WO2023284064A1 - Method for preparing fe@cumoo4nwa/cu catalyst and application - Google Patents

Method for preparing fe@cumoo4nwa/cu catalyst and application Download PDF

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WO2023284064A1
WO2023284064A1 PCT/CN2021/113396 CN2021113396W WO2023284064A1 WO 2023284064 A1 WO2023284064 A1 WO 2023284064A1 CN 2021113396 W CN2021113396 W CN 2021113396W WO 2023284064 A1 WO2023284064 A1 WO 2023284064A1
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nwa
cumoo
catalyst
water
concentration
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PCT/CN2021/113396
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French (fr)
Chinese (zh)
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薛晓东
冷艳秋
庄云飞
姜云鹏
李超
刘国祥
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山东省环境保护科学研究设计院有限公司
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Publication of WO2023284064A1 publication Critical patent/WO2023284064A1/en

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    • 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
    • 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
    • C25B11/091—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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention belongs to the technical field of inorganic nano-array catalysts, and in particular relates to a preparation method and application of a Fe@CuMoO 4 NWA/Cu catalyst.
  • Hydrogen energy that is, hydrogen, has become the most ideal secondary energy source to replace fossil energy because of its high calorific value per unit mass and its non-polluting products.
  • Electrocatalytic water splitting for hydrogen production is the use of electrical energy as the driving force for water splitting to produce hydrogen, which has received more and more attention.
  • electric energy is no longer only relying on the burning of fossil fuels, but can be directly generated in a variety of ways, and the stable electric energy obtained by using renewable energy (solar energy, wind energy, tidal energy, etc.) has no pollution to the environment. Since the overpotential of hydrogen production by electrolysis of water is very high, electrocatalysts are used to reduce the problem of excessive power consumption during the electrolysis process.
  • the present invention provides a method for preparing Fe@CuMoO nanowire arrays by redoxing Cu(OH) 2 nanowire arrays at room temperature on foamed copper, followed by hydrothermal ion exchange, and its electrocatalytic water splitting for hydrogen production Applications.
  • one of the purposes of the present invention is to propose a method for preparing Fe@CuMoO 4 NWA/Cu catalyst, comprising the following steps:
  • the molybdenum source reagent and the iron source reagent are dissolved in water to obtain a mixed solution, then Cu(OH) 2 NWA/Cu is added to the mixed solution, and the Fe@CuMoO 4 NWA/Cu catalyst is obtained by hydrothermal reaction.
  • the oxidant is ammonium persulfate or hydrogen peroxide
  • the molybdenum source reagent is one or more of sodium molybdate, ammonium molybdate tetrahydrate or lithium molybdate
  • the iron source reagent is iron sulfate , one or more of ferrous sulfate, ferric chloride, ferric nitrate or ferric oxide.
  • the immersion in the foamed copper is specifically: the immersion time of the foamed copper at room temperature is 0.5-30 minutes, and then cleaned several times.
  • the hydrothermal method is carried out at a temperature of 100-160° C. for 4-72 hours, and the obtained product is washed several times after the reaction.
  • the concentration of sodium hydroxide is 0.1-2 mol/L; the concentration of the ammonium persulfate dissolved in water is 0.1-2 mol/L; the peroxide
  • the mass concentration of hydrogen dissolved in water is 0.1-30%.
  • the molybdenum source reagent has a concentration of 0.1-2.0 mol/L
  • the iron source reagent has a concentration of 0.1-2.0 mol/L.
  • the second purpose of the present invention is to propose an application of Fe@CuMoO 4 NWA/Cu catalyst in electrocatalytic water splitting for hydrogen production.
  • the electrocatalytic water splitting hydrogen production is specifically as follows: using a three-electrode system, testing with an electrochemical workstation, using Fe@CuMoO 4 NWA/Cu as a working electrode, using a carbon rod as a counter electrode, and using Ag/AgCl or The Hg/HgO electrode is used as the reference electrode, and sodium hydroxide solution or sodium sulfate solution is used as the electrolyte to carry out the electrocatalytic hydrogen production reaction.
  • the present invention oxidizes copper into positive divalent Cu 2+ through the reasonable ratio of ammonium persulfate (NH 4 ) 2 S 2 O 8 and sodium hydroxide Na(OH), and the generated Cu 2+ immediately reacts with sodium hydroxide Na
  • the (OH) reaction generates nanowire arrays, thereby exposing more catalytically active sites, which is beneficial to the subsequent electrocatalytic process.
  • Adopting the technical solution of the present invention the synthesis of the Cu(OH) 2 NWA/Cu precursor is carried out at room temperature.
  • the precursor synthesized by this method Compared with the traditional high-temperature and high-pressure environment, the precursor synthesized by this method has the characteristics of low energy consumption and superior performance, and the improved The precursor material synthesized by this method has good stability and can better provide a good chemical reaction site for the next step of catalyst preparation.
  • Copper foam is a new multifunctional material with a large number of connected or disconnected pores evenly distributed in the copper matrix.
  • the present invention provides a method for preparing Fe-doped CuMoO 4 nanowire arrays Fe@CuMoO 4 NWA/Cu by hydrothermal ion exchange after preparing Cu(OH) 2 nanowire arrays on foamed copper at room temperature, exemplarily , see the following examples.
  • a preparation method of Fe@CuMoO 4 NWA/Cu catalyst exemplarily, 50mL deionized water is added in the clean beaker, ammonium persulfate is added (exemplarily, the concentration of ammonium persulfate after adding is 0.1mol /L) and sodium hydroxide (the concentration of sodium hydroxide after adding is 0.1mol/L), stirred for 30min to form a clear and transparent solution, after foam copper was pretreated by ultrasonic cleaning in hydrochloric acid solution, immersed in the clear and transparent solution, at room temperature After soaking for 5 minutes, after the reaction, the obtained product was rinsed with ultrapure water and ethanol for 3 to 5 times respectively to obtain a Cu(OH) 2 nanowire array Cu(OH) 2 NWA/Cu grown on foamed copper;
  • the polarization curve test is carried out in a three-electrode system.
  • the electrolyte is sodium sulfate solution.
  • the polarization curve test voltage range is -1.8 ⁇ 0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 90mV (The lower the overpotential, the better the performance).
  • the application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system.
  • the production rate is 1mol/h
  • the electrolyte is sodium sulfate solution.
  • the potential was set at 90 mV (relative to reversible hydrogen potential, vs. RHE) and the run time was 1 hour.
  • a preparation method of Fe@CuMoO 4 NWA/Cu catalyst Exemplarily, 50mL deionized water is added to a cleaned beaker, and ammonium persulfate is added (exemplarily, the concentration of ammonium persulfate after adding is 2mol/ L) and sodium hydroxide (concentration 2mol/L of sodium hydroxide after adding), stir 30min to form clear and transparent solution, the foam copper of pretreatment is immersed in the above-mentioned solution, soak 10min at room temperature, after reaction finishes, will obtain The product was washed with ultrapure water and ethanol for 3 to 5 times respectively to obtain Cu(OH) 2 nanowire array Cu(OH) 2 NWA/Cu grown on foamed copper;
  • the hydrothermal reaction kettle has a stainless steel shell and a polytetrafluoroethylene lining, and puts Cu(OH) 2 NWA/Cu, 0.5g iron sulfate (concentration: 2.0mol/L), and 35mL ultrapure water. After sealing the hydrothermal autoclave, it was placed in an oven at 100 °C for 48 hours. After natural cooling, it was washed with deionized water and absolute ethanol, and dried in vacuum to obtain Fe@CuMoO 4 NWA/Cu.
  • the polarization curve test is carried out in a three-electrode system.
  • the electrolyte is sodium sulfate solution.
  • the polarization curve test voltage range is -1.8 ⁇ 0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 86mV .
  • the long-term electrocatalytic water splitting hydrogen yield was tested in a three-electrode system.
  • the electrolyte was sodium sulfate solution, and the potential was set to 86mV (relative to the reversible hydrogen potential, vs. RHE) run time is 1 hour.
  • the application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system.
  • the production rate is 0.8mol/h.
  • the electrolyte is sodium sulfate solution.
  • the potential was set at 85 mV (relative to the reversible hydrogen potential, vs. RHE) and the run time was 1 hour.
  • the electrolytic cell for electrocatalytic hydrogen production is connected with the barometer sensor, the real-time pressure data in the pressure gauge is output on the computer, and the amount of the gas is calculated by the Clapeyron equation, and then the catalyst is calculated.
  • the faradaic efficiency of hydrogen production in electrocatalytic water splitting is 99.3%.
  • the polarization curve test is carried out in a three-electrode system.
  • the electrolyte is sodium sulfate solution.
  • the polarization curve test voltage range is -1.8 ⁇ 0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 70mV .
  • the application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system, and the electrolyte is sodium sulfate solution.
  • the potential was set at 70 mV (relative to the reversible hydrogen potential, vs. RHE) and the run time was 1 hour.
  • the polarization curve test is carried out in a three-electrode system.
  • the electrolyte is sodium sulfate solution.
  • the polarization curve test voltage range is -1.8 ⁇ 0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 70mV .
  • the application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system.
  • the electrolyte is a sodium sulfate solution, and the potential is set to 70mV (relative to the reversible Hydrogen potential, vs. RHE) run time was 1 hour.
  • the polarization curve test is carried out in a three-electrode system.
  • the electrolyte is sodium sulfate solution.
  • the polarization curve test voltage range is -1.8 ⁇ 0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 85mV .
  • the copper foam has good conductivity, which is helpful for electron transport during the catalytic process, and the Fe@CuMoO 4 nanowire array structure exposes a higher active area, which helps to improve the catalytic efficiency.
  • the application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the
  • the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system, and the electrolyte is sodium sulfate solution.
  • the potential was set at 70 mV (relative to reversible hydrogen potential, vs. RHE) and the run time was 1.5 hours.

Abstract

A method for preparing a Fe-doped CuMoO4 nanowire array on copper foam (Fe@CuMoO4NWA/Cu) catalyst, and an application. The method comprises the following steps: dissolving an oxidant and sodium hydroxide in water, and then immersing copper foam into same to obtain a Cu(OH)2 nanowire array grown on copper foam (Cu(OH)2NWA/Cu); and dissolving a molybdenum source reagent and an iron source reagent in water to obtain a mixed solution, then adding the Cu(OH)2NWA/Cu into the mixed solution, and using a hydrothermal method for reaction to obtain a Fe@CuMoO4NWA/Cu catalyst. Synthesis of the Cu(OH)2NWA/Cu precursor is performed at room temperature; compared with a conventional high-temperature and high-pressure environment, the precursor synthesized using the method has features such as low energy consumption and excellent properties; and the precursor material synthesized using the method has good stability, and can better provide a good chemical reaction place for the next step of catalyst preparation.

Description

一种Fe@CuMoO 4NWA/Cu催化剂的制备方法及应用 A Fe@CuMoO Preparation and Application of 4NWA/Cu Catalyst 技术领域technical field
本发明属于无机纳米阵列催化剂技术领域，特别涉及一种Fe@CuMoO 4NWA/Cu催化剂的制备方法及应用。 The invention belongs to the technical field of inorganic nano-array catalysts, and in particular relates to a preparation method and application of a Fe@CuMoO 4 NWA/Cu catalyst.
背景技术Background technique
能源是人类社会生存和发展的物质基础，也是经济发展的原动力，在国民经济中占有特别重要的战略地位。一直以来，化石能源作为能源的主体。但是，化学能源属于不可再生能源并且他们的储量有限。随着全球经济的迅速发展，世界人口的快速增长以及人们对物质需求的增加，化石能源的储量急剧减少并且化石能源燃烧的主要产物是二氧化碳、一氧化碳、硫氧化合物、氮氧化合物以及不完全燃烧颗粒物，其中，二氧化碳的大量排放是引起温室效应的主要因素，硫氧化合物、氮氧化合物以及不完全燃烧颗粒物是空气中的主要污染物，是雾霾产生的罪魁祸首，能源问题成为全世界关注的焦点。所以，人们开始更加迫切地寻找开发绿色、高效、可持续循环的可再生能源。氢能、风能、太阳能、地热能、水能、核能等多种新型能源，作为二次能源，具有清洁无污染以及可再生性，引起众多科研工作者的关注。氢能，即氢气，因为单位质量燃烧热值高产物无污染，更是成为替代化石能源的最理想的二次能源。Energy is the material basis for the survival and development of human society, as well as the driving force for economic development, and occupies a particularly important strategic position in the national economy. For a long time, fossil energy has been the main body of energy. However, chemical energy sources are non-renewable energy sources and their reserves are limited. With the rapid development of the global economy, the rapid growth of the world's population and the increase in people's demand for materials, the reserves of fossil energy have decreased sharply and the main products of fossil energy combustion are carbon dioxide, carbon monoxide, sulfur oxides, nitrogen oxides and incomplete combustion. Particulate matter, among which, a large amount of carbon dioxide emission is the main factor causing the greenhouse effect. Sulfur oxides, nitrogen oxides and incomplete combustion particles are the main pollutants in the air and the culprit of smog. Energy issues have become the focus of the world hot spot. Therefore, people began to look for the development of green, efficient and sustainable renewable energy more urgently. Hydrogen energy, wind energy, solar energy, geothermal energy, water energy, nuclear energy and other new energy sources, as secondary energy sources, are clean, non-polluting and renewable, and have attracted the attention of many scientific researchers. Hydrogen energy, that is, hydrogen, has become the most ideal secondary energy source to replace fossil energy because of its high calorific value per unit mass and its non-polluting products.
电催化水分解制氢是将电能作为水分解的动力制备氢气，已受到越来越多的关注。现在电能已经不再仅仅依靠化石燃料燃烧，可以依靠多种方式直接产生，利用可再生能源(太阳能、风能、潮汐能等)转化得到的稳定的电能，对环境没有污染。由于电解水制氢的过电势很高，于是利用电催化剂来降低电解过程中电能消耗过大的问题。Electrocatalytic water splitting for hydrogen production is the use of electrical energy as the driving force for water splitting to produce hydrogen, which has received more and more attention. Now electric energy is no longer only relying on the burning of fossil fuels, but can be directly generated in a variety of ways, and the stable electric energy obtained by using renewable energy (solar energy, wind energy, tidal energy, etc.) has no pollution to the environment. Since the overpotential of hydrogen production by electrolysis of water is very high, electrocatalysts are used to reduce the problem of excessive power consumption during the electrolysis process.
纳米材料由于独特的尺寸赋予了材料许多新颖的性能，应用于电催化领域表现出优异的活性。贵金属纳米材料的析氢性能虽然优异，但是其价格昂贵，储量低。因此，生产非贵金属的纳米结构催化剂用于电催化水分解制氢的研究备受关注，近几年在能源领域一直是最大热门。鉴于此，本发明提供了一种在泡沫铜上常温氧化还原制备Cu(OH) 2纳米线阵列后用水热离子交换后生成Fe@CuMoO 4纳米线阵列的制备方法及其电催化水分解制氢的应用。 Due to their unique size, nanomaterials endow materials with many novel properties, and exhibit excellent activity in the field of electrocatalysis. Although noble metal nanomaterials have excellent hydrogen evolution performance, they are expensive and have low reserves. Therefore, the research on the production of non-noble metal nanostructured catalysts for electrocatalytic water splitting to hydrogen production has attracted much attention, and has been the hottest topic in the energy field in recent years. In view of this, the present invention provides a method for preparing Fe@CuMoO nanowire arrays by redoxing Cu(OH) 2 nanowire arrays at room temperature on foamed copper, followed by hydrothermal ion exchange, and its electrocatalytic water splitting for hydrogen production Applications.
发明内容Contents of the invention
针对上述问题，本发明目的之一在于提出一种Fe@CuMoO 4NWA/Cu催化剂的制备方法，包括以下步骤： In view of the above problems, one of the purposes of the present invention is to propose a method for preparing Fe@CuMoO 4 NWA/Cu catalyst, comprising the following steps:
将氧化剂和氢氧化钠溶解于水中，再浸入泡沫铜得到在泡沫铜上生长了Cu(OH) 2的纳米线阵列Cu(OH) 2NWA/Cu； Dissolving the oxidizing agent and sodium hydroxide in water, and then immersing in foamed copper to obtain Cu(OH) 2 NWA/Cu nanowire arrays with Cu(OH) 2 grown on the foamed copper;
将钼源试剂和铁源试剂溶于水中得到混合溶液，再将Cu(OH) 2NWA/Cu加入到所述混合溶液中，采用水热法反应得到所述Fe@CuMoO 4NWA/Cu催化剂。 The molybdenum source reagent and the iron source reagent are dissolved in water to obtain a mixed solution, then Cu(OH) 2 NWA/Cu is added to the mixed solution, and the Fe@CuMoO 4 NWA/Cu catalyst is obtained by hydrothermal reaction.
优选地，所述氧化剂为过硫酸铵或过氧化氢；所述钼源试剂为钼酸钠、四水合钼酸铵或钼酸锂中的一种或几种；所述铁源试剂为硫酸铁、硫酸亚铁、氯化铁、硝酸铁或三氧化二铁中的一种或者几种。Preferably, the oxidant is ammonium persulfate or hydrogen peroxide; the molybdenum source reagent is one or more of sodium molybdate, ammonium molybdate tetrahydrate or lithium molybdate; the iron source reagent is iron sulfate , one or more of ferrous sulfate, ferric chloride, ferric nitrate or ferric oxide.
优选地，所述浸入泡沫铜具体为：室温下泡沫铜浸入时间为0.5～30min，再清洗若干次。Preferably, the immersion in the foamed copper is specifically: the immersion time of the foamed copper at room temperature is 0.5-30 minutes, and then cleaned several times.
优选地，所述水热法于100～160℃温度下进行反应4～72h，反应结束后将所得产物清洗若干次。Preferably, the hydrothermal method is carried out at a temperature of 100-160° C. for 4-72 hours, and the obtained product is washed several times after the reaction.
优选地，所述将氧化剂和氢氧化钠溶解于水中后，氢氧化钠的浓度为0.1～2mol/L；所述过硫酸铵溶于水后的浓度为0.1～2mol/L；所述过氧化氢溶于水后的质量浓度为0.1～30％。Preferably, after the oxidant and sodium hydroxide are dissolved in water, the concentration of sodium hydroxide is 0.1-2 mol/L; the concentration of the ammonium persulfate dissolved in water is 0.1-2 mol/L; the peroxide The mass concentration of hydrogen dissolved in water is 0.1-30%.
优选地，所述钼源试剂的浓度为0.1～2.0mol/L，所述铁源试剂的浓度为0.1～2.0mol/L。Preferably, the molybdenum source reagent has a concentration of 0.1-2.0 mol/L, and the iron source reagent has a concentration of 0.1-2.0 mol/L.
本发明目的之二在于提出一种Fe@CuMoO 4NWA/Cu催化剂在电催化水分解制氢的应用。 The second purpose of the present invention is to propose an application of Fe@CuMoO 4 NWA/Cu catalyst in electrocatalytic water splitting for hydrogen production.
优选地，所述电催化水分解制氢具体为：采用三电极体系，通过电化学工作站进行测试，以Fe@CuMoO 4NWA/Cu为工作电极，以碳棒为对电极，以Ag/AgCl或Hg/HgO电极为参比电极，以氢氧化钠溶液或硫酸钠溶液为电解液，进行电催化产氢反应。 Preferably, the electrocatalytic water splitting hydrogen production is specifically as follows: using a three-electrode system, testing with an electrochemical workstation, using Fe@CuMoO 4 NWA/Cu as a working electrode, using a carbon rod as a counter electrode, and using Ag/AgCl or The Hg/HgO electrode is used as the reference electrode, and sodium hydroxide solution or sodium sulfate solution is used as the electrolyte to carry out the electrocatalytic hydrogen production reaction.
本发明通过过硫酸铵(NH 4) 2S 2O 8和氢氧化钠Na(OH)的合理配比，使铜氧化成正二价的Cu 2+，生成的Cu 2+立即与氢氧化钠Na(OH)反应生成纳米线阵列，从而暴露出更多的催化活性位点，有利于后续的电催化过程。采用本发明技术方案，Cu(OH) 2NWA/Cu前驱体的合成是常温下进行的，相对于传统的高温高压 环境，该方法合成的前驱体具有能耗小、性能优越等特点，且改方式合成的前驱体材料稳定性好，能更好的为下一步的催化剂制备提供良好的化学反应场所。 The present invention oxidizes copper into positive divalent Cu 2+ through the reasonable ratio of ammonium persulfate (NH 4 ) 2 S 2 O 8 and sodium hydroxide Na(OH), and the generated Cu 2+ immediately reacts with sodium hydroxide Na The (OH) reaction generates nanowire arrays, thereby exposing more catalytically active sites, which is beneficial to the subsequent electrocatalytic process. Adopting the technical solution of the present invention, the synthesis of the Cu(OH) 2 NWA/Cu precursor is carried out at room temperature. Compared with the traditional high-temperature and high-pressure environment, the precursor synthesized by this method has the characteristics of low energy consumption and superior performance, and the improved The precursor material synthesized by this method has good stability and can better provide a good chemical reaction site for the next step of catalyst preparation.
本发明的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention.
具体实施方式detailed description
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地说明，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. the embodiment. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
泡沫铜是一种在铜基体中均匀分布着大量连通或不连通孔洞的新型多功能材料。本发明提供了一种在泡沫铜上常温氧化还原制备Cu(OH) 2纳米线阵列后用水热离子交换生成Fe掺杂CuMoO 4纳米线阵列Fe@CuMoO 4NWA/Cu的制备方法，示例性地，见如下实施例。 Copper foam is a new multifunctional material with a large number of connected or disconnected pores evenly distributed in the copper matrix. The present invention provides a method for preparing Fe-doped CuMoO 4 nanowire arrays Fe@CuMoO 4 NWA/Cu by hydrothermal ion exchange after preparing Cu(OH) 2 nanowire arrays on foamed copper at room temperature, exemplarily , see the following examples.
实施例1：Example 1:
一种Fe@CuMoO 4NWA/Cu催化剂的制备方法，示例性地，将50mL去离子水加入到洗净的烧杯中，加入过硫酸铵(示例性地，加入后过硫酸铵的浓度为0.1mol/L)和氢氧化钠(加入后氢氧化钠的浓度0.1mol/L)，搅拌30min形成澄清透明溶液，将泡沫铜于盐酸溶液超声清洗预处理后，浸入该澄清透明溶液中，在室温下浸泡5min，反应结束后，将得到的产物用超纯水、乙醇分别冲洗3～5次，得到在泡沫铜上生长的Cu(OH) 2纳米线阵列Cu(OH) 2NWA/Cu； A preparation method of Fe@CuMoO 4 NWA/Cu catalyst, exemplarily, 50mL deionized water is added in the clean beaker, ammonium persulfate is added (exemplarily, the concentration of ammonium persulfate after adding is 0.1mol /L) and sodium hydroxide (the concentration of sodium hydroxide after adding is 0.1mol/L), stirred for 30min to form a clear and transparent solution, after foam copper was pretreated by ultrasonic cleaning in hydrochloric acid solution, immersed in the clear and transparent solution, at room temperature After soaking for 5 minutes, after the reaction, the obtained product was rinsed with ultrapure water and ethanol for 3 to 5 times respectively to obtain a Cu(OH) 2 nanowire array Cu(OH) 2 NWA/Cu grown on foamed copper;
将30mL去离子水加入到洗净的烧杯中，加入钼酸钠(0.2086g，1mmol，浓度为0.1mol/L)和0.5g硝酸铁，浓度为0.1mol/L，搅拌30min形成澄清透明溶液，将上述溶液转移到实验室用50mL高温水热反应釜，水热反应釜具有不锈钢外壳，聚四氟乙烯内衬，放入Cu(OH) 2NWA/Cu，密封水热高压釜后将其置于120℃的烘箱内保温24h，自然冷却后，所得产物分别用去离子水、无水乙醇洗涤、真空干燥后得到Fe@CuMoO 4NWA/Cu催化剂。 Add 30mL of deionized water to the cleaned beaker, add sodium molybdate (0.2086g, 1mmol, the concentration is 0.1mol/L) and 0.5g ferric nitrate, the concentration is 0.1mol/L, stir for 30min to form a clear and transparent solution, The above solution was transferred to a 50mL high-temperature hydrothermal reaction kettle for the laboratory. The hydrothermal reaction kettle had a stainless steel shell and a polytetrafluoroethylene lining, and Cu(OH) 2 NWA/Cu was put into it. After sealing the hydrothermal autoclave, it was placed After heat preservation in an oven at 120°C for 24 hours, after natural cooling, the obtained product was washed with deionized water and absolute ethanol, and vacuum-dried to obtain Fe@CuMoO 4 NWA/Cu catalyst.
以Fe@CuMoO 4NWA/Cu为工作电极，在三电极体系中进行极化曲线测试，电解液是硫酸钠溶液，极化曲线测试电压区间为-1.8～0V，最高电位0V，最 低电位-1.8V，开始电位为0V，终止电位为-1.8V，扫描速率为0.005V/s，采样间隔为0.001V，静置时间为2s，当电流密度是10mA/cm 2时，需要的过电势为90mV(过电势越低，性能越优越)。 Using Fe@CuMoO 4 NWA/Cu as the working electrode, the polarization curve test is carried out in a three-electrode system. The electrolyte is sodium sulfate solution. The polarization curve test voltage range is -1.8～0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 90mV (The lower the overpotential, the better the performance).
基于上述方法制备得到的Fe@CuMoO 4NWA/Cu催化剂在电催化产氢上的应用，示例性地，通过电化学工作站进行测试，以Fe@CuMoO 4NWA/Cu为工作电极，以碳棒为对电极，以Ag/AgCl或Hg/HgO电极为参比电极，在三电极体系中进行长时间电催化水分解氢气产率的测试，产率为1mol/h，电解液是硫酸钠溶液。电位设置为90mV(相对于可逆氢电势，vs.RHE)运行时间为1小时。 The application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system. The production rate is 1mol/h, and the electrolyte is sodium sulfate solution. The potential was set at 90 mV (relative to reversible hydrogen potential, vs. RHE) and the run time was 1 hour.
实施例2：Example 2:
一种Fe@CuMoO 4NWA/Cu催化剂的制备方法，示例性地，将50mL去离子水加入到洗净的烧杯中，加入过硫酸铵(示例性地，加入后过硫酸铵的浓度为2mol/L)和氢氧化钠(加入后氢氧化钠的浓度2mol/L)，搅拌30min形成澄清透明溶液，将预处理的泡沫铜浸入上述溶液中，在室温下浸泡10min，反应结束后，将得到的产物用超纯水、乙醇分别冲洗3～5次，得到在泡沫铜上生长的Cu(OH) 2纳米线阵列Cu(OH) 2NWA/Cu； A preparation method of Fe@CuMoO 4 NWA/Cu catalyst. Exemplarily, 50mL deionized water is added to a cleaned beaker, and ammonium persulfate is added (exemplarily, the concentration of ammonium persulfate after adding is 2mol/ L) and sodium hydroxide (concentration 2mol/L of sodium hydroxide after adding), stir 30min to form clear and transparent solution, the foam copper of pretreatment is immersed in the above-mentioned solution, soak 10min at room temperature, after reaction finishes, will obtain The product was washed with ultrapure water and ethanol for 3 to 5 times respectively to obtain Cu(OH) 2 nanowire array Cu(OH) 2 NWA/Cu grown on foamed copper;
将30mL去离子水加入到洗净的烧杯中，加入钼酸钠(0.2086g，1mmol，浓度为2.0mol/L)，搅拌30min形成澄清透明溶液，将上述溶液转移到实验室用50mL高温水热反应釜，水热反应釜具有不锈钢外壳，聚四氟乙烯内衬，放入Cu(OH) 2NWA/Cu，0.5g硫酸铁(浓度为2.0mol/L)，35mL超纯水。密封水热高压釜后将其置于100℃的烘箱内保温48h，自然冷却后，分别用去离子水、无水乙醇洗涤、真空干燥后得到Fe@CuMoO 4NWA/Cu。 Add 30mL of deionized water to the cleaned beaker, add sodium molybdate (0.2086g, 1mmol, concentration: 2.0mol/L), stir for 30min to form a clear and transparent solution, transfer the above solution to the laboratory and heat it with 50mL of high-temperature water The reaction kettle, the hydrothermal reaction kettle has a stainless steel shell and a polytetrafluoroethylene lining, and puts Cu(OH) 2 NWA/Cu, 0.5g iron sulfate (concentration: 2.0mol/L), and 35mL ultrapure water. After sealing the hydrothermal autoclave, it was placed in an oven at 100 °C for 48 hours. After natural cooling, it was washed with deionized water and absolute ethanol, and dried in vacuum to obtain Fe@CuMoO 4 NWA/Cu.
以Fe@CuMoO 4NWA/Cu为工作电极，在三电极体系中进行极化曲线测试，电解液是硫酸钠溶液，极化曲线测试电压区间为-1.8～0V，最高电位0V，最低电位-1.8V，开始电位为0V，终止电位为-1.8V，扫描速率为0.005V/s，采样间隔为0.001V，静置时间为2s，当电流密度是10mA/cm 2时，需要的过电势为86mV。 Using Fe@CuMoO 4 NWA/Cu as the working electrode, the polarization curve test is carried out in a three-electrode system. The electrolyte is sodium sulfate solution. The polarization curve test voltage range is -1.8～0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 86mV .
以Fe@CuMoO 4NWA/Cu为工作电极，在三电极体系中进行长时间电催化水分解氢气产率的测试，电解液是硫酸钠溶液，电位设置为86mV(相对于可 逆氢电势，vs.RHE)运行时间为1小时。 Using Fe@CuMoO 4 NWA/Cu as the working electrode, the long-term electrocatalytic water splitting hydrogen yield was tested in a three-electrode system. The electrolyte was sodium sulfate solution, and the potential was set to 86mV (relative to the reversible hydrogen potential, vs. RHE) run time is 1 hour.
基于上述方法制备得到的Fe@CuMoO 4NWA/Cu催化剂在电催化产氢上的应用，示例性地，通过电化学工作站进行测试，以Fe@CuMoO 4NWA/Cu为工作电极，以碳棒为对电极，以Ag/AgCl或Hg/HgO电极为参比电极，在三电极体系中进行长时间电催化水分解氢气产率的测试，产率为0.8mol/h电解液是硫酸钠溶液。电位设置为85mV(相对于可逆氢电势，vs.RHE)运行时间为1小时。电催化产氢过程中将电催化产氢用电解槽与气压表传感器相连，将压力表中的实时压力数据在电脑上输出，通过克拉伯龙方程式计算出气体的物质的量，然后计算该催化剂在电催化水分解产氢的法拉第效率为99.3％。 The application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system. The production rate is 0.8mol/h. The electrolyte is sodium sulfate solution. The potential was set at 85 mV (relative to the reversible hydrogen potential, vs. RHE) and the run time was 1 hour. In the process of electrocatalytic hydrogen production, the electrolytic cell for electrocatalytic hydrogen production is connected with the barometer sensor, the real-time pressure data in the pressure gauge is output on the computer, and the amount of the gas is calculated by the Clapeyron equation, and then the catalyst is calculated. The faradaic efficiency of hydrogen production in electrocatalytic water splitting is 99.3%.
实施例3：Example 3:
将50mL去离子水加入到洗净的烧杯中，加入过氧化氢(示例性地，过氧化氢质量浓度为10％)和氢氧化钠(加入后氢氧化钠的浓度1mol/L)，搅拌30min形成澄清透明溶液，将预处理的泡沫铜浸入上述溶液中，在室温下浸泡15min，反应结束后，将得到的产物用超纯水、乙醇分别冲洗3～5次，得到在泡沫铜上生长的Cu(OH) 2纳米线阵列Cu(OH) 2NWA/Cu。 Add 50mL of deionized water to the cleaned beaker, add hydrogen peroxide (for example, the mass concentration of hydrogen peroxide is 10%) and sodium hydroxide (the concentration of sodium hydroxide after adding is 1mol/L), and stir for 30min Form a clear and transparent solution, immerse the pretreated foamed copper in the above solution, and soak it at room temperature for 15 minutes. After the reaction is over, rinse the obtained product with ultrapure water and ethanol for 3 to 5 times respectively to obtain the copper foam grown on the foamed copper. Cu(OH) 2 nanowire array Cu(OH) 2 NWA/Cu.
将30mL去离子水加入到洗净的烧杯中，加入钼酸钠(0.2086g，1mmol，浓度为2.0mol/L)，三氧化二铁(0.5mmol，浓度为0.1mol/L)，搅拌30min形成澄清透明溶液，将上述溶液转移到实验室用50mL高温水热反应釜，水热反应釜具有不锈钢外壳，聚四氟乙烯内衬，放入Cu(OH) 2NWA/Cu。密封水热高压釜后将其置于160℃的烘箱内保温4h。自然冷却后，分别用去离子水、无水乙醇洗涤、真空干燥后得到Fe@CuMoO 4NWA/Cu。 Add 30mL of deionized water to a cleaned beaker, add sodium molybdate (0.2086g, 1mmol, concentration 2.0mol/L), ferric oxide (0.5mmol, concentration 0.1mol/L), and stir for 30min to form Clarify the transparent solution, and transfer the above solution to a 50mL high-temperature hydrothermal reaction kettle for laboratory use. The hydrothermal reaction kettle has a stainless steel shell and a polytetrafluoroethylene lining, and puts Cu(OH) 2 NWA/Cu. After sealing the hydrothermal autoclave, place it in an oven at 160°C for 4 hours. After natural cooling, the Fe@CuMoO 4 NWA/Cu was obtained after washing with deionized water and absolute ethanol, respectively, and vacuum drying.
以Fe@CuMoO 4NWA/Cu为工作电极，在三电极体系中进行极化曲线测试，电解液是硫酸钠溶液，极化曲线测试电压区间为-1.8～0V，最高电位0V，最低电位-1.8V，开始电位为0V，终止电位为-1.8V，扫描速率为0.005V/s，采样间隔为0.001V，静置时间为2s，当电流密度是10mA/cm 2时，需要的过电势为70mV。 Using Fe@CuMoO 4 NWA/Cu as the working electrode, the polarization curve test is carried out in a three-electrode system. The electrolyte is sodium sulfate solution. The polarization curve test voltage range is -1.8～0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 70mV .
基于上述方法制备得到的Fe@CuMoO 4NWA/Cu催化剂在电催化产氢上的应用，示例性地，通过电化学工作站进行测试，以Fe@CuMoO 4NWA/Cu为工作电极，以碳棒为对电极，以Ag/AgCl或Hg/HgO电极为参比电极，在三电极 体系中进行长时间电催化水分解氢气产率的测试，电解液是硫酸钠溶液。电位设置为70mV(相对于可逆氢电势，vs.RHE)运行时间为1小时。将上述电催化产氢用的电解槽与气压表传感器相连，将压力表中的实时压力数据在电脑上输出，通过克拉伯龙方程式计算出气体的物质的量，然后计算该催化剂在电催化水分解产氢的法拉第效率为99.5％。 The application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system, and the electrolyte is sodium sulfate solution. The potential was set at 70 mV (relative to the reversible hydrogen potential, vs. RHE) and the run time was 1 hour. Connect the above-mentioned electrolytic cell for electrocatalytic hydrogen production to the barometer sensor, output the real-time pressure data in the pressure gauge on the computer, calculate the amount of the gas substance through the Clapeyron equation, and then calculate the catalyst in the electrocatalytic water The Faradaic efficiency of decomposition to produce hydrogen is 99.5%.
实施例4：Example 4:
将50mL去离子水加入到洗净的烧杯中，加入过氧化氢(示例性地，过氧化氢质量浓度为20％)和氢氧化钠(加入后氢氧化钠的浓度0.5mol/L)，搅拌30min形成澄清透明溶液，将预处理的泡沫铜浸入上述溶液中，在室温下浸泡15min，反应结束后，将得到的产物用超纯水、乙醇分别冲洗3～5次，得到在泡沫铜上生长的Cu(OH) 2纳米线阵列Cu(OH) 2NWA/Cu。 Add 50mL of deionized water to the cleaned beaker, add hydrogen peroxide (for example, the mass concentration of hydrogen peroxide is 20%) and sodium hydroxide (the concentration of sodium hydroxide after adding is 0.5mol/L), stir After 30 minutes to form a clear and transparent solution, immerse the pretreated foamed copper in the above solution, and soak it at room temperature for 15 minutes. After the reaction is completed, rinse the obtained product with ultrapure water and ethanol for 3 to 5 times respectively, and obtain the product grown on the foamed copper. Cu(OH) 2 nanowire arrays Cu(OH) 2 NWA/Cu.
将30mL去离子水加入到洗净的烧杯中，加入钼酸锂1mmol，浓度为0.1mol/L，氯化铁0.2mmol，浓度为2.0mol/L，搅拌30min形成澄清透明溶液，将上述溶液转移到实验室用50mL高温水热反应釜，水热反应釜具有不锈钢外壳，聚四氟乙烯内衬，放入Cu(OH) 2NWA/Cu，密封水热高压釜后将其置于130℃的烘箱内保温32h，自然冷却后，分别用去离子水、无水乙醇洗涤、真空干燥后得到Fe@CuMoO 4NWA/Cu。 Add 30mL of deionized water into the cleaned beaker, add 1mmol of lithium molybdate, the concentration is 0.1mol/L, 0.2mmol of ferric chloride, the concentration is 2.0mol/L, stir for 30min to form a clear and transparent solution, transfer the above solution Use a 50mL high-temperature hydrothermal reaction kettle in the laboratory. The hydrothermal reaction kettle has a stainless steel shell and a polytetrafluoroethylene lining. Put Cu(OH) 2 NWA/Cu into it. After sealing the hydrothermal autoclave, place it in a 130°C Insulate in the oven for 32h, cool naturally, wash with deionized water and absolute ethanol, and dry in vacuum to obtain Fe@CuMoO 4 NWA/Cu.
以Fe@CuMoO 4NWA/Cu为工作电极，在三电极体系中进行极化曲线测试，电解液是硫酸钠溶液，极化曲线测试电压区间为-1.8～0V，最高电位0V，最低电位-1.8V，开始电位为0V，终止电位为-1.8V，扫描速率为0.005V/s，采样间隔为0.001V，静置时间为2s，当电流密度是10mA/cm 2时，需要的过电势为70mV。 Using Fe@CuMoO 4 NWA/Cu as the working electrode, the polarization curve test is carried out in a three-electrode system. The electrolyte is sodium sulfate solution. The polarization curve test voltage range is -1.8～0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 70mV .
基于上述方法制备得到的Fe@CuMoO 4NWA/Cu催化剂在电催化产氢上的应用，示例性地，通过电化学工作站进行测试，以Fe@CuMoO 4NWA/Cu为工作电极，以碳棒为对电极，以Ag/AgCl或Hg/HgO电极为参比电极，在三电极体系中进行长时间电催化水分解氢气产率的测试，电解液是硫酸钠溶液，电位设置为70mV(相对于可逆氢电势，vs.RHE)运行时间为1小时。将电催化水分解氢气产率的测试用的电解槽与气压表传感器相连，将压力表中的实时压力数据在电脑上输出，通过克拉伯龙方程式计算出气体的物质的量，然后计算该 催化剂在电催化水分解产氢的法拉第效率为99.5％。 The application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system. The electrolyte is a sodium sulfate solution, and the potential is set to 70mV (relative to the reversible Hydrogen potential, vs. RHE) run time was 1 hour. Connect the electrolytic cell used for the test of the electrocatalytic water splitting hydrogen yield to the barometer sensor, output the real-time pressure data in the pressure gauge on the computer, calculate the amount of the gas substance through the Clapeyron equation, and then calculate the catalyst The Faradaic efficiency in electrocatalytic water splitting for hydrogen production is 99.5%.
实施例5：Example 5:
将50mL去离子水加入到洗净的烧杯中，加入过硫酸铵(示例性地，加入后过硫酸铵的浓度为0.5mol/L)和氢氧化钠(加入后氢氧化钠的浓度1.2mol/L)，硝酸铁(0.02mol)，搅拌30min形成澄清透明溶液，将预处理的泡沫铜浸入上述溶液中，在室温下浸泡30min，反应结束后，将得到的产物用超纯水、乙醇分别冲洗3～5次，得到在泡沫铜上生长的Cu(OH) 2纳米线阵列Fe@Cu(OH) 2NWA/Cu。 50mL deionized water is added in the cleaned beaker, ammonium persulfate is added (exemplarily, the concentration of ammonium persulfate after adding is 0.5mol/L) and sodium hydroxide (the concentration of sodium hydroxide after adding is 1.2mol/L) L), ferric nitrate (0.02mol), stirred for 30min to form a clear and transparent solution, the pretreated foam copper was immersed in the above solution, soaked at room temperature for 30min, after the reaction was over, the product obtained was rinsed with ultrapure water and ethanol respectively 3-5 times to obtain a Cu(OH) 2 nanowire array Fe@Cu(OH) 2 NWA/Cu grown on foamed copper.
将30mL去离子水加入到洗净的烧杯中，加入四水合钼酸铵(1mmol，浓度为0.18mol/L)，硫酸亚铁(0.25mmol，浓度为0.15mol/L)，搅拌30min形成澄清透明溶液，将上述溶液转移到实验室用50mL高温水热反应釜，水热反应釜具有不锈钢外壳，聚四氟乙烯内衬，放入Fe@Cu(OH) 2NWA/Cu，密封水热高压釜后将其置于120℃的烘箱内保温24h，自然冷却后，分别用去离子水、无水乙醇洗涤、真空干燥后得到Fe@CuMoO 4NWA/Cu。 Add 30mL of deionized water to the cleaned beaker, add ammonium molybdate tetrahydrate (1mmol, the concentration is 0.18mol/L), ferrous sulfate (0.25mmol, the concentration is 0.15mol/L), stir for 30min to form a clear and transparent solution, transfer the above solution to a 50mL high-temperature hydrothermal reaction kettle for laboratory use, the hydrothermal reaction kettle has a stainless steel shell, and a polytetrafluoroethylene lining, put Fe@Cu(OH) 2 NWA/Cu, and seal the hydrothermal autoclave Afterwards, it was kept in an oven at 120°C for 24 hours, cooled naturally, washed with deionized water and absolute ethanol, and dried in vacuum to obtain Fe@CuMoO 4 NWA/Cu.
以Fe@CuMoO 4NWA/Cu为工作电极，在三电极体系中进行极化曲线测试，电解液是硫酸钠溶液，极化曲线测试电压区间为-1.8～0V，最高电位0V，最低电位-1.8V，开始电位为0V，终止电位为-1.8V，扫描速率为0.005V/s，采样间隔为0.001V，静置时间为2s，当电流密度是10mA/cm 2时，需要的过电势为85mV。 Using Fe@CuMoO 4 NWA/Cu as the working electrode, the polarization curve test is carried out in a three-electrode system. The electrolyte is sodium sulfate solution. The polarization curve test voltage range is -1.8～0V, the highest potential is 0V, and the lowest potential is -1.8 V, the start potential is 0V, the end potential is -1.8V, the scan rate is 0.005V/s, the sampling interval is 0.001V, the rest time is 2s, when the current density is 10mA/ cm2 , the required overpotential is 85mV .
综上，Fe@CuMoO 4NWA/Cu催化剂中，泡沫铜导电性好，有助于催化过程中电子传输，Fe@CuMoO 4纳米线阵列结构暴露更高的活性面积，有助于提高催化效率。 In summary, in the Fe@CuMoO 4 NWA/Cu catalyst, the copper foam has good conductivity, which is helpful for electron transport during the catalytic process, and the Fe@CuMoO 4 nanowire array structure exposes a higher active area, which helps to improve the catalytic efficiency.
基于上述方法制备得到的Fe@CuMoO 4NWA/Cu催化剂在电催化产氢上的应用，示例性地，通过电化学工作站进行测试，以Fe@CuMoO 4NWA/Cu为工作电极，以碳棒为对电极，以Ag/AgCl或Hg/HgO电极为参比电极，在三电极体系中进行长时间电催化水分解氢气产率的测试，电解液是硫酸钠溶液。电位设置为70mV(相对于可逆氢电势，vs.RHE)运行时间为1.5小时。将上述电催化产氢用的电解槽与气压表传感器相连，将压力表中的实时压力数据在电脑上输出，通过克拉伯龙方程式计算出气体的物质的量，然后计算该催化剂在电 催化水分解产氢的法拉第效率为99.1％。 The application of the Fe@CuMoO 4 NWA/Cu catalyst prepared based on the above method in electrocatalytic hydrogen production is exemplarily tested by an electrochemical workstation, with Fe@CuMoO 4 NWA/Cu as the working electrode and carbon rod as the For the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the long-term electrocatalytic water splitting hydrogen production rate is tested in the three-electrode system, and the electrolyte is sodium sulfate solution. The potential was set at 70 mV (relative to reversible hydrogen potential, vs. RHE) and the run time was 1.5 hours. Connect the above-mentioned electrolytic cell for electrocatalytic hydrogen production to the barometer sensor, output the real-time pressure data in the pressure gauge on the computer, calculate the amount of the gas substance through the Clapeyron equation, and then calculate the catalyst in the electrocatalytic water The Faradaic efficiency of hydrogen decomposition is 99.1%.
尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Although the present invention has been described in detail with reference to the aforementioned embodiments, those of ordinary skill in the art should understand that: it can still modify the technical solutions described in the aforementioned embodiments, or perform equivalent replacements for some of the technical features; and these The modification or replacement does not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims (8)

  1. 一种Fe@CuMoO 4NWA/Cu催化剂的制备方法，其特征在于，包括以下步骤： A preparation method of Fe@CuMoO 4 NWA/Cu catalyst, characterized in that it comprises the following steps:
    将氧化剂和氢氧化钠溶解于水中，再浸入泡沫铜得到在泡沫铜上生长了Cu(OH) 2的纳米线阵列Cu(OH) 2NWA/Cu； Dissolving the oxidizing agent and sodium hydroxide in water, and then immersing in foamed copper to obtain Cu(OH) 2 NWA/Cu nanowire arrays with Cu(OH) 2 grown on the foamed copper;
    将钼源试剂和铁源试剂溶于水中得到混合溶液，再将Cu(OH) 2NWA/Cu加入到所述混合溶液中，采用水热法反应得到所述Fe@CuMoO 4NWA/Cu催化剂。 The molybdenum source reagent and the iron source reagent are dissolved in water to obtain a mixed solution, then Cu(OH) 2 NWA/Cu is added to the mixed solution, and the Fe@CuMoO 4 NWA/Cu catalyst is obtained by hydrothermal reaction.
  2. 根据权利要求1所述的Fe@CuMoO 4NWA/Cu催化剂的制备方法，其特征在于，所述氧化剂为过硫酸铵或过氧化氢；所述钼源试剂为钼酸钠、四水合钼酸铵或钼酸锂中的一种或几种；所述铁源试剂为硫酸铁、硫酸亚铁、氯化铁、硝酸铁或三氧化二铁中的一种或者几种。 The preparation method of Fe@CuMoO 4 NWA/Cu catalyst according to claim 1, wherein the oxidant is ammonium persulfate or hydrogen peroxide; the molybdenum source reagent is sodium molybdate, ammonium molybdate tetrahydrate or one or more of lithium molybdate; the iron source reagent is one or more of ferric sulfate, ferrous sulfate, ferric chloride, ferric nitrate or ferric oxide.
  3. 根据权利要求1所述的Fe@CuMoO 4NWA/Cu催化剂的制备方法，其特征在于，所述浸入泡沫铜具体为：室温下泡沫铜浸入时间为0.5～30min，再清洗若干次。 The preparation method of Fe@CuMoO 4 NWA/Cu catalyst according to claim 1, characterized in that said immersing in foamed copper is specifically: immersing foamed copper at room temperature for 0.5-30 minutes, and then cleaning several times.
  4. 根据权利要求1所述的Fe@CuMoO 4NWA/Cu催化剂的制备方法，其特征在于，所述水热法于100～160℃温度下进行反应4～72h，反应结束后将所得产物清洗若干次。 The preparation method of Fe@CuMoO 4 NWA/Cu catalyst according to claim 1, characterized in that the hydrothermal method is carried out at a temperature of 100-160°C for 4-72 hours, and the obtained product is washed several times after the reaction .
  5. 根据权利要求2所述的Fe@CuMoO 4NWA/Cu催化剂的制备方法，其特征在于，所述将氧化剂和氢氧化钠溶解于水中后，氢氧化钠的浓度为0.1～2mol/L；所述过硫酸铵溶于水后的浓度为0.1～2mol/L；所述过氧化氢溶于水后的质量浓度为0.1～30％。 The preparation method of Fe@CuMoO 4 NWA/Cu catalyst according to claim 2, characterized in that, after the oxidizing agent and sodium hydroxide are dissolved in water, the concentration of sodium hydroxide is 0.1-2mol/L; The concentration of the ammonium persulfate dissolved in water is 0.1-2 mol/L; the mass concentration of the hydrogen peroxide dissolved in water is 0.1-30%.
  6. 根据权利要求1-5任一所述的Fe@CuMoO 4NWA/Cu催化剂的制备方法，其特征在于，所述钼源试剂的浓度为0.1～2.0mol/L，所述铁源试剂的浓度为0.1～2.0mol/L。 According to the preparation method of Fe@CuMoO 4 NWA/Cu catalyst described in any one of claims 1-5, it is characterized in that the concentration of the molybdenum source reagent is 0.1-2.0mol/L, and the concentration of the iron source reagent is 0.1～2.0mol/L.
  7. 一种根据权利要求1-6任一项所述Fe@CuMoO 4NWA/Cu催化剂在电催化水分解制氢的应用。 An application of the Fe@CuMoO 4 NWA/Cu catalyst according to any one of claims 1-6 in electrocatalytic water splitting for hydrogen production.
  8. 根据权利要求7所述的应用，其特征在于，所述电催化水分解制氢具体为：采用三电极体系，通过电化学工作站进行测试，以Fe@CuMoO 4NWA/Cu为工作电极，以碳棒为对电极，以Ag/AgCl或Hg/HgO电极为参比电极，以氢 氧化钠溶液或硫酸钠溶液为电解液，进行电催化产氢反应。 According to the application according to claim 7, it is characterized in that the electrocatalytic water splitting hydrogen production is specifically: using a three-electrode system, testing through an electrochemical workstation, using Fe@CuMoO 4 NWA/Cu as the working electrode, and using carbon The rod is the counter electrode, the Ag/AgCl or Hg/HgO electrode is used as the reference electrode, and the sodium hydroxide solution or sodium sulfate solution is used as the electrolyte to carry out the electrocatalytic hydrogen production reaction.
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