CN115057479B - A preparation method of CoAl2O4 electrocatalytic material and its application in ENRR - Google Patents
A preparation method of CoAl2O4 electrocatalytic material and its application in ENRR Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910019114 CoAl2O4 Inorganic materials 0.000 title 1
- 229910002515 CoAl Inorganic materials 0.000 claims abstract description 31
- 239000003245 coal Substances 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 10
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- 229910052596 spinel Inorganic materials 0.000 abstract description 8
- 239000011029 spinel Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000002341 toxic gas Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- 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
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Abstract
一种尖晶石CoAl2O4电催化材料的制备方法及其ENRR的应用，属于电催化固氮领域，包括前驱体机械混合，前驱体凝胶干燥，得到的发泡前驱体研磨后置于马弗炉中于800℃加热5h得到CoAl2O4粉末。本发明主要用于制备结晶度较好，且具有较好催化效果的CoAl2O4电催化固氮材料，解决了其他制备过程需用高成本原料且制备工艺复杂的问题，与其他合成方法相比，本发明使用原料少，合成工艺简单，安全性较高，合成过程不会产生有毒气体，且材料中Co的价态呈现+2价，其对于氮还原表现出优异的催化性能。A preparation method of spinel CoAl 2 O 4 electrocatalytic material and its application in ENRR, belonging to the field of electrocatalytic nitrogen fixation, including mechanical mixing of precursors, drying of precursor gel, and grinding of the obtained foamed precursor and placing it in a horse Heating at 800°C for 5 hours in a furnace to obtain CoAl 2 O 4 powder. The present invention is mainly used to prepare CoAl 2 O 4 electrocatalytic nitrogen-fixing materials with good crystallinity and good catalytic effect. It solves the problems of high-cost raw materials and complicated preparation processes in other preparation processes. Compared with other synthesis methods, , the present invention uses less raw materials, has a simple synthesis process, and is highly safe. The synthesis process does not produce toxic gases, and the valence state of Co in the material shows +2 valence, which shows excellent catalytic performance for nitrogen reduction.
Description
技术领域Technical field
本发明属于电催化还原氮气制氨领域，具体公开了用于ENRR的电催化材料CoAl2O4的制备方法。The invention belongs to the field of electrocatalytic reduction of nitrogen to produce ammonia, and specifically discloses a preparation method of electrocatalytic material CoAl 2 O 4 for ENRR.
背景技术Background technique
随着工业的不断发展，化石燃料和不可再生能源的过度使用使得环境受到极大的污染，因此，对于可再生能源和清洁能源的研究迫在眉睫。氨气是农业、药品和***等工业品的重要前驱体，作为氮循环中的重要环节促进人与自然的能量交换。作为一种清洁可再生的能量载体，能量密度达到51kcal g-1，氨气燃烧的产物主要是氮气和水，几乎不会产生有害气体，且其低的液化压力(0.8-1.0MPa)和更窄的***极限不但降低了运输过程的成本，更提高了安全性。因此，为了满足人类社会发展的需求，Haber-Bosch工艺的发展实现了人类大规模工业制氨，但是该过程需要在高温高压下进行，且反应过程中排放大量的CO2，对环境造成了极大的污染。为了实现人类社会的高效可持续发展，更加绿色可持续的高效固氮方法有待开发。With the continuous development of industry, the excessive use of fossil fuels and non-renewable energy has greatly polluted the environment. Therefore, research on renewable energy and clean energy is urgent. Ammonia is an important precursor for industrial products such as agriculture, pharmaceuticals, and explosives. As an important link in the nitrogen cycle, ammonia promotes energy exchange between humans and nature. As a clean and renewable energy carrier, the energy density reaches 51kcal g -1 . The products of ammonia combustion are mainly nitrogen and water, almost no harmful gases are produced, and its low liquefaction pressure (0.8-1.0MPa) and higher The narrow explosion limit not only reduces the cost of the transportation process, but also improves safety. Therefore, in order to meet the needs of the development of human society, the development of the Haber-Bosch process has enabled large-scale industrial ammonia production. However, this process needs to be carried out under high temperature and high pressure, and a large amount of CO 2 is emitted during the reaction, which has caused great harm to the environment. Big pollution. In order to achieve efficient and sustainable development of human society, more green and sustainable efficient nitrogen fixation methods need to be developed.
电催化还原氮气反应因以N2和H2O为原料合成NH3而备受关注，此过程不仅原料易得，且合成条件温和，设备简单，以可再生的电子作为驱动力，并且ENRR过程不会产生对环境有害的物质。但是N2分子具有极其难断裂的N≡N三键，其键能高达941kJ mol-1，且关键中间体*NNH的形成受到N≡N三键高键能的限制而成为限速步骤。此外N2分子的最高占据态和最低占据态之间的带隙较宽，使得电子难以进入其π反键轨道实现活化。因此，设计新型催化剂提高NRR对于电催化氮气还原十分重要。一般来说，催化剂的合成成本不仅要低，且要有好的导电性。本发明以六水合硝酸钴为钴源，以九水合硝酸铝作为铝源合成尖晶石CoAl2O4纳米颗粒，与水热法合成CoAl2O4的方法不同，本发明主要通过机械搅拌合成前驱体，且使用原料成本较低，实验工艺流程简单，材料中Co的价态体现为+2价，其对于ENRR表现出优异的催化性能，分别体现在优异的氨产率和法拉第效率上。The electrocatalytic nitrogen reduction reaction has attracted much attention because it uses N 2 and H 2 O as raw materials to synthesize NH 3. This process not only has easy-to-obtain raw materials, but also has mild synthesis conditions, simple equipment, renewable electrons as the driving force, and the ENRR process No substances harmful to the environment will be produced. However, the N molecule has an N≡N triple bond that is extremely difficult to break, with a bond energy as high as 941kJ mol -1 , and the formation of the key intermediate *NNH is limited by the high bond energy of the N≡N triple bond and becomes a rate-limiting step. In addition, the band gap between the highest occupied state and the lowest occupied state of the N molecule is wide, making it difficult for electrons to enter its π antibonding orbit for activation. Therefore, designing new catalysts to improve NRR is very important for electrocatalytic nitrogen reduction. Generally speaking, the synthesis cost of the catalyst must not only be low, but also must have good conductivity. The present invention uses cobalt nitrate hexahydrate as the cobalt source and aluminum nitrate nonahydrate as the aluminum source to synthesize spinel CoAl 2 O 4 nanoparticles. Different from the hydrothermal method of synthesizing CoAl 2 O 4 , the present invention mainly synthesizes it through mechanical stirring. Precursor, the cost of raw materials used is low, the experimental process is simple, the valence state of Co in the material is +2, and it shows excellent catalytic performance for ENRR, which is reflected in excellent ammonia yield and Faradaic efficiency respectively.
发明内容Contents of the invention
针对现有技术存在的缺陷，本发明旨在提供一种方便快捷地制备电催化固氮的尖晶石CoAl2O4的方法，能够在具有一定催化性能的同时，前期材料合成耗能较少，且工艺流程简单。In view of the shortcomings of the existing technology, the present invention aims to provide a method for conveniently and quickly preparing spinel CoAl 2 O 4 for electrocatalytic nitrogen fixation, which can have certain catalytic performance while consuming less energy for early material synthesis. And the process flow is simple.
为解决上述技术问题，本发明提供一种尖晶石CoAl2O4电催化材料的制备方法，包括以下步骤：In order to solve the above technical problems, the present invention provides a preparation method of spinel CoAl 2 O 4 electrocatalytic material, which includes the following steps:
(1)前驱体溶液的机械混合：将六水合硝酸钴、九水合硝酸铝、柠檬酸和去离子水机械混合；(1) Mechanical mixing of precursor solution: mechanically mix cobalt nitrate hexahydrate, aluminum nitrate nonahydrate, citric acid and deionized water;
(2)所得凝胶置于120℃烘箱中干燥6小时得到发泡前驱体；(2) The resulting gel is dried in an oven at 120°C for 6 hours to obtain a foaming precursor;
(3)将发泡前驱体研磨至粉末，置于马弗炉中于800℃条件下煅烧5小时得到CoAl2O4粉末；(3) Grind the foaming precursor to powder, place it in a muffle furnace and calcine it at 800°C for 5 hours to obtain CoAl 2 O 4 powder;
进一步的，步骤(1)所述六水合硝酸钴、九水合硝酸铝、柠檬酸和去离子水的用量分别为每1.75g六水合硝酸钴对应0.9g九水合硝酸铝混合于9ml 1.5M柠檬酸溶液中。所述机械混合是将混合溶液置于圆底烧瓶中恒温80℃加热5小时获得凝胶。Further, the amounts of cobalt nitrate hexahydrate, aluminum nitrate nonahydrate, citric acid and deionized water described in step (1) are respectively 0.9g aluminum nitrate nonahydrate for every 1.75g cobalt nitrate hexahydrate mixed with 9ml 1.5M citric acid. in solution. The mechanical mixing is to place the mixed solution in a round-bottomed flask and heat it at a constant temperature of 80°C for 5 hours to obtain a gel.
进一步的，步骤(2)所述干燥的具体过程为：将所得凝胶置于烘箱中，于120℃条件下干燥6小时得到发泡的前驱体。Further, the specific drying process in step (2) is: place the obtained gel in an oven and dry it at 120°C for 6 hours to obtain a foamed precursor.
步骤(3)所述煅烧的具体条件为：空气气氛下，于800℃下煅烧5h。The specific conditions for the calcination in step (3) are: calcination at 800°C for 5 hours in an air atmosphere.
本发明尖晶石CoAl2O4电催化材料用于ENRR的反应，即以氮气产氨的应用，以涂有CoAl2O4的碳纸为工作电极；以Ag/Agcl为参比电极；以铂网电极作为对电极；以HCl溶液(如浓度0.1M)作为电解液，在通入氮气的条件下，以HCl作为氢源，进行氮气产氨，电位设置为-0.1--0.5V vs.RHE。The spinel CoAl 2 O 4 electrocatalytic material of the present invention is used in the ENRR reaction, that is, the application of producing ammonia from nitrogen, using carbon paper coated with CoAl 2 O 4 as the working electrode; using Ag/Agcl as the reference electrode; The platinum mesh electrode is used as the counter electrode; HCl solution (such as concentration 0.1M) is used as the electrolyte. Under the condition of flowing nitrogen, HCl is used as the hydrogen source to produce ammonia from nitrogen. The potential is set to -0.1--0.5V vs. RHE.
本发明在保证制得的材料具有一定催化活性的同时，缩短了材料合成所需的时间、减小了制备过程能量的消耗且得到的材料微观形貌统一，尺寸分布集中(CoAl2O4电催化材料尖晶石结构)，在空气中能够稳定存在，上述特征有助于ENRR过程的深入研究。While ensuring that the produced material has a certain catalytic activity, the present invention shortens the time required for material synthesis and reduces the energy consumption in the preparation process. The obtained material has a uniform microscopic morphology and a concentrated size distribution (CoAl 2 O 4 electrolyte). The catalytic material spinel structure) can exist stably in the air. The above characteristics are helpful for in-depth research on the ENRR process.
附图说明Description of the drawings
图1为本发明用于ENRR的电催化材料CoAl2O4的微观形貌示意图；Figure 1 is a schematic diagram of the micromorphology of the electrocatalytic material CoAl 2 O 4 used for ENRR according to the present invention;
图2为本发明用于ENRR的电催化材料CoAl2O4的X射线衍射光谱示意图；Figure 2 is a schematic diagram of the X-ray diffraction spectrum of the electrocatalytic material CoAl 2 O 4 used for ENRR of the present invention;
图3为本发明用于ENRR的电催化材料CoAl2O4的X射线光电子能谱示意图；Figure 3 is a schematic diagram of the X-ray photoelectron spectrum of the electrocatalytic material CoAl 2 O 4 used for ENRR of the present invention;
图4为本发明用于ENRR的电催化材料CoAl2O4的拉曼光谱；Figure 4 is the Raman spectrum of the electrocatalytic material CoAl 2 O 4 used for ENRR of the present invention;
图5为本发明用于ENRR的电催化材料CoAl2O4的线性扫描伏安示意图；Figure 5 is a linear sweep voltammetry diagram of the electrocatalytic material CoAl 2 O 4 used for ENRR of the present invention;
图6为本发明用于ENRR的电催化材料CoAl2O4的计时安培示意图；Figure 6 is a timing ampere diagram of the electrocatalytic material CoAl 2 O 4 used for ENRR of the present invention;
图7为本发明用于ENRR的电催化材料CoAl2O4的氨产率示意图；Figure 7 is a schematic diagram of the ammonia production rate of the electrocatalytic material CoAl 2 O 4 used for ENRR of the present invention;
图8为本发明用于ENRR的电催化材料CoAl2O4的法拉第效率示意图；Figure 8 is a schematic diagram of the Faradaic efficiency of the electrocatalytic material CoAl 2 O 4 used for ENRR of the present invention;
图9为本发明用于ENRR的电解池结构示意图。Figure 9 is a schematic structural diagram of an electrolytic cell used for ENRR according to the present invention.
具体实施方式Detailed ways
下面通过具体实施方式进一步详细说明，但本发明并不限于以下实施例。The invention will be further described in detail below through specific embodiments, but the present invention is not limited to the following examples.
结合图1所示，一种用于ENRR的电催化材料CoAl2O4，该材料主要由尖晶石的纳米颗粒组成。As shown in Figure 1, an electrocatalytic material CoAl 2 O 4 for ENRR is mainly composed of spinel nanoparticles.
制备方法：将1.75g六水合硝酸钴、0.9g九水合硝酸铝混合于9ml 1.5M柠檬酸溶液中，置于圆底烧瓶中，在80℃加热条件下磁力搅拌5h，混合溶液逐渐粘稠并变为凝胶。将上述凝胶转移至反应皿中，置于120℃烘箱中干燥6小时得到发泡前驱体。将前驱体研磨至粉末状置于磁舟中放入马弗炉中进行煅烧，煅烧的具体条件为：800℃，5h，最后得到蓝色的CoAl2O4粉末。Preparation method: Mix 1.75g cobalt nitrate hexahydrate and 0.9g aluminum nitrate nonahydrate in 9ml 1.5M citric acid solution, place it in a round-bottomed flask, and stir magnetically under heating conditions at 80°C for 5 hours. The mixed solution gradually becomes viscous and thickens. Become a gel. Transfer the above gel to a reaction dish and dry it in a 120°C oven for 6 hours to obtain a foaming precursor. Grind the precursor until it is powdery, place it in a magnetic boat and put it into a muffle furnace for calcination. The specific conditions for calcination are: 800°C, 5h. Finally, blue CoAl 2 O 4 powder is obtained.
电极制备：称取5mg CoAl2O4粉末分散在混有20μL膜溶液(Nafion)、326μL超纯水和654μL无水乙醇的液体中超声1h得到油墨状液体，取其中20μL均匀涂敷在1*2cm的碳纸上，涂敷面积为1cm2。Electrode preparation: Weigh 5 mg of CoAl 2 O 4 powder and disperse it in a liquid mixed with 20 μL of membrane solution (Nafion), 326 μL of ultrapure water and 654 μL of absolute ethanol. Ultrasonicate for 1 hour to obtain an ink-like liquid. Take 20 μL of it and apply it evenly on 1* On 2cm carbon paper, the coating area is 1cm 2 .
电化学体系：以涂有CoAl2O4的碳纸为工作电极；以Ag/Agcl为参比电极；以铂网电极作为对电极；以HCl溶液(浓度为0.1M)作为电解液，。Electrochemical system: Use carbon paper coated with CoAl 2 O 4 as the working electrode; use Ag/Agcl as the reference electrode; use a platinum mesh electrode as the counter electrode; use HCl solution (concentration: 0.1M) as the electrolyte.
本实施例中，利用扫描电镜和透射电镜对电极进行了微观形貌表征及分析In this example, scanning electron microscopy and transmission electron microscopy were used to characterize and analyze the microscopic morphology of the electrode.
图1中可以看出材料主要以尖晶石纳米颗粒组成。It can be seen in Figure 1 that the material is mainly composed of spinel nanoparticles.
图2为本发明用于ENRR的电催化材料CoAl2O4的X射线衍射光谱示意图；Figure 2 is a schematic diagram of the X-ray diffraction spectrum of the electrocatalytic material CoAl 2 O 4 used for ENRR of the present invention;
图3是本发明材料CoAl2O4的X射线光电子能谱示意图；Figure 3 is a schematic diagram of the X-ray photoelectron spectrum of the material CoAl 2 O 4 of the present invention;
图4是本发明材料CoAl2O4的拉曼光谱图；Figure 4 is the Raman spectrum of CoAl 2 O 4 , the material of the present invention;
图5是本发明材料的线性扫描伏安示意图；具体实验参数为：起始电位为0V；终止电位为-1.8V；扫描速率为0.05V/s；取点间隔为0.001V；灵敏度为0.1A/V；不同气氛是以30mL/min的气体流速连续向如图8所示电解池中通气30min实现的。从图5中可以看出在氮气气氛下，材料的电流明显大于氩气气氛下，初步证明材料具有一定的电催化固氮性能。Figure 5 is a linear scan voltammetry diagram of the material of the present invention; the specific experimental parameters are: the starting potential is 0V; the ending potential is -1.8V; the scan rate is 0.05V/s; the point interval is 0.001V; the sensitivity is 0.1A /V; different atmospheres are achieved by continuously ventilating the electrolytic cell as shown in Figure 8 for 30 minutes at a gas flow rate of 30mL/min. It can be seen from Figure 5 that under nitrogen atmosphere, the current of the material is significantly greater than that under argon atmosphere, which preliminarily proves that the material has certain electrocatalytic nitrogen fixation properties.
图6是本发明材料的计时安培示意图；具体参数为：电位设置分别为-0.1、-0.2、-0.3、-0.4、-0.5V vs.RHE；取点间隔为0.05s；运行时间为7200s；灵敏度为0.1A/V。从图6中可以看出，在不同电位下，其对应的电流都在很小的范围内波动，证明材料具有一定的催化稳定性。Figure 6 is a timing ampere diagram of the material of the present invention; the specific parameters are: the potential settings are -0.1, -0.2, -0.3, -0.4, -0.5V vs. RHE respectively; the point-taking interval is 0.05s; the running time is 7200s; Sensitivity is 0.1A/V. It can be seen from Figure 6 that at different potentials, the corresponding currents fluctuate within a small range, proving that the material has a certain catalytic stability.
图7是本发明材料的产氨示意图；从图7中可以看出，在-0.2V vs.RHE的电位下，本发明材料产氨量最高达到了23.84μg h-1mgcat -1，证明本发明材料具有较为优异的电催化产氨性能。产氨量计算公式如下：Figure 7 is a schematic diagram of the ammonia production of the material of the present invention; it can be seen from Figure 7 that at the potential of -0.2V vs. RHE, the maximum ammonia production amount of the material of the present invention reaches 23.84μg h -1 mg cat -1 , proving that The material of the invention has relatively excellent electrocatalytic ammonia production performance. The calculation formula for ammonia production is as follows:
为产氨量，单位为/> 为电解液中NH4Cl的浓度，单位为μgmL-1；V为电解液体积，单位为mL；t为电解时间，单位为h；mcat为电极材料的质量，单位为mg。 is the amount of ammonia produced, the unit is/> is the concentration of NH 4 Cl in the electrolyte, in μgmL -1 ; V is the volume of the electrolyte, in mL; t is the electrolysis time, in h; m cat is the mass of the electrode material, in mg.
图8是本发明材料的法拉第效率示意图；从图8中可以看出，在-0.2V vs.RHE的电位下，本发明材料FE值最高达到了12.79％，证明了本发明材料具有更高的选择性。FE计算公式如下：Figure 8 is a schematic diagram of the Faradaic efficiency of the material of the present invention; it can be seen from Figure 8 that at the potential of -0.2V vs. RHE, the FE value of the material of the present invention reaches the highest 12.79%, proving that the material of the present invention has higher Selectivity. The FE calculation formula is as follows:
FE为法拉第效率，单位为％；F为法拉第常数，其值为96500C mol-1；Q为电解过程总的电荷消耗量，单位为C。FE is Faraday efficiency, the unit is %; F is Faraday constant, its value is 96500C mol -1 ; Q is the total charge consumption of the electrolysis process, the unit is C.
图9是本发明材料的电解池结构示意图。Figure 9 is a schematic structural diagram of an electrolytic cell made of materials of the present invention.
以上所述的仅是本发明的实施例，方案中公知的具体结构及特性等常识在此未作过多描述。应当指出，对于本领域的技术人员来说，在不脱离本发明结构的前提下，还可以做出若干变形和改进，这些也应该视为本发明的保护范围，这些都不会影响本发明实施的效果和专利的实用性。The above are only embodiments of the present invention, and common knowledge such as the known specific structures and characteristics of the solutions are not described in detail here. It should be pointed out that for those skilled in the art, several modifications and improvements can be made without departing from the structure of the present invention. These should also be regarded as the protection scope of the present invention and will not affect the implementation of the present invention. The effect and practicality of the patent.
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