WO2024093285A1 - 一种电催化水氧化同质双原子催化剂及其制备方法和应用 - Google Patents

一种电催化水氧化同质双原子催化剂及其制备方法和应用 Download PDF

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WO2024093285A1
WO2024093285A1 PCT/CN2023/103118 CN2023103118W WO2024093285A1 WO 2024093285 A1 WO2024093285 A1 WO 2024093285A1 CN 2023103118 W CN2023103118 W CN 2023103118W WO 2024093285 A1 WO2024093285 A1 WO 2024093285A1
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diatomic
homogeneous
metal
catalyst
carrier
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章福祥
范文俊
马哈茂德兰希德
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中国科学院大连化学物理研究所
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    • 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
    • C25B11/055—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
    • C25B11/067—Inorganic compound e.g. ITO, silica or titania
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • 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
    • C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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
    • 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
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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

Definitions

  • the invention belongs to the technical field of electrocatalysis and chemical engineering, and specifically relates to an electrocatalytic water oxidation homogeneous diatomic catalyst and a preparation method and application thereof.
  • renewable energy such as solar energy to generate electricity and converting a series of small molecules such as H2O , CO2 , N2 , O2 into high-value-added fuels and chemicals is one of the most important measures to replace fossil energy and achieve the "dual carbon" goal. It can not only alleviate the energy shortage caused by the excessive use of fossil fuels, but also improve the environmental problems caused by the combustion of fossil fuels.
  • water electrolysis to produce hydrogen as an example, the hydrogen energy industry has become an important part of China's energy strategic layout. Hydrogen energy can effectively connect and replace fossil resources from the technical route, and can promote the energy transformation process in the three roles of "secondary energy, energy carrier, and low-carbon raw materials".
  • Water electrolysis consists of two half reactions, the cathode hydrogen evolution reaction and the anode water oxidation reaction.
  • Water oxidation is a multi-electron, multi-proton multi-step reaction process with slow kinetics, which is the rate-controlling step of the reaction.
  • most water oxidation catalysts have an initial overpotential higher than 250 millivolts (mV), an intrinsic activity TOF lower than 1s -1 , and poor stability, which limits their large-scale application in hydrogen production by water electrolysis.
  • the single-atom catalysts developed in recent years have the advantages of 100% atomic utilization, unique electronic structure, high activity, etc., and have received widespread attention in the development of water oxidation catalysts.
  • Currently reported single-atom catalysts include precious metals and non-precious metal elements such as Ru, Ir, Ni, and Fe, and the carriers include carbon materials, hydroxides, phosphides, etc.
  • the single-atom catalysts reported so far have high overpotentials, low TOF values, and poor stability. Therefore, exploring cheap, highly active, and highly intrinsically active electrocatalytic water oxidation catalysts is of great significance for the industrial application of a series of energy catalytic conversion processes such as water electrolysis to produce hydrogen.
  • the purpose of the present invention is to provide a homogeneous diatomic catalyst and its preparation method and application, which can not only prepare The method is simple, and the prepared catalyst has high performance, especially high intrinsic activity, good universality, high stability and low price.
  • the present invention provides a homogeneous diatomic catalyst, which includes a carrier and a homogeneous diatomic active site with an adjacent structure, wherein the active site is anchored in the carrier; the carrier is one or more of an oxide, a hydroxide, and a hydroxyl oxide of a 3d transition metal; and a coordination structure is formed between the homogeneous diatomic catalyst and the carrier.
  • the present invention first synthesizes one or more oxides, hydroxides or hydroxy oxides of 3d transition metals as carriers, then mixes a precursor with a clear metal dimer structure and the oxide or hydroxide carrier of the 3d transition metal, and embeds the diatomic active sites into the skeleton of the 3d transition metal material through a roasting treatment to obtain a loaded structure with a homogeneous diatomic structure, in which the diatoms are adjacent and have oxidized ions, and a stable coordination structure is formed between the diatoms and the carrier.
  • the 3d transition metal is one or more of Ti, V, Mn, Fe, Co, Ni, Cu, and Zn, preferably one or more of V, Mn, Fe, Co, and Ni.
  • the homogeneous diatoms are the same metal elements, and in the catalyst, the atomic types of the diatoms are one or more of Ir, Ru, Ni, Fe, Co, and Mn, preferably one or more of Ir, Ni, Fe, and Co.
  • the distance between the atoms of the homogeneous diatomic atoms is Preferably
  • the metal loading of the homogeneous diatomic metal is 0.1 to 5.0 wt.%, preferably 0.2 to 2.0 wt.%.
  • the coordination number of the homogeneous diatoms is 3.0 to 6.0, preferably 4.0 to 5.0.
  • the homogeneous diatomic atoms exist in an ionic state, and their valence state is +2 to +7, preferably +2 to +5.
  • Another aspect of the present invention provides a method for preparing the above homogeneous diatomic catalyst, the method comprising the following steps:
  • the mass ratio of the carrier to the solvent I is 1:10 to 1:1000, preferably 1:100 to 1:500;
  • Solvent I is one or more of water, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, methanol, ethanol, isopropanol, cyclohexanone, toluene-cyclohexanone, acetone, methyl butyl ketone, methyl isobutyl ketone, acetonitrile and pyridine.
  • the metal dimer precursor has a structural formula as shown in Formula 1:
  • M is a metal, including one or more of Ir, Ru, Ni, Fe, Co, and Mn
  • R is a coordination atom, including any one of O, Cl, C, N, P, and S
  • the valence state of the metal in the metal dimer precursor is 0 to +5
  • the distance between the metal atoms is The coordination number of metal atoms is 2 to 7;
  • Solvent II is one or more of water, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, methanol, ethanol, isopropanol, cyclohexanone, toluene-cyclohexanone, acetone, methyl butyl ketone, methyl isobutyl ketone, acetonitrile and pyridine;
  • the mass ratio of the metal to the carrier in the metal dimer precursor is 1:20-1:1000, preferably 1:50-1:500;
  • the mass ratio of the metal dimer precursor to the solvent II is 1:10 to 1:1000, preferably 1:200 to 1:500.
  • the calcination treatment atmosphere is one or more of air, oxygen, nitrogen, and argon, preferably one or two of air and oxygen, the calcination temperature is 100-1200°C, and the calcination time is 10min-10h.
  • the present invention provides an application of the above homogeneous diatomic catalyst in (photo) electrolysis of water to produce hydrogen, (photo) electrocatalytic carbon dioxide reduction, and (photo) electrocatalytic nitrogen reduction.
  • the preparation method of the present invention is simple, and the prepared catalyst has high performance, especially high intrinsic activity, good universality, high stability and low price.
  • the present invention can obtain 3d transition metal oxide/hydroxide/hydroxyl oxide-loaded homogeneous diatomic (such as Ir, Ru, Ni, Fe, Co, Mn) catalysts, wherein the homogeneous diatomic is a structure of adjacent two-distributed atomic pairs of the same metal, and the prepared catalyst shows excellent catalytic performance in the electrocatalytic water oxidation reaction.
  • 3d transition metal oxide/hydroxide/hydroxyl oxide-loaded homogeneous diatomic such as Ir, Ru, Ni, Fe, Co, Mn
  • the homogeneous diatomic metal catalyst prepared by the present invention is mainly in an ionic state, the distance between atoms is controllable, the loading amount of diatoms is easy to regulate, and the synthesis method is simple and easy to mass produce.
  • the catalytic performance of the homogeneous diatomic dispersed catalytic material prepared by this method in electrocatalytic water oxidation can be comparable to that of photosynthetic system II in nature, and the catalytic stability is good, which has a strong application prospect.
  • the water oxidation starting potential of the catalyst of the present invention is only 170 mV, and the stability is maintained for 650 hours at a current density of 20 mA cm -2 .
  • FIG1 is a SEM image of the CoO x -supported diatomic Ru catalyst of Example 1;
  • FIG2 is a spherical aberration transmission electron microscope HAADF-STEM image of the diatomic Ru catalyst supported by CoO x in Example 1;
  • FIG3 is the Ru EXAFS extension edge fitting result of the diatomic catalyst Ru 2 -NiO x in Example 2;
  • FIG4 is a comparison of the electrocatalytic water oxidation activities of the double-atom catalyst Ru 2 -NiO x of Example 2, commercial IrO 2 , NiO x , and single-atom Ru 1 -NiO x ;
  • FIG5 is a comparison of the starting overpotential and TOF of the electrocatalytic water oxidation of the double-atom catalyst Mn 2 -Ni(OH) 2 of Example 3, commercial IrO 2 , Ni(OH) 2 and single-atom Mn 1 -Ni(OH) 2 ;
  • FIG6 shows the stability of the diatomic catalyst Mn 2 -Ni(OH) 2 of Example 3 at a current density of 20 mA cm -2 ;
  • FIG. 7 shows the stability of the diatomic catalyst Mn 2 -CoOOH of Example 6 at a current density of 20 mA cm -2 .
  • This embodiment provides a homogeneous diatomic catalyst for electrocatalytic water oxidation, which includes a 3d transition metal CoOx oxide support and a diatomic active center ruthenium (Ru), wherein the diatomic active center is anchored in the CoOx oxide support.
  • a homogeneous diatomic catalyst for electrocatalytic water oxidation which includes a 3d transition metal CoOx oxide support and a diatomic active center ruthenium (Ru), wherein the diatomic active center is anchored in the CoOx oxide support.
  • the preparation method of the above catalyst comprises the following steps:
  • This embodiment provides a homogeneous diatomic catalyst for electrocatalytic water oxidation, which includes a 3d transition metal NiOx oxide carrier and a diatomic active center Ru, wherein the diatomic active center is anchored in the NiOx oxide carrier.
  • the preparation method of the above catalyst comprises the following steps:
  • This embodiment provides a homogeneous diatomic catalyst for electrocatalytic water oxidation, which includes a 3d transition metal Ni(OH) 2 hydroxide carrier and a diatomic active center manganese (Mn), wherein the diatomic active center is anchored in the Ni(OH) 2 carrier.
  • a homogeneous diatomic catalyst for electrocatalytic water oxidation which includes a 3d transition metal Ni(OH) 2 hydroxide carrier and a diatomic active center manganese (Mn), wherein the diatomic active center is anchored in the Ni(OH) 2 carrier.
  • the preparation method of the above catalyst comprises the following steps:
  • Ni(OH) 2 was then exfoliated in an ethanol solution under ultrasound for 24 h, and then centrifuged and dried to obtain a two-dimensional Ni(OH) 2 nanosheet carrier.
  • This embodiment provides a homogeneous diatomic catalyst for electrocatalytic water oxidation, which includes a 3d transition metal CoOOH oxyhydroxide carrier and a diatomic active center manganese (Mn), wherein the diatomic active center is anchored in the CoOOH carrier.
  • a homogeneous diatomic catalyst for electrocatalytic water oxidation which includes a 3d transition metal CoOOH oxyhydroxide carrier and a diatomic active center manganese (Mn), wherein the diatomic active center is anchored in the CoOOH carrier.
  • the preparation method of the above catalyst comprises the following steps:
  • This embodiment provides a homogeneous diatomic catalyst for electrocatalytic water oxidation, which includes a 3d transition metal CoOOH oxyhydroxide carrier and a diatomic active center manganese (Mn), wherein the diatomic active center is anchored in the CoOOH carrier.
  • a homogeneous diatomic catalyst for electrocatalytic water oxidation which includes a 3d transition metal CoOOH oxyhydroxide carrier and a diatomic active center manganese (Mn), wherein the diatomic active center is anchored in the CoOOH carrier.
  • the preparation method of the above catalyst comprises the following steps:
  • This embodiment provides a homogeneous diatomic catalyst for electrocatalytic water oxidation, which includes a 3d transition metal CoOOH oxyhydroxide carrier and a diatomic active center manganese (Mn), wherein the diatomic active center is anchored in the CoOOH carrier.
  • a homogeneous diatomic catalyst for electrocatalytic water oxidation which includes a 3d transition metal CoOOH oxyhydroxide carrier and a diatomic active center manganese (Mn), wherein the diatomic active center is anchored in the CoOOH carrier.
  • the preparation method of the above catalyst comprises the following steps:
  • the catalytic material prepared in the above Example 2 was tested and evaluated in electrocatalytic water oxidation.
  • the test conditions were: electrochemical workstation of Shanghai Chenhua Instrument Co., Ltd., catalyst loading of 1 mg cm -2 , and electrolyte of 1 M KOH.
  • FIG4 is a comparison of the electrocatalytic water oxidation activities of the diatomic catalyst Ru 2 -NiO x in Example 2 with commercial IrO 2 , NiO x and single-atom Ru 1 -NiO x .
  • the diatomic structure of Ru 2 -NiO x has a lower overpotential and higher electrocatalytic water oxidation performance than commercial IrO 2 , NiO x and single-atom Ru 2 -NiO x .
  • the diatomic catalytic material prepared by the present invention has an intrinsic catalytic performance TOF in the electrocatalytic water oxidation reaction that is improved by 2-3 orders of magnitude, and has a very high industrial prospect.
  • the catalytic material prepared in the above Example 3 was tested and evaluated in electrocatalytic water oxidation.
  • the test conditions were: electrochemical workstation of Shanghai Chenhua Instrument Co., Ltd., catalyst loading of 1 mg cm -2 , and electrolyte of 1 M KOH.
  • Ni(OH) 2 supported diatomic Mn catalyst shown in Figure 5 shows lower overpotential and higher TOF value than commercial IrO 2 , Ni(OH) 2 and single atom Mn 1 -Ni(OH) 2 .
  • the catalytic material prepared in the above Example 4 was tested and evaluated in photoelectrocatalytic water oxidation.
  • the test conditions were: electrochemical workstation of Shanghai Chenhua Instrument Co., Ltd., catalyst loading of 1 mg cm -2 , and electrolyte of 1 M potassium borate.
  • the catalytic material prepared in the above Example 6 was tested and evaluated in electrocatalytic water oxidation.
  • the test conditions were: electrochemical workstation of Shanghai Chenhua Instrument Co., Ltd., catalyst loading of 1 mg cm -2 , and electrolyte of 1 M KOH.
  • the CoOOH-supported diatomic Mn catalyst showed high stability at a current density of 20 mA cm -2 for 650 h.
  • the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented.
  • the technicians in the technical field should understand that any improvement of the present invention, the equivalent replacement of the raw materials of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

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Abstract

本发明属于电催化和化工技术领域，具体涉及一种电催化水氧化同质双原子催化剂及其制备方法和应用。所述催化剂包括载体和具有相邻结构的同质双原子活性位点，所述活性位点锚定在载体中；所述载体为3d过渡金属的氧化物、氢氧化物、羟基氧化物中的一种或两种以上；所述双原子和载体之间形成配位结构。该方法制备的双原子分散的催化材料在电催化水氧化反应中的本征活性和目前效率最高的自然光合系统II相当，同时水氧化起始电位仅为170mV，在20mA cm-2-电流密度下稳定性保持650小时；且该方法制备简单，成本低廉。

Description

一种电催化水氧化同质双原子催化剂及其制备方法和应用 技术领域
本发明属于电催化和化工技术领域，具体涉及一种电催化水氧化同质双原子催化剂及其制备方法和应用。
背景技术
利用太阳能等可再生能源发电，将H2O、CO2、N2、O2等一系列小分子转化为高附加值的燃料和化学品是替代化石能源实现“双碳”目标的最重要措施之一，不仅可以缓解由于化石燃料过度使用带来的能源紧张，同时能够改善化石燃料燃烧引起的环境问题。以电解水制氢为例，氢能产业已成为我国能源战略布局的重要组成，氢能从技术路线上能够有效衔接替代化石资源，能在“二次能源、能源载体、低碳原料”三种角色助推能源转型进程，到2050年全社会“绿氢”需求或将接近1亿吨。当前我国氢能产业主要来自“灰氢”(约占总产量95％)，尽管其生产成本较低、技术简单，但需要通过化石燃料(如天然气)制备，在生产过程中存在大量CO2等温室气体排放，而通过太阳能、风电等可再生清洁能源电解水制“绿氢”能够实现零碳排放，具有绿色环保、生产灵活、纯度高等特点，具有无可比拟的优越性。在现有的电解水技术中，碱性电解技术最为成熟,然而其单位能耗高，电价占到总成本的70％以上，其中最关键的原因在于电解水催化剂过电位高、长时间稳定性差。电解水由两个半反应组成，阴极析氢反应和阳极水氧化反应，其中水氧化是一个多电子、多质子的多步反应过程，动力学缓慢，是反应的速控步。目前，大部分水氧化催化剂起始过电位高于250毫伏(mV)，本征活性TOF低于1s-1，且稳定性较差，限制其电解水制氢的大规模应用。
近些年发展的单原子催化剂具有100％的原子利用率、独特的电子结构、高活性等优势，在水氧化催化剂开发中受到了广泛的关注。目前已报道的单原子催化剂包括Ru，Ir，Ni，Fe等贵金属和非贵金属元素，载体包含碳材料，氢氧化物，磷化物等。但由于水氧化反应较高的能垒、反应路径复杂，导致目前报道的单原子催化剂过电位高、TOF值低、稳定性差。因此，探索廉价、高活性和高本征活性的电催化水氧化催化剂对于电解水制氢等系列能源催化转化过程工业化应用具有重要意义。
发明内容
本发明的目的在于提供一种同质双原子催化剂及其制备方法和应用，不仅制备 方法简单，且所制备的催化剂性能尤其是本征活性高、普适性好、稳定性高、价格低廉。
为实现上述目的，本发明采用的技术方案为：
本发明一方面提供一种同质双原子催化剂，所述催化剂包括载体和具有相邻结构的同质双原子活性位点，所述活性位点锚定在载体中；所述载体为3d过渡金属的氧化物、氢氧化物、羟基氧化物中的一种或两种以上；所述同质双原子和载体之间形成配位结构。
本发明通过先合成3d过渡金属的氧化物、氢氧化物或羟基氧化物一种或两种以上作为载体，再将具有明确金属二聚体结构的前驱物和3d过渡金属的氧化物或氢氧化物载体混合，通过焙烧处理将双原子活性位点嵌入到3d过渡金属材料骨架当中，获得具有同质双原子结构的负载型结构，同质双原子结构中的双原子为相邻的、具有氧化态离子，双原子和载体之间形成了稳定的配位结构。
上述技术方案中，进一步地，所述3d过渡金属为Ti、V、Mn、Fe、Co、Ni、Cu、Zn中的一种或两种以上，优选为V、Mn、Fe、Co、Ni中的一种或两种以上。
上述技术方案中，进一步地，所述同质双原子为同种金属元素，所述催化剂中，双原子的原子种类为Ir、Ru、Ni、Fe、Co、Mn中的一种或两种以上，优选为Ir、Ni、Fe、Co中的一种或两种以上。
上述技术方案中，进一步地，所述同质双原子的原子之间距离为优选为
上述技术方案中，进一步地，所述同质双原子的金属载量为0.1～5.0wt.％，优选为0.2～2.0wt.％。
上述技术方案中，进一步地，所述同质双原子的配位数为3.0～6.0，优选为4.0～5.0。
上述技术方案中，进一步地，所述同质双原子的存在形式为离子状态，其价态为+2～+7价，优选为+2～+5价。
本发明另一方面提供一种上述同质双原子催化剂的制备方法，所述方法包括如下步骤：
(1)将载体分散在溶剂Ⅰ中，形成悬液A；
(2)将金属二聚体前驱物溶于溶剂Ⅱ中，缓慢加入悬液A中，充分混合，再用过滤、离心、冷冻干燥、旋转蒸发或加热蒸发中的一种或几种方法除去混合物中的溶剂，得到产物B；
(3)对产物B进行研磨，随后焙烧，得到所述催化剂。
上述技术方案中，进一步地，所述步骤(1)中，载体与溶剂Ⅰ的质量比为1:10～1:1000，优选为1:100～1:500；
溶剂Ⅰ为水、苯、甲苯、二甲苯、氯苯、二氯苯、甲醇、乙醇、异丙醇、环己酮、甲苯环己酮、丙酮、甲基丁酮、甲基异丁酮、乙腈、吡啶中的一种或二种以上。
上述技术方案中，进一步地，所述步骤(2)中，金属二聚体前驱物结构式如式1：
其中，M为金属，包括Ir，Ru，Ni，Fe，Co，Mn中的一种或两种以上，R为配位原子，包括O、Cl、C、N、P、S中的任意一种，金属二聚体前驱物中金属的价态为0～+5价，金属原子之间的距离为金属原子的配位数为2～7；
溶剂Ⅱ为水、苯、甲苯、二甲苯、氯苯、二氯苯、甲醇、乙醇、异丙醇、环己酮、甲苯环己酮、丙酮、甲基丁酮、甲基异丁酮、乙腈、吡啶中的一种或二种以上；
金属二聚体前驱物中金属与载体的质量比为1:20-1：1000，优选为1:50～1:500；
金属二聚体前驱物与溶剂Ⅱ的质量比为1:10～1:1000，优选为1:200～1:500。
上述技术方案中，进一步地，所述步骤(3)中，焙烧处理气氛为空气、氧气、氮气、氩气中的一种或两种以上，优选为空气、氧气中一种或两种，焙烧温度为100～1200℃，焙烧时间10min～10h。
本发明再一方面提供一种上述同质双原子催化剂在(光)电解水制氢、(光)电催化二氧化碳还原、(光)电催化氮气还原中的应用。
本发明的有益效果为：
1、本发明制备方法简单，且所制备的催化剂性能尤其是本征活性高、普适性好、稳定性高、价格低廉。
2、本发明能够获得3d过渡金属氧化物/氢氧化物/羟基氧化物负载的同质双原子(如Ir、Ru、Ni、Fe、Co、Mn)催化剂，其中同质双原子为同种金属的邻近两两分布的原子对结构，制备的催化剂在电催化水氧化反应中显示出优越的催化性能。
3、本发明制备得到的催化剂同质双原子金属主要是离子状态，原子间距离可控，双原子的担载量易于调控，且合成方法简单，易于规模化生产。该方法制备的同质双原子分散催化材料在电催化水氧化中的催化性能可以和自然界光合系统II相当，且催化稳定性能好，具有很强的应用前景。
4、本发明催化剂水氧化起始电位仅为170mV，在20mA cm-2-电流密度下稳定性保持650小时。
附图说明
图1为实施例1CoOx负载的双原子Ru催化剂SEM图；
图2为实施例1CoOx负载的双原子Ru催化剂球差透射电镜HAADF-STEM图；
图3为实施例2双原子催化剂Ru2-NiOx的Ru EXAFS拓展边拟合结果；
图4为实施例2双原子催化剂Ru2-NiOx与商业IrO2、NiOx以及单原子Ru1-NiOx电催化水氧化活性对比；
图5为实施例3双原子催化剂Mn2-Ni(OH)2与商业IrO2、Ni(OH)2以及单原子Mn1-Ni(OH)2电催化水氧化起始过电位和TOF对比；
图6为实施例3双原子催化剂Mn2-Ni(OH)2在20mA cm-2电流密度下的稳定性；
图7为实施例6双原子催化剂Mn2-CoOOH在20mA cm-2电流密度下的稳定性。
具体实施方式
为了进一步说明本发明，列举以下实施例并结合附图进行说明，但它并不限制各附加权利要求所定义的发明范围。
如无特别说明，实施例中采用的手段均为本领域公知的技术手段。
实施例1
本实施例提供了一种电催化水氧化同质双原子催化剂，该催化剂包括3d过渡金属CoOx氧化物载体和双原子活性中心钌(Ru)，双原子活性中心锚定在CoOx氧化物载体中。
上述催化剂的制备方法包括如下步骤：
(1)将12mmol的十六烷基三甲基溴化铵(CTAB)溶于25mL水中，加入1mmol的六水硝酸钴，搅拌15min，得到A溶液；
(2)在A溶液中加入1.5mmol的硼氢化钠，充分搅拌6h后用水，乙醇洗涤干燥，得到CoOx载体；
(3)称取20mg CoOx载体，分散在10mL乙醇中，然后再加入1mg二氯苯基钌(II)二聚体，充分超声1h、搅拌10h后在70℃下加热将溶剂蒸发，得到混合物B；
(4)将混合物B放入管式炉中，在300℃下空气环境中焙烧5h，最终得到CoOx负载的双原子钌电催化水氧化催化剂。
图1和图2给出的扫描电镜和球差透射电镜图中可以看出，我们合成的催化剂中金属Ru主要为双原子分散在CoOx骨架中。
实施例2
本实施例提供了一种电催化水氧化同质双原子催化剂，该催化剂包括3d过渡金属NiOx氧化物载体和双原子活性中心Ru，双原子活性中心锚定在NiOx氧化物载体中。
上述催化剂的制备方法包括如下步骤：
(1)将12mmol的CTAB溶于25mL水中，加入1mmol的六水硝酸镍，搅拌15min，得到A溶液；
(2)在A溶液中加入1.5mmol的硼氢化钠，充分搅拌6h后用水，乙醇洗涤干燥，得到NiOx载体；
(3)称取20mg NiOx载体，分散在10mL乙醇中，然后再加入1mg二氯苯基钌(II)二聚体，充分超声1h、搅拌10h后在70℃下加热将溶剂蒸发，得到混合物B；
(4)将混合物B放入管式炉中，在300℃下空气环境中焙烧5h，最终得到NiOx负载的双原子钌电催化水氧化催化剂。
图3和表1给出的同步辐射X射线吸收谱拓展边和拟合结果表明同质双原子Ru结构中Ru和Ru的距离为
表1
实施例3
本实施例提供了一种电催化水氧化同质双原子催化剂，该催化剂包括3d过渡金属Ni(OH)2氢氧化物载体和双原子活性中心锰(Mn)，双原子活性中心锚定在Ni(OH)2载体中。
上述催化剂的制备方法包括如下步骤：
(1)将0.4g NiCl2加入到40mL乙醇中，充分搅拌后在150℃下水热12h得到Ni(OH)2，然后将Ni(OH)2在乙醇溶液中超声下剥离24h，再离心干燥，得到二维Ni(OH)2二维纳米片载体；
(2)称取20mg Ni(OH)2载体，分散在10mL乙醇中，然后再加入1mg三羰基(Η-环戊二烯基)合锰二聚体，充分超声1h、搅拌10h后在70℃下加热将溶剂蒸发，得到混合物A；
(3)将混合物A放入管式炉中，在100℃下空气环境中焙烧5h，最终得到Ni(OH)2负载的双原子Mn电催化水氧化催化剂。
实施例4
本实施例提供了一种电催化水氧化同质双原子催化剂，该催化剂包括3d过渡金属CoOOH羟基氧化物载体和双原子活性中心锰(Mn)，双原子活性中心锚定在CoOOH载体中。
上述催化剂的制备方法包括如下步骤：
(1)将0.3g Co(NO3)2·6H2O加入到200mL水中，充分搅拌后，加入30mL 1M NaOH，搅拌30min；随后再加入6mL NaOCl，搅拌1h，得到的沉淀通过离心和洗涤收集，干燥得到CoOOH；
(2)称取20mg CoOOH载体，分散在10mL乙醇中，然后再加入1mg三羰基(Η-环戊二烯基)合锰二聚体，充分超声1h、搅拌10h后在70℃下加热将溶剂蒸发，得到混合物A；
(3)将混合物A放入管式炉中，在100℃下空气环境中焙烧5h，最终得到CoOOH负载的双原子Mn电催化水氧化催化剂。
实施例5
本实施例提供了一种电催化水氧化同质双原子催化剂，该催化剂包括3d过渡金属CoOOH羟基氧化物载体和双原子活性中心锰(Mn)，双原子活性中心锚定在CoOOH载体中。
上述催化剂的制备方法包括如下步骤：
(1)将0.3g Co(NO3)2·6H2O加入到200mL水中，充分搅拌后，加入30mL 1M NaOH，搅拌30min；随后再加入6mL NaOCl，搅拌1h，得到的沉淀通过离心和洗涤收集，干燥得到；
(2)称取20mg CoOOH载体，分散在10mL乙醇中，然后再加入1mg三羰基(Η-环戊二烯基)合锰二聚体，充分超声1h、搅拌10h后在70℃下加热将溶剂蒸发，得到混合物A；
(3)将混合物A放入管式炉中，在100℃下空气环境中焙烧5h，最终得到CoOOH负载的双原子Mn电催化水氧化催化剂。
实施例6
本实施例提供了一种电催化水氧化同质双原子催化剂，该催化剂包括3d过渡金属CoOOH羟基氧化物载体和双原子活性中心锰(Mn)，双原子活性中心锚定在CoOOH载体中。
上述催化剂的制备方法包括如下步骤：
(1)将0.3g Co(NO3)2·6H2O加入到200mL水中，充分搅拌后，加入30mL 1M NaOH，搅拌30min；随后再加入6mL NaOCl，搅拌1h，得到的沉淀通过离心和洗涤收集，干燥得到；
(2)称取30mg CoOOH载体，分散在10mL乙醇中，然后再加入2mg三羰基(Η-环戊二烯基)合锰二聚体，充分超声1h、搅拌10h后在70℃下加热将溶剂蒸发，得到混合物A；
(3)将混合物A放入管式炉中，在100℃下50％空气和50％氧气环境中焙烧4h，最终得到CoOOH负载的双原子Mn电催化水氧化催化剂。
测试例1
上述实施例2制备的催化材料在电催化水氧化中进行测试评价。测试条件为：上海辰华仪器有限公司的电化学工作站，催化剂负载量为1mg cm-2，电解液为1M KOH。
图4为实施例2双原子催化剂Ru2-NiOx与商业IrO2、NiOx以及单原子Ru1-NiOx电催化水氧化活性对比。从图4可以看出，双原子结构的Ru2-NiOx具有比商业IrO2，NiOx和单原子Ru2-NiOx更低的过电位以及更高的电催化水氧化性能。由此可见，相比于传统方法制备的催化剂，本发明制备的双原子催化材料在电催化水氧化反应中本征的催化性能TOF提高了2-3个数量级，具有很高的工业化前景。
测试例2
上述实施例3制备的催化材料在电催化水氧化中进行测试评价。测试条件为：上海辰华仪器有限公司的电化学工作站，催化剂负载量为1mg cm-2，电解液为1M KOH。
图5给出的Ni(OH)2负载的双原子Mn催化剂显示出比商业IrO2，Ni(OH)2和单原子Mn1-Ni(OH)2更低的过电位和更高的TOF值。
测试例3
上述实施例4制备的催化材料在光电催化水氧化中进行测试评价。测试条件为：上海辰华仪器有限公司的电化学工作站，催化剂负载量为1mg cm-2，电解液为1M硼酸钾。
如图6所示，在BiVO4光阳极上担载双原子催化剂Mn2-CoOOH作为助催化剂后，其光电催化分解水性能得到显著提升，大大高于用CoOOH作为催化剂的光阳极性能。
测试例4
上述实施例6制备的催化材料在电催化水氧化中进行测试评价。测试条件为：上海辰华仪器有限公司的电化学工作站，催化剂负载量为1mg cm-2，电解液为1M KOH。
如图7所示，CoOOH负载的双原子Mn催化剂在20mA cm-2电流密度下650小时内显示出高稳定性。
申请人申明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所述技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种同质双原子催化剂，其特征在于：
    所述催化剂包括载体和具有相邻结构的同质双原子活性位点，所述活性位点锚定在载体中；所述载体为3d过渡金属的氧化物、氢氧化物、羟基氧化物中的一种或两种以上；所述双原子和载体之间形成配位结构。
  2. 根据权利要求1所述的同质双原子催化剂，其特征在于：
    所述3d过渡金属为Ti、V、Mn、Fe、Co、Ni、Cu、Zn中的一种或两种以上；所述同质双原子为同种金属元素，所述催化剂中，双原子的原子种类为Ir、Ru、Ni、Fe、Co、Mn中的一种或两种以上。
  3. 根据权利要求1所述的同质双原子催化剂，其特征在于：
    所述同质双原子的原子之间距离为
  4. 根据权利要求1所述的同质双原子催化剂，其特征在于：
    所述同质双原子的金属载量为0.1～5.0wt.％。
  5. 根据权利要求1所述的同质双原子催化剂，其特征在于：
    所述同质双原子的配位数为3.0～6.0；
    所述同质双原子的存在形式为离子状态，其价态为+2～+7价。
  6. 一种权利要求1-5任一项所述同质双原子催化剂的制备方法，其特征在于：所述方法包括如下步骤：
    (1)将载体分散在溶剂Ⅰ中，形成悬液A；
    (2)将金属二聚体前驱物溶于溶剂Ⅱ中，缓慢加入悬液A中，充分混合，再用过滤、离心、冷冻干燥、旋转蒸发或加热蒸发中的一种或几种方法除去混合物中的溶剂，得到产物B；
    (3)对产物B进行研磨，随后焙烧，得到所述催化剂。
  7. 根据权利要求6所述的制备方法，其特征在于：
    所述步骤(1)中，载体与溶剂Ⅰ的质量比为1:10～1:1000；
    溶剂Ⅰ为水、苯、甲苯、二甲苯、氯苯、二氯苯、甲醇、乙醇、异丙醇、环己酮、甲苯环己酮、丙酮、甲基丁酮、甲基异丁酮、乙腈、吡啶中的一种或二种以上。
  8. 根据权利要求6所述的制备方法，其特征在于：
    所述步骤(2)中，金属二聚体前驱物结构式如式1：
    其中，M为金属，包括Ir，Ru，Ni，Fe，Co，Mn中的一种或两种以上，R为配位原子，包括O、Cl、C、N、P、S中的任意一种，金属二聚体前驱物中金属的价态为0～+5价，金属原子之间的距离为金属原子的配位数为2～7；
    溶剂Ⅱ为水、苯、甲苯、二甲苯、氯苯、二氯苯、甲醇、乙醇、异丙醇、环己酮、甲苯环己酮、丙酮、甲基丁酮、甲基异丁酮、乙腈、吡啶中的一种或二种以上；
    金属二聚体前驱物中金属与载体的质量比为1:20-1：1000；
    金属二聚体前驱物与溶剂Ⅱ的质量比为1:10～1:1000。
  9. 根据权利要求6所述的制备方法，其特征在于：
    所述步骤(3)中，焙烧处理气氛为空气、氧气、氮气、氩气中的一种或两种以上，焙烧温度为100～1200℃，焙烧时间10min～10h。
  10. 一种权利要求1-5任一项所述同质双原子催化剂在(光)电解水制氢、(光)电催化二氧化碳还原、(光)电催化氮气还原中的应用。
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