 ℃, taking out foam iron after the reaction is finished, washing the foam iron for a plurality of times by deionized water and absolute ethyl alcohol, and drying to obtain a PdPtCoFe (EDTA) Cl/IF precursor in which Pd, pt, co and Fe are dispersed in an atomic level and compact.
C. Placing PdPtCoFe (EDTA) Cl/IF precursor prepared in the step B and 0.15g thiourea in a tube furnace at the same time, sealing the tube furnace, introducing gas at a flow rate of 10mL/min, and heating at 5 ℃ for min -1 The temperature rise rate of (2) is heated to 350 ℃, the calcination treatment is carried out for 2 hours, and after cooling, a sample is taken out to obtain the noble metal PdPt-based thin film electrocatalyst with small particle size, high dispersion, compactness and firm combination, which is expressed as PdPtCoFeOSC/IF.
The catalysts were tested for HER performance in 1M KOH, 1M PBS, and 0.5. 0.5M H as in example 1 2 SO 4 The solution has higher HER performance, reaching 700mA cm -2 The overpotential required for the current density is as low as 92, 234 and 87mV, respectively.
The HER performance of the catalysts prepared in examples 1-8 was summarized and the results are shown in table 1.
TABLE 1
Figure BDA0004189908750000111

Claims (4)

1. A self-supporting multicomponent high-dispersion noble metal film electrocatalyst is characterized by that said catalyst is expressed as M 1 M 2 OAC/F, where M 1 Is noble metal, M 2 Is non-noble metal, O is oxygen, A is non-metallic element, C is carbon, F is conductive substrate; the catalyst is characterized in that the film is compact, the noble metal and non-noble metal compound particles are small in size, the noble metal dispersity is high, the film and the conductive substrate are firmly combined, and the film is not easy to fall off;
said M 1 One or two of Pd, pt, au, rh, ru, ir; said M 2 One or two of Ni, co, fe, sc, ti, V, cr, W, cu, nb, mo, ta, la, ce; the A is one or two of N, P, S, se, B; and F is nickel, copper, iron, cobalt and alloy metal sheets, silk screens or metal foam thereof.
2. The self-supporting multicomponent highly dispersed noble metal thin film electrocatalyst according to claim 1, characterized in that M 1 Is any one or two of Pt, ru and Ir; said M 2 Is one or two of Ni, co and Mo; a is one or two of P, se and B; and F is foam nickel, foam iron and foam nickel iron.
3. A method for preparing the self-supporting multicomponent highly dispersed noble metal thin film electrocatalyst according to claim 1, comprising the steps of:
A. will be soluble M 1 Dissolving salt into acid solution to obtain uniform solution, wherein M 1 And [ H ] + ]The molar ratio is 0.1-5:1; sequentially adding the slow release agent and the acid ligand to obtain M 1 Solution, wherein the slow release agent and M 1 The molar ratio of (2) to (20) to (1); acidic ligand and M 1 The molar ratio of (2) is 1-15:1;
the soluble M 1 The salt is one or two of chlorate, chloride, nitrate, sulfate and acetate of Pd, pt, au, rh, ru, ir;
the acid solution is any one of hydrochloric acid, sulfuric acid and nitric acid, and the concentration is 0.5-3 mol/L;
the slow release agent is urea or hexamethylenetetramine;
the acid ligand is abbreviated as D and is any one of ethylenediamine tetraacetic acid, citric acid, oxalic acid, lactic acid, salicylic acid, aminosalicylic acid and glycine;
B. will M 2 Adding salt solution into the reactor, vertically placing the pretreated conductive substrate F into M 2 Heating in salt solution at 50-100 deg.c for 0.2-2 hr to activate the conducting substrate; adding M again 1 Solution into a reactor, M 2 And M is as follows 1 The molar ratio of (2) to (10:1) is 0.2-10, and M in the reaction solution 1 The ratio of the mass of the polymer to the area of the conductive substrate is 0.05-2 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Continuing to react for 3-9 hours at 60-100 ℃, wherein the substrate is etched by weak acidity of the solution, and M 1 、M 2 With D and Cl - Formation of complex M 1 M 2 DCl, gradually forming a layer of noble metal M on the surface of the F substrate 1 Non-noble metal M 2 A thin film that is atomically dispersed; taking out the conductive substrate after the reaction is finished, washing the conductive substrate with deionized water and absolute ethyl alcohol for 6 to 9 times, and drying the conductive substrate to obtain compact M 1 M 2 DCl/F precursor film;
the M is 2 The salt solution being soluble M 2 Solution of salt and deionized water, wherein M 2 The concentration of (2) is 0.1-50 mmol/L; soluble M 2 The salt is one or two of Ni, co, fe, sc, ti, V, cr, W, cu, nb, mo, ta, la, ce chlorides;
the conductive substrate F is nickel, copper, iron, cobalt and alloy metal sheets, silk screens or metal foams with the thickness of 0.02-3 mm; the pretreatment method of the conductive substrate comprises the following steps: ultrasonic treating the conductive substrate in 1-10 mol/L hydrochloric acid or sulfuric acid for 5-15 min to eliminate surface oxide layer, ultrasonic treating in absolute ethyl alcohol and deionized water for 3-5 min, and washing with deionized water to neutrality;
C. m prepared in step B 1 M 2 The DCl/F precursor film and the source A are simultaneously placed in a reaction furnace, wherein the molar ratio of the source A to the noble metal is 2-40:1; sealing the reaction furnace, introducing gas at a flow rate of 10-1000 mL/min at a temperature of 1-10 ℃ for min -1 Heating to 250-600 deg.c,calcining for 1-5 hours, cooling and taking out a sample to obtain the self-supporting multicomponent high-dispersion noble metal thin film electrocatalyst M 1 M 2 OAC/F; the catalyst is characterized in that the film is compact, the noble metal and non-noble metal compound particles are small in size, the noble metal dispersity is high, the film and the conductive substrate are firmly combined, and the film is not easy to fall off;
the source A is any one of nonmetallic element raw materials, namely sodium hypophosphite, red phosphorus, sulfur powder, thiourea, thioacetamide, selenium powder, sodium selenite, ammonium selenide, sodium borohydride, boron powder, sodium hypoborate, urea, dicyandiamide and melamine;
the gas is any one of nitrogen, ammonia, hydrogen-nitrogen mixed gas and hydrogen-argon mixed gas, wherein the volume of hydrogen in the hydrogen-nitrogen mixed gas and the hydrogen-argon mixed gas is less than 20%; the gas is used to prevent oxidation of the conductive substrate during calcination.
4. The method for self-supporting multicomponent highly dispersed noble metal thin film electrocatalyst according to claim 3, characterized by
M described in step A 1 And [ H ] + ]The molar ratio of the slow release agent to M is 0.4-2:1 1 The molar ratio of the acid ligand to M is 5-10:1 1 The molar ratio of (2) is 3-8:1; the soluble M 1 The salt is any one or two of chloropalladate, chloroplatinic acid, chloroauric acid, chloroiridium acid and ruthenium trichloride; the acid ligand is salicylic acid and aminosalicylic acid;
step B. M in the reaction solution in the reactor 2 And M is as follows 1 The molar ratio of (2) is 1-4:1, and M 1 The ratio of the mass of (C) to the area of the conductive substrate is 0.3-1 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The M is 2 The concentration of the salt solution is 1-10 mmol/L; soluble M 2 One of the chlorides of salt Ni, co, cr, mo; the conductive substrate F is foam nickel, foam iron and foam nickel iron;
in the step C, the molar ratio of the source A to the noble metal is 10-20:1.
CN202310429449.9A 2023-04-20 2023-04-20 Self-supporting multicomponent high-dispersion noble metal film electrocatalyst and preparation method thereof Pending CN116377502A (en)

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