技术领域technical field
本发明属于电解水催化剂技术领域，具体涉及Mo/Nb双掺杂Co中空介孔碳纳米盒催化剂制备方法及在电解水装置中的应用。The invention belongs to the technical field of electrolytic water catalysts, and in particular relates to a method for preparing a Mo/Nb double-doped Co hollow mesoporous carbon nanobox catalyst and its application in an electrolytic water device.
背景技术Background technique
21世纪，随着工业的发展，能源的开采与利用推动着人类的文明进步，各国对能源的需求越来越迫切，当前的能源结构主要有：天然气、煤炭、石油等。但过度开采，已经造成化石能源的快速枯竭，能源危机凸显，环境污染和一系列气候问题也逐渐浮出水面，因此需要对生态危机密切关注。众所周知，经济发展和能源密不可分。随着传统能源的日趋耗竭和由之带来的全球气候变暖、酸雨、雾霾等环境问题，人类的健康生活受到了严重的影响，同时也影响着国家经济持续增长的潜能。这就需要开发绿色、可持续的能源，合理设计高效的可再生能源转换系统是实现能源高效、可持续利用的关键。其中，高效的利用自然资源也是关键的手段，但世界上存在的自然资源，例如：太阳能、风能、地热能、生物质能等存在不稳定性、不连续性且受地域限制，若大规模的应用到全国，可能存在一些安全性及设施浪费的问题。石油能源的有限性和应用对环境保护的危害是不可避免的，因此开发一种可替代的、可持续的、清洁的能源技术来供应或替代化石能源是极其必要的。电化学储能装置的出现，可以说为解决这个问题提供了关键性的方向。In the 21st century, with the development of industry, the exploitation and utilization of energy promote the progress of human civilization, and the demand for energy in various countries is becoming more and more urgent. The current energy structure mainly includes: natural gas, coal, oil, etc. However, over-exploitation has caused the rapid depletion of fossil energy, the energy crisis has become prominent, environmental pollution and a series of climate problems have gradually surfaced, so it is necessary to pay close attention to the ecological crisis. As we all know, economic development and energy are inseparable. With the depletion of traditional energy sources and the resulting environmental problems such as global warming, acid rain, and smog, human health has been seriously affected, and it has also affected the potential for sustained economic growth of the country. This requires the development of green and sustainable energy, and the rational design of efficient renewable energy conversion systems is the key to efficient and sustainable use of energy. Among them, the efficient use of natural resources is also a key means, but the natural resources that exist in the world, such as: solar energy, wind energy, geothermal energy, biomass energy, etc., are unstable, discontinuous and subject to geographical restrictions. If they are applied on a large scale to the whole country, there may be some problems of safety and waste of facilities. The limitation of petroleum energy and the harm of its application to environmental protection are inevitable, so it is extremely necessary to develop an alternative, sustainable and clean energy technology to supply or replace fossil energy. The emergence of electrochemical energy storage devices can be said to provide a key direction for solving this problem.
在全球经济快速发展的时代，人类随环境污染越来越重视，而其中，化石能源污染是一个不容小觑的方面。氢作为一种零排放的能源，被认为是替代化石燃料能源的替代能源载体，近几年，各个国家均制定了氢能的发展规划。而在工业上制氢的主要方法有：热解天然气或水煤气制氢，但是这些方法在实际中不仅能耗巨大，还会对环境产生一定的污染；而电解水制氢生产安全且可靠，生产的氢气较纯，污染小。相较而言，电解水技术也显得尤为重要了。In the era of rapid global economic development, human beings are paying more and more attention to environmental pollution, and among them, fossil energy pollution is an aspect that cannot be underestimated. As a zero-emission energy source, hydrogen is considered to be an alternative energy carrier to replace fossil fuel energy. In recent years, various countries have formulated hydrogen energy development plans. The main methods of hydrogen production in industry are: pyrolysis of natural gas or water gas to produce hydrogen, but these methods not only consume a lot of energy in practice, but also cause certain pollution to the environment; hydrogen production by electrolysis of water is safe and reliable, and the hydrogen produced is relatively pure and has little pollution. In comparison, electrolysis of water technology is particularly important.
通过可再生能源获取电能，然后利用电解水技术将电能转化为化学能储存于氢气中，随后氢气被分装至全社会，经过燃料电池反应将化学能重新转化为电能并被利用，这就可以建立起基于氢气-水循环的全程清洁无污染的新能源系统。在这其中氢气作为一种高能量密度的能源载体而存在。电解水制氢是实现这一循环的重要技术组成部分。传统的甲烷蒸汽重整制氢技术虽然更为廉价，但其本质依然依赖于使用化石燃料并且会产生与释放CO2。随着可再生能源利用规模的逐渐扩大，电解水技术也具有着更加广泛的应用前景Obtain electrical energy through renewable energy, then use electrolysis water technology to convert electrical energy into chemical energy and store it in hydrogen, then hydrogen is distributed to the whole society, and the chemical energy is reconverted into electrical energy through the fuel cell reaction and used, which can establish a clean and pollution-free new energy system based on hydrogen-water cycle. Among them, hydrogen exists as an energy carrier with high energy density. Hydrogen production by electrolysis of water is an important technical component to realize this cycle. Although the traditional methane steam reforming hydrogen production technology is cheaper, its essence still relies on the use of fossil fuels and produces and releases CO2 . With the gradual expansion of the utilization scale of renewable energy, electrolysis of water technology also has a wider application prospect
电解水制氢由阳极(氧析出OER)和阴极(氢析出HER)组成，这种方法因其几乎零排放量，被认为是一种很有发展前景的方法。Hydrogen production from water electrolysis, which consists of an anode (oxygen evolution OER) and a cathode (hydrogen evolution HER), is considered a promising approach due to its almost zero emissions.
阳极：2H2O→O2+4H++4e-Anode: 2H2 O→O2 +4H+ +4e-
阴极：2H++2e-→H2Cathode: 2H+ +2e- → H2
总反应：2H2O→O2+2H2Total reaction: 2H2 O→O2 +2H2
析氧反应(OER)主要包括三个主要步骤:The oxygen evolution reaction (OER) mainly consists of three main steps:
(1)H2O/OH-在电催化剂表面的吸附(1) Adsorption of H2 O/OH- on the surface of electrocatalyst
(2)反应中间体的形成(2) Formation of reaction intermediates
(3)O2分子的释放。在电解水中，理论上的热力学势能为1.23V，但由于电解水中电池电压需要一个过大的电位，这会导致反应过程电荷传递速率变慢，产氢产氧的过程变得迟缓，从而导致能量额外消耗，结果就是热力学势能远远大于1.23V。贵金属，如Ru,Pt和Ir基材料，由于其巨大的表面积；出色的电催化反应和优异的导电性是燃料电池水分解过程的理想选择。然而，稳定性、来源不足和成本限制了其商业化。为了避免这些问题，在过去的几十年里，科学家们正努力寻找易于合成和大量可用的替代品，以显著降低OER过程的过度潜力。所以电解水制氢技术要与传统制氢行业竞争，这就需要要探索合适的、稳定的、廉价的 OER/HER催化剂，来降低额外消耗的能量，保持较低的过电位，提高反应速率，使电解水过程更环保。(3) Release ofO2 molecules. In electrolyzed water, the theoretical thermodynamic potential energy is 1.23V, but because the battery voltage in electrolyzed water requires an excessive potential, this will slow down the charge transfer rate during the reaction process, and the process of hydrogen and oxygen production will become slow, resulting in additional energy consumption. The result is that the thermodynamic potential energy is much greater than 1.23V. Noble metals, such as Ru, Pt, and Ir-based materials, are ideal for the water-splitting process in fuel cells due to their huge surface area; excellent electrocatalytic reactions and excellent electrical conductivity. However, stability, insufficient sources, and cost limit its commercialization. In order to avoid these problems, over the past decades, scientists are striving to find easily synthesized and abundantly available alternatives to significantly reduce the excess potential of the OER process. Therefore, in order to compete with the traditional hydrogen production industry, electrolytic water hydrogen production technology needs to explore suitable, stable, and cheap OER/HER catalysts to reduce additional energy consumption, maintain low overpotential, increase reaction rate, and make the water electrolysis process more environmentally friendly.
发明内容Contents of the invention
本发明以碳正立方体作为导电网络，钼、铌元素掺杂形成的金属氧酸盐、金属氧化物颗粒负载于导电碳网络上，获得一种高比表面积、活性位点多、电化学性能良好的Mo和Nb元素双掺杂Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8/Nb2O5异质结催化剂，并应用于电解水装置中。In the present invention, a carbon cube is used as a conductive network, and oxometalate and metal oxide particles formed by doping molybdenum and niobium elements are loaded on the conductive carbon network to obtain a Mo and Nb double-doped Co hollow mesoporous carbon nanobox with high specific surface area, many active sites, and good electrochemical performance. The oxygen-containing vacancy Co2 Mo3 O8 /Nb2 O5 heterojunction catalyst is grown and applied to a water electrolysis device.
为了实现上述发明目的，本发明提供了一种Mo/Nb双掺杂Co中空介孔碳纳米盒催化剂制备方法，具体包括如下步骤：In order to achieve the above-mentioned purpose of the invention, the present invention provides a method for preparing a Mo/Nb double-doped Co hollow mesoporous carbon nanobox catalyst, which specifically includes the following steps:
步骤一、钴基沸石咪唑酯骨架材料(ZIF-67)的制备：将钴过渡金属盐、十六烷基三甲基溴化铵的水溶液和二甲基咪唑的水溶液混合，搅拌反应并离心，置于真空烘箱中干燥后得到前驱体正立方体ZIF-67；Step 1. Preparation of cobalt-based zeolite imidazolate framework material (ZIF-67): Mix cobalt transition metal salt, cetyltrimethylammonium bromide aqueous solution and dimethylimidazole aqueous solution, stir for reaction and centrifuge, and dry in a vacuum oven to obtain the precursor cube ZIF-67;
步骤二、Co中空介孔碳纳米盒催化剂的制备(Co@MCNBs)：将步骤一产物在惰性气体氛围的管式炉中退火得到Co@MCNBs；Step 2. Preparation of Co hollow mesoporous carbon nanobox catalysts (Co@MCNBs): anneal the product of step 1 in a tube furnace in an inert gas atmosphere to obtain Co@MCNBs;
步骤三、Co中空介孔碳纳米盒生长着含氧空位Nb2O5异质结催化剂的制备(Co(Nb)@MCNBs)：将含ZIF-67的乙醇溶液和含钴过渡金属盐、铌过渡金属盐的乙醇溶液混合搅拌后，通过高压反应釜水热反应负载铌元素，离心收集固体，将其置于真空烘箱中干燥后再在惰性气体氛围的在管式炉中退火得到Co(Nb)@MCNBs；Step 3. Preparation of Co(Nb)@MCNBs heterojunction catalysts with oxygen vacancies growing on Cohollowmesoporous carbon nanoboxes: After mixing and stirring the ethanol solution containing ZIF-67 and the ethanol solution containing cobalt transition metal salt and niobium transition metal salt, the niobium element was loaded by hydrothermal reaction in an autoclave, and the solid was collected by centrifugation, dried in a vacuum oven, and then annealed in a tube furnace in an inert gas atmosphere to obtain Co(Nb)@MCNBs;
步骤四、Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8异质结催化剂的制备(Co(Mo) @MCNBs)：将含ZIF-67的乙醇溶液和含钴过渡金属盐、钼过渡金属盐的乙醇溶液混合搅拌后，通过高压反应釜水热反应负载钼元素，离心收集固体，将其置于真空烘箱中干燥后再在惰性气体氛围的在管式炉中退火得到Co(Mo)@MCNBs；Step 4. Preparation ofCo2Mo3O8 heterojunction catalysts with oxygen vacancies growing in Co hollowmesoporous carbon nanoboxes (Co(Mo)@MCNBs): After mixing and stirring the ethanol solution containing ZIF-67 and the ethanol solution containing cobalt transition metal salts and molybdenum transition metal salts, the molybdenum element was loaded by hydrothermal reaction in an autoclave, and the solid was collected by centrifugation, dried in a vacuum oven, and then annealed in a tube furnace in an inert gas atmosphere to obtain Co(Mo)@MCNBs;
步骤五、Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8和Nb2O5异质结催化剂的制备 (Co(Mo,Nb)@MCNBs)：将含ZIF-67的乙醇溶液和含钴过渡金属盐、钼过渡金属盐、铌过渡金属盐的乙醇溶液混合搅拌后，通过高压反应釜水热反应负载钼元素和铌元素，离心收集固体，将其置于真空烘箱中干燥后再在惰性气体氛围管式炉中退火得到Co(Mo,Nb)@MCNBs。Step 5. Preparation of Co2 Mo3 O8 and Nb2 O5 heterojunction catalysts with oxygen vacancies in Co hollow mesoporous carbon nanoboxes (Co(Mo,Nb)@MCNBs): After mixing and stirring the ethanol solution containing ZIF-67 and the ethanol solution containing cobalt transition metal salts, molybdenum transition metal salts, and niobium transition metal salts, the molybdenum and niobium elements were loaded by hydrothermal reaction in an autoclave reactor, and the solids were collected by centrifugation, dried in a vacuum oven, and then placed in an inert gas atmosphere tube. Co(Mo,Nb)@MCNBs were obtained by annealing in a conventional furnace.
作为优选，步骤一中所述钴过渡金属盐溶液、十六烷基三甲基溴化铵、二甲基咪唑、水质量比为0.2-1：0.2-1：0.2-1：20-40。Preferably, the cobalt transition metal salt solution, cetyltrimethylammonium bromide, dimethylimidazole, and water mass ratio in step 1 are 0.2-1:0.2-1:0.2-1:20-40.
作为优选，步骤三中所述的ZIF-67、钴过渡金属盐溶液、铌过渡金属盐溶液、乙醇的质量比为0.2-1：0.2-1：0.2-1：10-100。Preferably, the mass ratio of ZIF-67, cobalt transition metal salt solution, niobium transition metal salt solution and ethanol in step three is 0.2-1:0.2-1:0.2-1:10-100.
作为优选步骤四中所述的ZIF-67、钴过渡金属盐溶液、钼过渡金属盐溶液、乙醇的质量比为0.2-1：0.2-1：0.2-1：10-100。Preferably, the mass ratio of ZIF-67, cobalt transition metal salt solution, molybdenum transition metal salt solution and ethanol described in Step 4 is 0.2-1:0.2-1:0.2-1:10-100.
作为优选，步骤五中所述的ZIF-67、钴过渡金属盐溶液、钼过渡金属盐溶液、铌过渡金属盐溶液、乙醇的质量比为0.2-1：0.2-1：0.2-1：0.2-1：10-100。Preferably, the mass ratio of ZIF-67, cobalt transition metal salt solution, molybdenum transition metal salt solution, niobium transition metal salt solution and ethanol in step five is 0.2-1:0.2-1:0.2-1:0.2-1:10-100.
作为优选，步骤一中的钴过渡金属盐采用Co(NO3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2、 CoCl2、CoSO4·7H2O、CoSO4·H2O中的一种或几种。Preferably, one or more of Co(NO3 )2 ·6H2 O, CoCl2 ·6H2 O, Co(CH3 COO)2 , CoCl2 , CoSO4 ·7H2 O, CoSO4 ·H2 O is used as the cobalt transition metal salt in step 1.
作为优选，步骤二、三、四、五中，所述惰性气体氛围为N2、Ar、He中的一种或几种；Preferably, in steps 2, 3, 4, and 5, the inert gas atmosphere is one or more of N2 , Ar, and He;
作为优选，步骤二、三、四、五中所述退火工艺为在惰性气氛中以1℃/min升温速率到 600～700℃保温3h。As a preference, the annealing process described in steps 2, 3, 4, and 5 is to heat at 600-700°C for 3 hours at a heating rate of 1°C/min in an inert atmosphere.
如上述所述Mo/Nb双掺杂Co中空介孔碳纳米盒催化剂作为电解水电极材料的应用，将其与Co中空介孔碳纳米盒一起应用于电解水装置OER和HER反应，所述通过金属双掺杂方式有效负载含氧空位的铌氧化物和钼钴氧酸盐异质结，同时铌元素起协同促进作用，含铌异质结可以促进与其他异质结的合作，发挥出1+1＞2的效果；氧空位的出现更有益于氢氧根的吸附，从而促进OER反应；空心纳米盒结构，可以使更多的活性位点暴露，提高了活性位点的活性，增加催化剂的电催化性能。As mentioned above, the Mo/Nb double-doped Co hollow mesoporous carbon nanobox catalyst is used as an electrode material for electrolysis of water. It is used together with Co hollow mesoporous carbon nanoboxes in the OER and HER reactions of electrolyzed water devices. The niobium oxide and molybdenum cobalt oxomate heterojunctions containing oxygen vacancies are effectively supported by metal double doping. At the same time, the niobium element plays a synergistic role. The niobium-containing heterojunction can promote cooperation with other heterojunctions, exerting the effect of 1+1>2; the appearance of oxygen vacancies is more beneficial to the adsorption of hydroxide ions. Thereby promoting the OER reaction; the hollow nano-box structure can expose more active sites, improve the activity of the active sites, and increase the electrocatalytic performance of the catalyst.
相对于现有技术，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明用Co源代替贵金属是Pt、Ir和Ru基等贵金属材料，大大降低了成本，扩大应用范围。(1) The present invention uses the Co source to replace noble metals such as Pt, Ir and Ru-based noble metal materials, which greatly reduces the cost and expands the scope of application.
(2)目前在电催化剂中研究较多的金属是Fe、Ni、V等，对一些不常见且在地球上储量丰富的元素的探索较少。在本发明中，我们探索了Nb这种元素，Nb由于其活性和复杂的化学性质，可以与其他主相活性物质形成很好的连接，在电催化领域是一种开发协同促进剂。(2) At present, the most studied metals in electrocatalysts are Fe, Ni, V, etc., and the exploration of some uncommon and abundant elements on the earth is less. In this invention, we explore the element Nb, which can form a good connection with other main phase active substances due to its activity and complex chemical properties, and is a developmental synergistic accelerator in the field of electrocatalysis.
(3)本发明中通过在Co中空介孔碳纳米盒外面生长两种异质结，既不会改变原有纳米盒中空有微孔的形貌，而且通过异质结间的化学协同作用，使生长的颗粒更加均匀化、有序化，从而引入缺陷，造成了氧空位的增加，提高对氢氧根的吸附，增强电化学OER性能。(3) In the present invention, two kinds of heterojunctions are grown outside the Co hollow mesoporous carbon nanobox, which neither changes the morphology of the original nanobox with hollow micropores, but also makes the grown particles more uniform and orderly through the chemical synergy between the heterojunctions, thereby introducing defects, resulting in the increase of oxygen vacancies, improving the adsorption of hydroxide ions, and enhancing the electrochemical OER performance.
附图说明Description of drawings
图1为实施例1制备的Mo和Nb元素双掺杂Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8/Nb2O5异质结催化剂于扫描电子显微镜下(SEM)的微观形貌；Figure 1 is the microscopic morphology oftheCo2Mo3O8 /Nb2O5 heterojunction catalyst containing oxygen vacancies grown onMo and Nb elements double-doped Co hollow mesoporous carbon nanoboxes prepared in Example 1 under a scanning electronmicroscope (SEM);
图2为对比例1和实施例1，2，3样品和商业RuO2催化剂的析氧反应(OER)的线性扫描伏安测试图(LSV)；Fig. 2 is comparative example 1 and embodiment 1,2,3 sample and commercialRuO The linear sweep voltammetry test figure (LSV) of the oxygen evolution reaction (OER) of catalyst;
图3为对比例1和实施例1，2，3样品催化剂的析氢反应反应(HER)的线性扫描伏安测试图(LSV)。Fig. 3 is the linear sweep voltammetry test graph (LSV) of the hydrogen evolution reaction (HER) of the sample catalysts of Comparative Example 1 and Examples 1, 2, and 3.
具体实施方式Detailed ways
为了使本发明的目的、技术方案和有益技术效果更加清晰，下面结合附图和具体实施方式，对本发明Mo/Nb双掺杂Co中空介孔碳纳米盒催化剂制备方法及其在电解水中应用的有益效果进行详细说明。应当理解的是，本说明书中描述的实施例仅仅是为了解释本发明，并非为了限定本发明，实施例的参数、比例等可因地制宜做出选择而对结果并无实质性影响。In order to make the purpose, technical scheme and beneficial technical effects of the present invention clearer, the preparation method of the Mo/Nb double-doped Co hollow mesoporous carbon nanobox catalyst of the present invention and its beneficial effects of application in electrolyzed water will be described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the embodiments described in this specification are only for explaining the present invention, not for limiting the present invention, and the parameters and proportions of the embodiments can be selected according to local conditions and have no substantial influence on the results.
对比例1：一种负载Co颗粒的中空介孔碳纳米盒催化剂的制备，具体包括以下步骤：Comparative Example 1: The preparation of a hollow mesoporous carbon nanobox catalyst loaded with Co particles specifically comprises the following steps:
(1)ZIF-67的合成：(1) Synthesis of ZIF-67:
以0.292g的Co(NO3)2.6H2O为Co源溶解在10mL的去离子水(DI)中，该去离子水包含4mg 的十六烷基三甲基溴化铵(CTAB)。然后将该溶液快速注入70mL的含4.54g 2-甲基咪唑(2-MIM)的水溶液中，并在室温下搅拌30分钟。通过以12000rpm离心3分钟收集产物，用乙醇洗涤几次。0.292 g of Co(NO3 )2 .6H2 O as a Co source was dissolved in 10 mL of deionized water (DI) containing 4 mg of cetyltrimethylammonium bromide (CTAB). The solution was then quickly poured into 70 mL of an aqueous solution containing 4.54 g of 2-methylimidazole (2-MIM), and stirred at room temperature for 30 minutes. The product was collected by centrifugation at 12000 rpm for 3 minutes and washed several times with ethanol.
(2)负载Co颗粒的中空介孔碳纳米盒催化剂的合成：(2) Synthesis of hollow mesoporous carbon nanobox catalysts loaded with Co particles:
将上述制得的粉末在氩气流下以1℃min-1的加热速率在650℃下进一步退火3h，然后自然冷却至室温。The powder prepared above was further annealed at 650 °C for 3 h at a heating rate of 1 °C min under anargon flow, and then naturally cooled to room temperature.
实施例1：Mo/Nb双掺杂Co中空介孔碳纳米盒催化剂的制备，具体包括以下步骤：Embodiment 1: The preparation of Mo/Nb double-doped Co hollow mesoporous carbon nanobox catalyst specifically comprises the following steps:
(1)ZIF-67的合成：(1) Synthesis of ZIF-67:
以0.292g的Co(NO3)2.6H2O为Co源溶解在10mL的去离子水(DI)中，该去离子水包含4mg 的十六烷基三甲基溴化铵(CTAB)。然后将该溶液快速注入70mL的含4.54g 2-甲基咪唑(2-MIM)的水溶液中，并在室温下搅拌30分钟。通过以12000rpm离心3分钟收集产物，用乙醇洗涤几次。0.292 g of Co(NO3 )2 .6H2 O as a Co source was dissolved in 10 mL of deionized water (DI) containing 4 mg of cetyltrimethylammonium bromide (CTAB). The solution was then quickly poured into 70 mL of an aqueous solution containing 4.54 g of 2-methylimidazole (2-MIM), and stirred at room temperature for 30 minutes. The product was collected by centrifugation at 12000 rpm for 3 minutes and washed several times with ethanol.
(2)Mo和Nb元素双掺杂Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8/Nb2O5异质结催化剂的合成：(2) Synthesis of Co2 Mo3 O8 /Nb2 O5 heterojunction catalysts with Mo and Nb double-doped Co hollow mesoporous carbon nanoboxes grown with oxygen vacancies:
首先将0.06g的ZIF-67和5mL含0.05M(NH4)2MoS4溶于20ml的乙醇中，恒速搅拌1h。然后将10ml含Co(NO3)2.6H2O(6mM)和NbCl5(3mM)乙醇溶液缓慢滴加到上述溶液中，恒速搅拌3h。然后将上述溶液转移到衬有Teflon的不锈钢高压釜(50mL)中，并保持在200℃下保持6小时。冷却至室温后，离心收集产物，用乙醇洗涤几次，然后在70℃的烘箱中干燥。将制得的粉末在在氩气流下以1℃min-1的加热速率在650℃退火3h，然后自然冷却至室温，得到Mo和Nb元素双掺杂Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8/Nb2O5异质结催化剂 Co(Mo,Nb)@MCNBs。实验中，管式炉始终保持恒定压力。First, 0.06g of ZIF-67 and 5mL containing 0.05M (NH4 )2 MoS4 were dissolved in 20ml of ethanol, and stirred at a constant speed for 1h. Then 10ml of ethanol solution containing Co(NO3 )2 .6H2 O (6mM) and NbCl5 (3mM) was slowly added dropwise to the above solution, and stirred at a constant speed for 3h. The above solution was then transferred to a Teflon-lined stainless steel autoclave (50 mL) and kept at 200°C for 6 hours. After cooling to room temperature, the product was collected by centrifugation, washed several times with ethanol, and then dried in an oven at 70 °C. The as-prepared powder was annealed at 650°C for 3 h at a heating rate of 1°C min-1 under argon flow, and then naturally cooled to room temperature to obtain Co(Mo,Nb)@MCNBs, a heterojunction catalyst containing oxygen vacancies Co2 Mo3 O8 /Nb2 O5 grown in Mo and Nb double-doped Co hollow mesoporous carbon nanoboxes. During the experiment, the tube furnace was kept at a constant pressure.
通过扫描电子显微镜(SEM)对实施例1获得的Co(Mo,Nb)@MCNBs材料的形貌进行分析，结果如图1所示依旧保持立方体结构，异质结结构负载于表面。The morphology of the Co(Mo,Nb)@MCNBs material obtained in Example 1 was analyzed by scanning electron microscopy (SEM). As shown in Figure 1, the cubic structure is still maintained, and the heterojunction structure is supported on the surface.
实施例2：Nb掺杂Co中空介孔碳纳米盒催化剂的合成的制备，具体包括以下步骤：Embodiment 2: The preparation of the synthesis of Nb-doped Co hollow mesoporous carbon nanobox catalyst specifically comprises the following steps:
(1)ZIF-67的合成：(1) Synthesis of ZIF-67:
以0.292g的Co(NO3)2.6H2O为Co源溶解在10mL的去离子水(DI)中，该去离子水包含4mg 的十六烷基三甲基溴化铵(CTAB)。然后将该溶液快速注入70mL的含4.54g 2-甲基咪唑(2-MIM)的水溶液中，并在室温下搅拌30分钟。通过以12000rpm离心3分钟收集产物，用乙醇洗涤几次。0.292 g of Co(NO3 )2 .6H2 O as a Co source was dissolved in 10 mL of deionized water (DI) containing 4 mg of cetyltrimethylammonium bromide (CTAB). The solution was then quickly poured into 70 mL of an aqueous solution containing 4.54 g of 2-methylimidazole (2-MIM), and stirred at room temperature for 30 minutes. The product was collected by centrifugation at 12000 rpm for 3 minutes and washed several times with ethanol.
(2)Nb元素掺杂Co中空介孔碳纳米盒生长着含氧空位Nb2O5异质结催化剂的合成：(2) Synthesis of Nb-doped Co hollow mesoporous carbon nanoboxes with oxygen-vacancy Nb2 O5 heterojunction catalysts:
首先将0.06g的ZIF-67溶于20ml的乙醇中，恒速搅拌1h。然后将10ml含Co(NO3)2.6H2O(6mM) 和NbCl5(3mM)乙醇溶液缓慢滴加到上述溶液中，恒速搅拌3h。然后将上述溶液转移到衬有 Teflon的不锈钢高压釜(50mL)中，并保持在200℃下保持6小时。冷却至室温后，离心收集产物，用乙醇洗涤几次，然后在70℃的烘箱中干燥。将制得的粉末在在氩气流下以1℃min-1的加热速率在650℃退火3h，然后自然冷却至室温，得到Nb元素掺杂Co中空介孔碳纳米盒生长着含氧空位Nb2O5异质结催化剂Co(Nb)@MCNBs。实验中，管式炉始终保持恒定压力。First, 0.06 g of ZIF-67 was dissolved in 20 ml of ethanol, and stirred at a constant speed for 1 h. Then 10ml of ethanol solution containing Co(NO3 )2 .6H2 O (6mM) and NbCl5 (3mM) was slowly added dropwise to the above solution, and stirred at a constant speed for 3h. The above solution was then transferred to a Teflon-lined stainless steel autoclave (50 mL) and kept at 200°C for 6 hours. After cooling to room temperature, the product was collected by centrifugation, washed several times with ethanol, and then dried in an oven at 70 °C. The as-prepared powder was annealed at 650°C for 3 h at a heating rate of 1°C min-1 under argon flow, and then naturally cooled to room temperature to obtain Co(Nb)@MCNBs doped with Co hollow mesoporous carbon nanoboxes and grown with oxygen-vacancy Nb2 O5 heterojunction catalysts. During the experiment, the tube furnace was kept at a constant pressure.
实施例3：Mo掺杂Co中空介孔碳纳米盒催化剂的制备，具体包括以下步骤：Embodiment 3: the preparation of Mo-doped Co hollow mesoporous carbon nanobox catalyst specifically comprises the following steps:
(1)ZIF-67的合成：(1) Synthesis of ZIF-67:
以0.292g的Co(NO3)2.6H2O为Co源溶解在10mL的去离子水(DI)中，该去离子水包含4mg 的十六烷基三甲基溴化铵(CTAB)。然后将该溶液快速注入70mL的含4.54g 2-甲基咪唑(2-MIM)的水溶液中，并在室温下搅拌30分钟。通过以12000rpm离心3分钟收集产物，用乙醇洗涤几次。0.292 g of Co(NO3 )2 .6H2 O as a Co source was dissolved in 10 mL of deionized water (DI) containing 4 mg of cetyltrimethylammonium bromide (CTAB). The solution was then quickly poured into 70 mL of an aqueous solution containing 4.54 g of 2-methylimidazole (2-MIM), and stirred at room temperature for 30 minutes. The product was collected by centrifugation at 12000 rpm for 3 minutes and washed several times with ethanol.
(2)Mo元素掺杂Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8异质结催化剂的合成：(2) Synthesis of Co2 Mo3 O8 heterojunction catalysts with Mo doped Co hollow mesoporous carbon nanoboxes growing with oxygen vacancies:
首先将0.06g的ZIF-67和5mL含0.05M(NH4)2MoS4溶于20ml的乙醇中，恒速搅拌1h。然后将10ml含Co(NO3)2.6H2O(6mM)乙醇溶液缓慢滴加到上述溶液中，恒速搅拌3h。然后将上述溶液转移到衬有Teflon的不锈钢高压釜(50mL)中，并保持在200℃下保持6小时。冷却至室温后，离心收集产物，用乙醇洗涤几次，然后在70℃的烘箱中干燥。将制得的粉末在在氩气流下以1℃min-1的加热速率在650℃退火3h，然后自然冷却至室温，得到Mo元素掺杂Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8异质结催化剂Co(Mo)@MCNBs。实验中，管式炉始终保持恒定压力。First, 0.06g of ZIF-67 and 5mL containing 0.05M (NH4 )2 MoS4 were dissolved in 20ml of ethanol, and stirred at a constant speed for 1h. Then 10ml of ethanol solution containing Co(NO3 )2 .6H2 O (6mM) was slowly added dropwise to the above solution, and stirred at a constant speed for 3h. The above solution was then transferred to a Teflon-lined stainless steel autoclave (50 mL) and kept at 200°C for 6 hours. After cooling to room temperature, the product was collected by centrifugation, washed several times with ethanol, and then dried in an oven at 70 °C. The as-prepared powder was annealed at 650°C for 3 h at a heating rate of 1°C min-1 under an argon flow, and then cooled naturally to room temperature to obtain Co(Mo)@MCNBs, a heterojunction catalyst containing Mo element-doped Co hollow mesoporous carbon nanoboxes grown with oxygen vacancies Co2 Mo3 O8 . During the experiment, the tube furnace was kept at a constant pressure.
双功能催化性能评估：Bifunctional Catalytic Performance Evaluation:
所有的电化学测试使用的电化学工作站型号为CHI 760E测试体系，电化学测试都在室温下进行。The electrochemical workstation model used for all electrochemical tests is CHI 760E test system, and the electrochemical tests are all performed at room temperature.
工作电极的制备：准确称量5mg Mo和Nb元素双掺杂Co中空介孔碳纳米盒生长着含氧空位Co2Mo3O8/Nb2O5异质结催化剂、0.5mg乙炔黑、0.5mg聚偏二氟乙烯(PVDF)，然后混合溶解在750mL n-甲基-吡咯烷酮(NMP)中，将混合物超声处理30min，最后将上述制备的墨汁滴涂在面积0.5cm×0.5cm的碳纸表面，红外灯烘干后继续滴涂，重复，最后称量得负载量约为0.4mg。作为对照实验，商业RuO2催化剂也采用相同的制备方法进行制备并测试。Preparation of the working electrode: Accurately weigh 5 mg of Mo and Nb double-doped Co hollow mesoporous carbon nanoboxes grown with oxygen vacancies Co2 Mo3 O8 /Nb2 O5 heterojunction catalyst, 0.5 mg of acetylene black, 0.5 mg of polyvinylidene fluoride (PVDF), and then mix and dissolve in 750 mL of n-methyl-pyrrolidone (NMP). On the surface of carbon paper with a diameter of 0.5cm, after drying by infrared light, continue to drop-coat, repeat, and finally weigh the loading amount to be about 0.4mg. As a control experiment, commercialRuO2 catalysts were also prepared and tested by the same preparation method.
电化学性能测试：在测试过程中采用标准的三电极电化学测试体系，其中，对电极为Pt 网，参比电极为饱和甘汞电极(SCE)以及上述制备的工作电极。Electrochemical performance test: A standard three-electrode electrochemical test system was used during the test, wherein the counter electrode was a Pt mesh, the reference electrode was a saturated calomel electrode (SCE) and the working electrode prepared above.
利用电化学工作站分别测试了对比例1和实施例1，2，3样品在1.0M KOH溶液中的OER-LSV曲线如图2所示，对比例1和实施例1，2，3样品在电流密度为10mA cm-2时，OER 过电位分别为364mV，284mV，351mV和317mV。在相同测试条件下，比商业RuO2催化剂的过电位和空白碳纸低，说明Mo和Nb元素双掺杂Co中空介孔碳纳米盒生长着含氧空位 Co2Mo3O8/Nb2O5异质结催化剂样品具有优异的OER电催化活性，可以应用于电解水装置的正极中。The OER-LSV curves of Comparative Example 1 and Examples 1, 2, and 3 samples in 1.0M KOH solution were tested by electrochemical workstation, as shown in Figure 2. When the current density of Comparative Example 1 and Example 1, 2, and 3 samples was 10mA cm-2 , the OER overpotentials were 364mV, 284mV, 351mV and 317mV respectively. Under the same test conditions, the overpotential of the commercial RuO2 catalyst is lower than that of the blank carbon paper, indicating that the Mo and Nb element double-doped Co hollow mesoporous carbon nanobox grows an oxygen-vacancy Co2 Mo3 O8 /Nb2 O5 heterojunction catalyst sample with excellent OER electrocatalytic activity, which can be applied to the positive electrode of the water electrolysis device.
利用电化学工作站分别测试了对比例1和实施例1，2，3样品在1.0M KOH溶液中的HER-LSV曲线如图2所示，对比例1和实施例1，2，3样品在电流密度为10mA cm-2时，HER 过电位分别为206mV，229mV，314mV和245mV，说明负载Co颗粒的中空介孔碳纳米盒催化剂催化剂样品也有一定的HER电催化活性，可以应用于电解水装置的负极中。The HER-LSV curves of Comparative Example 1 and Examples 1, 2, and 3 samples in 1.0M KOH solution were tested by an electrochemical workstation, as shown in Figure 2. When the current density of Comparative Example 1 and Example 1, 2, and 3 samples was 10mA cm-2 , the HER overpotentials were 206mV, 229mV, 314mV, and 245mV, respectively. It is used in the negative electrode of the electrolyzed water device.
最后还应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各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，或者对其中部分或者全部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范围。Finally, it should also be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements to some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
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