CN114875442A - Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof - Google Patents

Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114875442A
CN114875442A CN202210577985.9A CN202210577985A CN114875442A CN 114875442 A CN114875442 A CN 114875442A CN 202210577985 A CN202210577985 A CN 202210577985A CN 114875442 A CN114875442 A CN 114875442A
Authority
CN
China
Prior art keywords
nickel
ruthenium
composite catalyst
molybdate
nanorod composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210577985.9A
Other languages
Chinese (zh)
Inventor
侯阳
陈月
杨彬
雷乐成
李中坚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
Original Assignee
Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU, Quzhou Research Institute of Zhejiang University filed Critical Zhejiang University ZJU
Priority to CN202210577985.9A priority Critical patent/CN114875442A/en
Publication of CN114875442A publication Critical patent/CN114875442A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/089—Alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention relates to the technical field of electrochemical materials, and discloses a ruthenium-modified molybdenum-nickel nanorod composite catalyst as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing nickel salt, molybdate and ruthenium salt in a solvent to obtain a solution, soaking foamed nickel in the solution to perform hydrothermal reaction to obtain a foamed nickel precursor, performing ultrasonic drying to obtain a ruthenium-loaded nickel molybdate precursor, and performing thermal reduction treatment to obtain a catalyst, wherein the catalyst has excellent electrocatalytic activity in an electrolytic water cathode hydrogen evolution reaction and can realize high current density>200mA/cm 2 ) The stability is excellent after long-term operation.

Description

Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a ruthenium-modified molybdenum-nickel nanorod composite catalyst and a preparation method and application thereof.
Background
Hydrogen (H) 2 ) Because of the advantages of high calorific value, no pollution of products after combustion and the like, the fuel becomes ideal clean energy and energy storage substances for replacing the traditional fossil fuel. Wherein, the hydrogen production (HER) by electrochemically decomposing water has high production efficiency, H 2 The purity is high, and the product is water and pollution-free, which is one of the most promising methods at present, and is widely researched. However, most of the current research on hydrogen evolution catalysts still stays at 10mA/cm 2 At class current density, unfavorable for industrial-scale high current density: (>200mA/cm 2 ) The use of (1). In recent years, much research effort has been devoted to developing low cost, simple to prepare high current density catalysts.
Among the catalysts, transition metals Ni and Mo are cheap, green and harmless metals, and have been reported to have better catalytic performance in hydrogen production by electrolyzing water for many times. For example, Chinese patent publication No. CN114059082A discloses N, P co-doped NF @ NiMoO 4 The preparation method of the hollow nanowire composite material and the application thereof are characterized in that firstly soluble nickel salt and soluble molybdenum salt are used as raw materials to prepare NF @ NiMoO through a hydrothermal method 4 The precursor is prepared by taking ammonium bicarbonate as a nitrogen source and sodium hypophosphite monohydrate as a phosphorus source through vapor deposition reaction under the protection of inert gas, and N, P codoped NF @ NiMoO is prepared 4 A hollow nanowire composite.
For example, publication No. CN 113802162A discloses Ni 3 Se 2 /MoSe 2 The preparation method and application of the bifunctional composite catalyst are that SeO is firstly used 2 、Na 2 MoO 4 And nickel acetate as originalPreparing a metal selenide nanocomposite in situ by an electrochemical method; the specific method comprises the following steps: (1) SeO is added according to a certain molar ratio 2 、Na 2 MoO 4 Adding nickel acetate into deionized water, and stirring to obtain saturated electrolyte; (2) in a standard three-electrode system, preparing a precursor sample by electrodeposition in the saturated electrolyte obtained in the step (1) by taking a graphite rod as a counter electrode, foam nickel as a working electrode and silver/silver chloride as a reference electrode; washing the precursor sample for multiple times, and drying to obtain Ni 3 Se 2 /MoSe 2 A bifunctional composite catalyst. Yuting Luo et al prepared MoO grown in situ on NF by hydrothermal and gas phase reduction 2 Nanosheet, Fe-modified Ni 4 Mo nanoparticles anchored on the nanosheets have very high electrocatalytic activity under alkaline conditions and high current densities (Energy environ. Sci.,2021,14,4610-
However, the performance of the pure molybdenum-nickel compound as an electrocatalyst is far from that of commercial noble metal catalysts such as Pt/C and the like under a high current density, and particularly, the stability problem under the high current density is difficult to solve, so that the pure molybdenum-nickel compound cannot meet the real industrial-grade hydrogen evolution condition.
Disclosure of Invention
Aiming at the problems that the catalytic activity of a molybdenum-nickel compound catalyst in the prior art needs to be improved, and particularly the catalytic activity and the stability under high current density are insufficient, the invention provides a preparation method of a ruthenium-modified molybdenum-nickel nanorod composite catalyst, and the obtained catalyst has high-efficiency adsorption and dissociation capacity of water molecules and can realize high current density (A)>200mA/cm 2 ) The stability is excellent after long-term operation.
In order to realize the purpose, the invention adopts the technical scheme that:
a preparation method of a ruthenium-modified molybdenum-nickel nanorod composite catalyst comprises the following steps:
step 1, mixing nickel salt, molybdate and ruthenium salt in a solvent to obtain a solution, soaking foam nickel in the solution to perform hydrothermal reaction to obtain a foam nickel precursor, and performing ultrasonic treatment and drying to obtain a ruthenium-loaded nickel molybdate precursor;
and 2, carrying out thermal reduction treatment on the ruthenium-loaded nickel molybdate precursor to obtain the ruthenium-modified molybdenum-nickel nanorod composite catalyst.
According to the invention, divalent nickel and molybdate ions react through a hydrothermal reaction to generate a nickel molybdate compound, ruthenium ions are adsorbed to form a ruthenium-doped nickel molybdate monoclinic system structure, and then a part of nickel molybdate is reduced to a molybdenum-nickel alloy through reduction gas heat treatment, so that the conductivity of the material is improved, ruthenium ions are reduced to ruthenium nanoparticles loaded on the surface of nickel molybdate, the specific surface area and active sites of the catalyst are increased, the electrocatalytic activity of the catalyst is further improved, and the ruthenium-modified nickel-molybdenum nanorod composite catalyst is obtained, and the catalyst shows excellent catalytic stability in an electrolytic water hydrogen evolution reaction, and can stably produce hydrogen for a long time especially under a large current density.
The nickel salt, the molybdate or the ruthenium salt are soluble salts;
the nickel salt comprises nitrate, chloride, sulfate, hydrate and the like of nickel, such as any one of nickel nitrate hexahydrate, nickel chloride hexahydrate and nickel sulfate hexahydrate;
the molybdate comprises any one of sodium molybdate or ammonium molybdate;
the ruthenium salt comprises any one of ruthenium acetylacetonate, ruthenium chloride trihydrate and ammonia hexachlororuthenate.
The molar ratio of the nickel salt to the molybdate is 1: 1-5, and the ratio of the nickel salt to the molybdate determines the three-dimensional structure of the obtained precursor. The ratio is too low, and the regular structure of the precursor is easily damaged by excessive molybdate radicals, so that the performance is reduced; the proportion is too high, the structure of the precursor is not uniform, the subsequent analysis treatment is not facilitated, and the structure of the precursor obtained in the proportion is more beneficial to the preparation of a later-stage catalyst;
preferably, the molar ratio of the nickel salt to the molybdate is 1:1-2, further preferably 1: 1.5;
preferably, the molar ratio of the ruthenium salt to the nickel salt is 1: 10-40, and more preferably 1: 20. When the content of ruthenium is too low, the dispersion is not uniform, the performance of the whole catalyst is not obviously improved, and when the content of ruthenium is too high, ruthenium particles are easy to gather, so that the exposure of active sites is not sufficient, the catalytic activity is reduced, and the subsequent research on a catalytic mechanism is not facilitated.
The volume mass ratio of the foamed nickel to the nickel salt is 1: 0.5-2. The proportion of the nickel salt to the nickel foam influences the uniform growth condition of the precursor on the nickel foam, but when the amount of the nickel foam is too low, a large amount of the precursor cannot grow on the nickel foam, and the raw material is wasted.
In the step 1, the nickel salt, the molybdate and the ruthenium salt are mixed in the solvent by magnetic stirring or ultrasonic to promote the nickel salt, the molybdate and the ruthenium salt to be uniformly dispersed, so that the obtained catalyst has better dispersion of active sites and higher catalytic activity. The stirring time is preferably 0.5 to 1 hour.
In the step 1, the solvent comprises at least one of water, ethanol and N, N-dimethylformamide.
The nickel salt, the molybdate and the ruthenium salt in the obtained solution are dissolved and mixed fully, preferably, the mass concentration of the nickel salt in the solution is 20-30 g/L, the mass concentration of the molybdate is 30-35 g/L, and the mass concentration of the added ammonia hexachlororuthenate is 0.5-3 g/L.
The temperature of the hydrothermal reaction in the step 1 is 150-. The hydrothermal reaction temperature has influence on the obtained precursor, for example, if the hydrothermal temperature is too low, the formation of nickel molybdate is not facilitated, and if the hydrothermal temperature is too high, the grain size of nickel molybdate is too large, and the exposure of the active sites of the catalyst is not facilitated. The hydrothermal time influences the growth of the catalyst on the foamed nickel, is too short, is not beneficial to the uniform growth of the catalyst on the foamed nickel, and is too long, so that the catalyst is easy to accumulate on the surface of the foamed nickel. The performance of the catalyst obtained by hydrothermal reaction at the temperature of 150 ℃ and 200 ℃ is excellent.
In the step 1, the ultrasonic time is 2-4 h. The ultrasonic process aims to remove the catalyst which is not firmly adhered to the surface and unreacted impurities, so that the subsequent reduction treatment is facilitated, and the active sites are more fully exposed.
In the step 2, the temperature of the thermal reduction treatment is 300-; the thermal reduction treatment atmosphere condition is H 2 Ar, the volume concentration of hydrogen is 3-10 percent. The molybdenum-nickel alloy and ruthenium particles can be better formed by controlling the temperature and the time, the nickel-molybdenum alloy with good conductivity and long-range order is not favorably formed at lower temperature, ruthenium oxide cannot be fully reduced into particles, but the ruthenium nanoparticles are easy to Ostwald ripening due to overhigh temperature, the number of catalytic active sites is reduced, and meanwhile, the components in the system are complex and are not favorable for subsequent analysis and treatment. Preferably, the thermal reduction treatment temperature is 350-550 ℃, more preferably 350-450 ℃, and the obtained catalyst has more excellent performance.
The invention also provides the ruthenium modified molybdenum-nickel nanorod composite catalyst obtained by the preparation method. The catalyst can be represented by the following chemical formula: Ru/Ni-Mo/NF, wherein Ru is ruthenium nanoparticles; Ni-Mo is nickel molybdate inner core and partially reduced molybdenum-nickel alloy; the catalyst consists of a nickel molybdate inner core, molybdenum-nickel alloy particles on the surface and ruthenium nanoparticles, and the catalytic activity of the dispersed ruthenium nanoparticles, the chemical stability of nickel molybdate and the conductivity of the molybdenum-nickel alloy obviously improve the hydrogen evolution activity and stability of the catalyst under high current density.
The invention also provides application of the ruthenium modified molybdenum-nickel nanorod composite catalyst in an alkaline solution for an electrolytic water hydrogen evolution reaction.
Specifically, in the electrolytic water cathode HER reaction, a three-electrode system is adopted, specifically, an Ag/AgCl electrode is used as a reference electrode, a carbon rod is used as a counter electrode, the ruthenium modified nickel-molybdenum nanorod composite catalyst is used as a working electrode, a 1.0M potassium hydroxide solution is used as an electrolyte, and water is electrolyzed to separate out hydrogen.
The method can also comprise the following steps: in the electrolytic simulation of seawater cathode HER reaction, a three-electrode system is adopted, specifically, an Ag/AgCl electrode is used as a reference electrode, a carbon rod is used as a counter electrode, the ruthenium modified nickel-molybdenum nanorod composite catalyst provided by the invention is used as a working electrode, and 1.0M potassium hydroxide and 0.5M sodium chloride solution are used as electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
(1) the ruthenium-modified nickel-molybdenum nanorod composite catalyst provided by the invention takes foamed nickel as a substrate and adopts a hydrothermal methodAnd reduction treatment, the binding force of the composite material and the substrate can be increased, the contact area of the electrode and electrolyte is increased by the foamed nickel substrate, more active sites are exposed, the adsorption and dissociation capability of the foamed nickel substrate on water molecules is effectively improved, the electrocatalytic activity of the ruthenium modified nickel-molybdenum nanorod composite catalyst is further increased, the obtained catalyst has high-efficiency electrocatalytic activity and good stability, and excellent catalytic performance is shown when water is electrolyzed under an alkaline condition, for example, the current density is 500mA/cm -2 In the process, the overpotential of the cathode is only about 90mV, no obvious potential attenuation can be maintained for 12h, the high-efficiency electrocatalytic activity and good stability are achieved, and the possibility of hydrogen energy development and utilization is further improved.
(2) The ruthenium-modified nickel-molybdenum nanorod composite catalyst provided by the invention has high-efficiency electrocatalytic activity in alkaline simulated seawater, such as current density of 500mA/cm -2 In the process, the overpotential of the cathode is only about 98mV, which provides reference for the direct electrolytic hydrogen production technology without desalination in situ of seawater.
(3) The ruthenium modified nickel-molybdenum nanorod composite catalyst provided by the invention is simple in preparation method, excellent in performance and beneficial to industrial large-scale application.
Drawings
FIG. 1 is an SEM image of the ruthenium-modified nickel molybdenum nanorod composite catalyst prepared in example 1.
FIG. 2 is a TEM image of the ruthenium-modified nickel molybdenum nanorod composite catalyst prepared in example 1.
FIG. 3 is an XRD pattern of the ruthenium-modified nickel molybdenum nanorod composite catalyst prepared in example 1.
FIG. 4 is a polarization curve diagram of the electrolytic water hydrogen evolution reaction of the catalysts prepared in example 1 and comparative examples 1-4 in the application example.
FIG. 5 is a graph of voltage variation with time at a constant current of 0.01A for electrolytic water reduction of the ruthenium-modified nickel molybdenum nanorod composite catalyst prepared in example 1.
FIG. 6 is a graph of voltage variation with time at 0.05A constant current for electrolytic water reduction of the ruthenium-modified nickel molybdenum nanorod composite catalyst prepared in example 1.
FIG. 7 is a graph of voltage variation with time at 0.1A constant current for electrolytic water reduction of the ruthenium-modified nickel molybdenum nanorod composite catalyst prepared in example 1.
FIG. 8 is a graph of the voltage variation with time of the ruthenium-modified nickel molybdenum nanorod composite catalyst prepared in example 1 at 60 ℃ under a constant current of 0.05A for the reduction of 6M KOH electrolyzed water.
FIG. 9 is a polarization curve diagram of the hydrogen evolution reaction of seawater simulated by the electrolysis alkalinity of the catalyst prepared in example 1 in an application example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiments are all commercially available.
Example 1
(1) Weighing 1.09g of nickel nitrate hexahydrate solid particles, 0.07g of ammonia hexachlororuthenate solid particles and 1.159g of ammonium molybdate solid particles, dissolving in 37.5ml of deionized water, and mixing for 30min to form a precursor solution;
(2) transferring the precursor solution into a 50mL hydrothermal kettle, placing 2 x 4cm of foamed nickel into a reaction kettle, carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at 160 ℃, taking out the foamed nickel precursor, carrying out ultrasonic treatment in ultrapure water for about 1 hour, placing the washed foamed nickel precursor into the oven, and drying at 60 ℃ for 10 hours to obtain a ruthenium-containing nickel molybdate precursor;
(3) the prepared nickel molybdate precursor containing ruthenium and loaded on the surface of the foamed nickel is placed in the center of a horizontal tube furnace in H 2 Heating at 350 deg.C for 1h under Ar (5%/95%) atmosphere, and heating to 450 deg.C at a heating rate of 5 deg.C/min for 1 h. After the reaction is finished, cooling to room temperature to obtain the ruthenium modified nickel-molybdenum nanorod composite catalyst,is recorded as Ru/Ni-Mo/NF.
The prepared catalyst is observed for the microscopic morphology through a scanning electron microscope SEM and a transmission electron microscope TEM, the SEM result is shown in figure 1, and the TEM image is shown in figure 2. It can be seen from FIGS. 1-2 that the nickel molybdate particles are uniformly dispersed on the surface of the rod-shaped nickel molybdate. The X-ray diffraction XRD pattern of the ruthenium-modified nickel-molybdenum nanorod composite catalyst prepared in this example is shown in fig. 3, and it can be seen that the composite structure includes various crystal phases of nickel molybdate and molybdenum-nickel alloy.
Comparative example 1
According to the process of the embodiment 1, the difference is that ammonia hexachlororuthenate solid particles are not added in the step (1), so that the molybdenum-nickel nanorod composite catalyst loaded on the nickel foam is obtained and is recorded as Ni-Mo/NF.
Comparative example 2
The process of example 1 was followed except that no ammonium molybdate solid particles were added in step (1) to yield a ruthenium modified nickel composite catalyst, designated Ru/Ni/NF.
Comparative example 3
The process of example 1 was followed except that nickel nitrate hexahydrate solid particles were not added in step (1) to yield a ruthenium modified molybdenum composite catalyst, designated as Ru/Mo/NF.
Comparative example 4
The process of example 1 was followed except that only ammonia hexachlororuthenate solid particles were added in step (1) to give a ruthenium modified nickel foam catalyst, designated Ru/NF.
Application example 1
(1) Using a three-electrode system, the catalyst prepared in example 1 or comparative examples 1-4 was used as the working electrode, the counter electrode was a carbon rod, the reference electrode was a saturated Ag/AgCl electrode, and the electrolyte was 1.0M KOH;
(2) CV activation: the electrochemical workstation of Shanghai Chenghua CHI 660E was used, and nitrogen was introduced into the electrolyte for 30min before the test. Adopting CV program, testing interval is 0-0.8V vs. RHE, sweep speed is 50mV/s, circulating for 20 circles, and the electrode reaches stable state;
the catalysts prepared in example 1 and comparative examples 1 to 4 and commercial PtC (noble metal TANAKA in Japan, 20% platinum-carbon catalyst) were subjected to cyclic scanningAfter the activation of the voltammetry (CV) test, the switching program is an LSV program, the test interval is 0 to-0.8V vs. RHE, the sweep rate is 5mV/s, and the overpotential is 0V and 500mA/cm relative to the reversible hydrogen electrode -2 The difference in potential was measured. As shown in FIG. 4, the polarization curve of the reaction of Ru/Ni-Mo/NF with Ni-Mo/NF, Ru/Ni/NF, Ru/Mo/NF and Ru/NF in 1.0MKOH is shown in FIG. 4. As can be seen from FIG. 4, the overpotential of the Ru/Ni-Mo/NF catalyst prepared in example 1 is only 89mV (eta.) in alkaline electrolyte 500mA/cm2 ) Whereas the commercial PtC overpotential was 163mV, comparative examples 1-4 were 257mV, 364mV, 430mV, and 344mV, respectively. It can be seen that the effect of example 1 is obviously better than that of other comparative catalysts, even better than that of commercial PtC catalysts, while the best effect cannot be obtained in comparative examples 1-4 due to the lack of one element or two elements, and thus the lack of ruthenium, nickel and molybdenum is not enough.
The catalyst prepared in example 1 was subjected to stability test
After CV activation, the switching program was the CP program, with current set at 0.01A and time set at 234000 s. As shown in fig. 5, the catalyst had a small change in overpotential, demonstrating its good stability.
In order to test the stability of the sample under industrial-grade high current density, the current is adjusted to be 0.05A and 0.1A, and the current density is respectively 500mA cm -2 And 1A cm -2 . Because the current density is large, the gas production rate is accelerated, and the electrolyte needs to be supplemented in time. As shown in FIGS. 6 and 7, the Ru/Ni-Mo/NF ratio can be in excess of 500mA cm -2 The good electrocatalysis performance of the continuous hydrogen production for 100 hours under the industrial current density is still maintained, and the potential of the electrocatalysis is proved to be suitable for industrial application.
As the industrial hydrogen evolution conditions are high concentration and high temperature, the current is set to be 0.05A, the temperature is adjusted to be 60 ℃, the electrolyte concentration is 6M KOH, and the time is set to be 7200 s. As shown in fig. 8, the overpotential change of the catalyst is not large, and its good stability under industrial hydrogen evolution conditions is sufficiently demonstrated.
Application example 2
(1) Using a three-electrode system, the catalyst prepared in example 1 was used as the working electrode, the counter electrode was a carbon rod, the reference electrode was a saturated Ag/AgCl electrode, and the electrolyte was 1.0M KOH +0.5M NaCl;
(2) CV activation: the electrochemical workstation of Shanghai Chenghua CHI 660E was used, and nitrogen was introduced into the electrolyte for 30min before the test. Adopting CV program, testing interval is 0-0.8V vs. RHE, sweep speed is 50mV/s, circulating for 20 circles, and the electrode reaches stable state;
after activation of the catalyst prepared in example 1 by cyclic sweep voltammetry (CV) tests, the procedure was switched to the LSV procedure with a test interval of 0 to-0.8V vs. RHE, a sweep rate of 5mV/s and an overpotential of 0V and 500mA/cm relative to the reversible hydrogen electrode -2 The difference in potential was measured. As shown in FIG. 9, the polarization curve of the hydrogen evolution reaction of the Ru/Ni-Mo/NF catalyst in 1.0M KOH +0.5M NaCl solution provided by this example is shown in FIG. 9. it can be seen from FIG. 9 that the overpotential of the Ru/Ni-Mo/NF catalyst in the alkaline electrolyte is only 89mV (eta. sup. 500mA/cm2 ) The performance difference of the method is not great from that of the method in a 1M KOH solution, which shows the application prospect of the method in directly electrolyzing seawater to prepare hydrogen.
Example 2
The embodiment provides a ruthenium-modified nickel-molybdenum nanorod composite catalyst, which is different from the embodiment 1 in the amount of added Ru precursor and is prepared according to the following steps:
(1) weighing 1.09g of nickel nitrate hexahydrate solid particles, 0.035g of ammonia hexachlororuthenate solid particles and 1.159g of ammonium molybdate solid particles, dissolving in 37.5ml of deionized water, and mixing for 30min to form a precursor solution;
(2) transferring the precursor solution into a 50mL hydrothermal kettle, placing 2 x 4cm of foamed nickel into a reaction kettle, carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at 160 ℃, taking out the foamed nickel precursor, carrying out ultrasonic treatment in ultrapure water for about 1 hour, placing the washed foamed nickel precursor into the oven, and drying at 60 ℃ for 10 hours to obtain a ruthenium-containing nickel molybdate precursor;
(3) the prepared nickel molybdate precursor containing ruthenium and loaded on the surface of the foamed nickel is placed in the center of a horizontal tube furnace in H 2 Heating at 350 deg.C for 1h under Ar (5%/95%) atmosphere, and heating to 450 deg.C at a heating rate of 5 deg.C/min for 1 h. After the reaction is finished, cooling to room temperature,the ruthenium modified nickel-molybdenum nanorod composite catalyst is obtained and is marked as Ru/Ni-Mo/NF.
Example 3
The embodiment provides a ruthenium-modified nickel-molybdenum nanorod composite catalyst, which is different from the embodiment 2 in the amount of added Ru precursor and is prepared according to the following steps:
(1) weighing 1.09g of nickel nitrate hexahydrate solid particles, 0.105g of ammonia hexachlororuthenate solid particles and 1.159g of ammonium molybdate solid particles, dissolving in 37.5ml of deionized water, and mixing for 30min to form a precursor solution;
(2) transferring the precursor solution into a 50mL hydrothermal kettle, placing 2 x 4cm of foamed nickel into a reaction kettle, carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at 160 ℃, taking out the foamed nickel precursor, carrying out ultrasonic treatment in ultrapure water for about 1 hour, placing the washed foamed nickel precursor into the oven, and drying at 60 ℃ for 10 hours to obtain a ruthenium-containing nickel molybdate precursor;
(3) the prepared nickel molybdate precursor containing ruthenium and loaded on the surface of the foamed nickel is placed in the center of a horizontal tube furnace in H 2 Heating at 350 deg.C for 1h under Ar (5%/95%) atmosphere, and heating to 450 deg.C at a heating rate of 5 deg.C/min for 1 h. And after the reaction is finished, cooling to room temperature to obtain the ruthenium modified nickel-molybdenum nanorod composite catalyst, which is marked as Ru/Ni-Mo/NF.
Example 4
The embodiment provides a ruthenium-modified nickel-molybdenum nanorod composite catalyst, which is different from the embodiment 1 in thermal reduction temperature and is prepared according to the following steps:
(1) weighing 1.09g of nickel nitrate hexahydrate solid particles, 0.07g of ammonia hexachlororuthenate solid particles and 1.159g of ammonium molybdate solid particles, dissolving in 37.5ml of deionized water, and mixing for 30min to form a precursor solution;
(2) transferring the precursor solution into a 50mL hydrothermal kettle, placing 2 x 4cm of foamed nickel into a reaction kettle, carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at 160 ℃, taking out the foamed nickel precursor, carrying out ultrasonic treatment in ultrapure water for about 1 hour, placing the washed foamed nickel precursor into the oven, and drying at 60 ℃ for 10 hours to obtain a ruthenium-containing nickel molybdate precursor;
(3) the prepared nickel molybdate precursor containing ruthenium and loaded on the surface of the foamed nickel is placed in the center of a horizontal tube furnace in H 2 Heating to 350 ℃ at a heating rate of 5 ℃/min for 2h under an/Ar (5%/95%) atmosphere. And after the reaction is finished, cooling to room temperature to obtain the ruthenium modified nickel-molybdenum nanorod composite catalyst, which is marked as Ru/Ni-Mo/NF.
Example 5
The embodiment provides a ruthenium-modified nickel-molybdenum nanorod composite catalyst, which is different from the embodiment 4 in thermal reduction temperature and is prepared according to the following steps:
(1) weighing 1.09g of nickel nitrate hexahydrate solid particles, 0.07g of ammonia hexachlororuthenate solid particles and 1.159g of ammonium molybdate solid particles, dissolving in 37.5ml of deionized water, and mixing for 30min to form a precursor solution;
(2) transferring the precursor solution into a 50mL hydrothermal kettle, placing 2 x 4cm of foamed nickel into a reaction kettle, carrying out hydrothermal reaction for 6 hours in an explosion-proof constant-temperature oven at 160 ℃, taking out the foamed nickel precursor, carrying out ultrasonic treatment in ultrapure water for about 1 hour, placing the washed foamed nickel precursor into the oven, and drying at 60 ℃ for 10 hours to obtain a ruthenium-containing nickel molybdate precursor;
(3) the prepared nickel molybdate precursor containing ruthenium and loaded on the surface of the foamed nickel is placed in the center of a horizontal tube furnace in H 2 Heating at 350 deg.C for 1h under Ar (5%/95%) atmosphere, and heating to 550 deg.C at a heating rate of 5 deg.C/min for 1 h. And after the reaction is finished, cooling to room temperature to obtain the ruthenium modified nickel-molybdenum nanorod composite catalyst, which is marked as Ru/Ni-Mo/NF.
The catalysts of examples 2-5 were tested for catalytic performance as in application example 1, and after cyclic sweep voltammetry (CV) test activation, the program was switched to the LSV program at a test current density of 500mA cm -2 The overpotentials of the catalysts of examples 2-5 were 134mV, 124mV, 155mV, and 124mV, respectively, and the effects were superior to those of comparative examples 1-4, and even superior to those of commercial products.

Claims (10)

1. A preparation method of a ruthenium-modified molybdenum-nickel nanorod composite catalyst is characterized by comprising the following steps:
step 1, mixing nickel salt, molybdate and ruthenium salt in a solvent to obtain a solution, soaking foam nickel in the solution to perform hydrothermal reaction to obtain a foam nickel precursor, and performing ultrasonic treatment and drying to obtain a ruthenium-loaded nickel molybdate precursor;
and 2, carrying out thermal reduction treatment on the ruthenium-loaded nickel molybdate precursor to obtain the ruthenium-modified molybdenum-nickel nanorod composite catalyst.
2. The method of preparing the ruthenium-modified molybdenum-nickel nanorod composite catalyst according to claim 1, wherein the nickel salt comprises any one of nickel nitrate hexahydrate, nickel chloride hexahydrate, and nickel sulfate hexahydrate; the molybdate comprises sodium molybdate or ammonium molybdate; the ruthenium salt comprises any one of ruthenium acetylacetonate, ruthenium chloride trihydrate and ammonia hexachlororuthenate.
3. The preparation method of the ruthenium-modified molybdenum-nickel nanorod composite catalyst according to claim 1, wherein the molar ratio of the nickel salt to the molybdate is 1: 1-5; the molar ratio of the ruthenium salt to the nickel salt is 1: 10-40.
4. The preparation method of the ruthenium-modified molybdenum-nickel nanorod composite catalyst according to claim 1, wherein the mass ratio of the nickel foam to the nickel salt is 1: 0.5-2.
5. The method for preparing the ruthenium-modified molybdenum-nickel nanorod composite catalyst according to claim 1, wherein the solvent in the step 1 comprises at least one of water, ethanol and N, N-dimethylformamide.
6. The method for preparing the ruthenium modified molybdenum-nickel nanorod composite catalyst as claimed in claim 1, wherein the hydrothermal reaction temperature in step 1 is 150-200 ℃ and the reaction time is 5-10 h.
7. The preparation method of the ruthenium-modified molybdenum-nickel nanorod composite catalyst according to claim 1, wherein the ultrasonic time in the step 1 is 2-4 hours.
8. The method for preparing the ruthenium-modified molybdenum-nickel nanorod composite catalyst as claimed in claim 1, wherein the thermal reduction treatment temperature in step 2 is 300-600 ℃ for 1-3 h; the thermal reduction treatment atmosphere condition is H 2 Ar, the volume concentration of hydrogen is 3-10%.
9. The ruthenium modified molybdenum-nickel nanorod composite catalyst obtained by the preparation method according to any one of claims 1-8.
10. The use of the ruthenium-modified molybdenum-nickel nanorod composite catalyst of claim 9 in an alkaline solution for an electrolytic hydrolysis hydrogen evolution reaction.
CN202210577985.9A 2022-05-25 2022-05-25 Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof Pending CN114875442A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210577985.9A CN114875442A (en) 2022-05-25 2022-05-25 Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210577985.9A CN114875442A (en) 2022-05-25 2022-05-25 Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114875442A true CN114875442A (en) 2022-08-09

Family

ID=82678383

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210577985.9A Pending CN114875442A (en) 2022-05-25 2022-05-25 Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114875442A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115044920A (en) * 2022-08-16 2022-09-13 河南师范大学 Preparation method of self-supporting ultralow-crystallinity nano-array electrocatalyst for hydrogen production by water electrolysis
CN116043267A (en) * 2023-01-31 2023-05-02 青岛中石大新能源科技有限公司 Ferronickel composite defect type molybdenum oxide electrocatalyst and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111871427A (en) * 2020-07-16 2020-11-03 清华-伯克利深圳学院筹备办公室 Precious metal/molybdenum-nickel composite material and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111871427A (en) * 2020-07-16 2020-11-03 清华-伯克利深圳学院筹备办公室 Precious metal/molybdenum-nickel composite material and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115044920A (en) * 2022-08-16 2022-09-13 河南师范大学 Preparation method of self-supporting ultralow-crystallinity nano-array electrocatalyst for hydrogen production by water electrolysis
CN115044920B (en) * 2022-08-16 2022-11-01 河南师范大学 Preparation method of self-supporting ultralow-crystallinity nano-array electrocatalyst for hydrogen production by water electrolysis
CN116043267A (en) * 2023-01-31 2023-05-02 青岛中石大新能源科技有限公司 Ferronickel composite defect type molybdenum oxide electrocatalyst and preparation method and application thereof
CN116043267B (en) * 2023-01-31 2023-08-29 青岛中石大新能源科技有限公司 Ferronickel composite defect type molybdenum oxide electrocatalyst and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN108385124B (en) Preparation method of transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction
CN110479329B (en) Preparation and application of phosphorus-doped cobalt telluride nano material
CN109954503B (en) Nickel selenide and ternary nickel-iron selenide composite electrocatalyst, preparation method and application
CN106732649A (en) A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst
CN113005469B (en) Ruthenium-loaded amorphous nickel hydroxide/nickel phosphide composite electrode and preparation method and application thereof
CN112481653B (en) Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof
CN108554426B (en) Difunctional cobalt diselenide material and preparation and application thereof
CN109852992B (en) Efficient electrocatalytic full-decomposition water nanosheet array electrode and preparation method and application thereof
CN113437314B (en) Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof
CN114875442A (en) Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof
CN110314690B (en) Bimetallic sulfide Ni with heterogeneous interface coupling3S2/FeS composite material and preparation method and application thereof
CN112080759B (en) Preparation method of bismuth-doped bimetallic sulfide electrode for electrocatalytic oxidation of urea
CN111701607A (en) MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof
CN113862693A (en) Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst
CN110565113B (en) Preparation method of composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution
CN113512738B (en) Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof
CN113174053B (en) Mn-MOF based on urotropine and preparation method and application thereof
CN112023922B (en) Pt-MnO2Material, preparation method and application thereof
CN110137523B (en) Hydrogen-making hydrazine hydrate fuel cell device
CN115807241A (en) Ultrathin iridium-based nanosheet catalyst, and preparation method and application thereof
CN108654655A (en) A kind of phosphatization rhodium catalyst and preparation method being used to prepare the special hydrogen of fuel cell
CN113930800A (en) Heterostructure electrocatalytic hydrogen evolution material and preparation method and application thereof
CN114214636B (en) Method for preparing cobalt-based nanosheet self-supporting electrode by selenium-containing ligand and application of cobalt-based nanosheet self-supporting electrode
CN115074774B (en) Rhodium-based hollow porous microsphere/nickel foam electrode and preparation method and application thereof
CN114892206B (en) Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination