CN114032579B - Application of a copper-tin double metal hydroxide catalyst in the electrocatalytic ammoxidation of nitrogen - Google Patents

Application of a copper-tin double metal hydroxide catalyst in the electrocatalytic ammoxidation of nitrogen Download PDF

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CN114032579B
CN114032579B CN202111204948.5A CN202111204948A CN114032579B CN 114032579 B CN114032579 B CN 114032579B CN 202111204948 A CN202111204948 A CN 202111204948A CN 114032579 B CN114032579 B CN 114032579B
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康鹏
候静
程荧荧
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Abstract

本发明涉及一种铜锡双金属氢氧化物催化剂在电催化氨氧化制氮气中的应用，铜锡双金属氢氧化物催化剂为CuSn(OH)6；称取CuSn(OH)6分散在易挥发溶剂中，并向其中加入萘酚溶液，超声得到均匀分散的分散液；取电极分散液均匀滴涂在碳纸电极上；以Pt电极作为对电极，汞/***电极为参比电极，所制作的电极为工作电极，构成标准三电极体系，氨为底物，硫酸钾溶液为电解液，保持溶液pH为9～13进行电解测试，得到氮气法拉第效率和分电流密度在最优电位下分别能达到70％和1mA·cm‑2以上。应用于电催化氨氧化具有较低的氧化起峰电位0.85V vs.Hg/HgO，较高的电催化氨氧化制氮气的法拉第效率。

Figure 202111204948

The present invention relates to the application of a kind of copper tin double metal hydroxide catalyst in electrocatalytic ammoxidation nitrogen production, copper tin double metal hydroxide catalyst is CuSn(OH) 6 ; Take CuSn(OH) 6 and disperse in volatile Naphthol solution was added to the solvent, and a uniformly dispersed dispersion was obtained by ultrasonication; the electrode dispersion was evenly drip-coated on the carbon paper electrode; the Pt electrode was used as the counter electrode, and the mercury/mercuric oxide electrode was used as the reference electrode. The electrode produced is the working electrode, which constitutes a standard three-electrode system. Ammonia is the substrate, potassium sulfate solution is the electrolyte, and the pH of the solution is kept at 9-13 for electrolysis tests. It can reach 70% and above 1mA·cm ‑2 . It has a lower oxidation peak potential of 0.85V vs. Hg/HgO applied to electrocatalytic ammonia oxidation, and a higher Faraday efficiency of electrocatalytic ammonia oxidation to nitrogen.

Figure 202111204948

Description

一种铜锡双金属氢氧化物催化剂在电催化氨氧化制氮气中的 应用Electrocatalytic ammonia oxidation of a copper-tin double metal hydroxide catalyst in nitrogen production application

技术领域technical field

本发明属于电催化氨氧化制氮气领域，具体地说即一种催化剂在电催化氨氧化制氮气领域的应用方法。特别是涉及一种铜锡双金属氢氧化物催化剂在电催化氨氧化制氮气中的应用。The invention belongs to the field of nitrogen production by electrocatalytic ammoxidation, specifically an application method of a catalyst in the field of nitrogen production by electrocatalytic ammoxidation. In particular, it relates to the application of a copper-tin double metal hydroxide catalyst in electrocatalytic ammoxidation for nitrogen production.

背景技术Background technique

氮循环平衡对于维持良好生态环境具有重要作用。工业以及生活中含氮废水的过量排放容易导致水体富营养化，同时也会对水体氮循环平衡造成不良影响。目前，处理含氮废水主要通过折点氯法和微生物分解法。但是复杂的硝化-反硝化过程导致微生物法耗时长，而折点氯法产生的氯胺和卤代物副产物易对环境造成二次污染。直接电化学氨氧化法(dAOR)由于其操作简单、无含氯试剂添加成为具有广阔应用前景的方法。除了废水处理，直接氨氧化还被应用于直接氨燃料电池以及氨传感器等方面。但是由于缺少高效的电化学氨氧化催化剂以及其自身缓慢的动力学限制，目前直接电化学氨氧化还未实现工业化应用。Nitrogen cycle balance plays an important role in maintaining a good ecological environment. Excessive discharge of nitrogen-containing wastewater in industry and life can easily lead to eutrophication of water bodies, and at the same time have adverse effects on the nitrogen cycle balance of water bodies. At present, the treatment of nitrogenous wastewater is mainly through the breakpoint chlorine method and microbial decomposition method. However, the complex nitrification-denitrification process leads to a long time-consuming microbial method, and the chloramine and halogenated by-products produced by the breakpoint chlorine method are likely to cause secondary pollution to the environment. Direct electrochemical ammonia oxidation (dAOR) has become a method with broad application prospects due to its simple operation and no addition of chlorine-containing reagents. In addition to wastewater treatment, direct ammonia oxidation has also been applied to direct ammonia fuel cells and ammonia sensors. However, due to the lack of efficient electrochemical ammoxidation catalysts and its own slow kinetic limitations, the direct electrochemical ammoxidation has not yet achieved industrial application.

传统贵金属(如Pt、Ir)具有低的dAOR过电位和高的催化活性，但是价格昂贵、资源匮乏限制了其大规模应用。因此，开发非贵金属基催化剂应用于电催化氨氧化领域成为研究热点。Xuan Jiang等人研究发现Cu(OH)2催化剂应用于电催化氨氧化时表现出较低的氨去除速率，且易催化氨氧化形成过氧化产物-硝酸盐。硝酸盐也是一种废水污染物。虽然理论计算的研究表明在廉价过渡金属元素中Cu被认为具有较高的dAOR活性，但是由于Cu表面对于NH3的吸附能力较弱，阻碍了NH3分子去质子化过程(The Journal of PhysicalChemistry C,2015.119(26),14692-14701)。并且废水中所含氨氮浓度较低，一般在0.001～0.1mol/L。，因此电催化氨氧化领域中氨吸附也是一个重要挑战。以往研究表明Sn基材料对NH3分子具有较强的吸附能力(The Journal of Physical Chemistry C,2011.115(46),23050-23056)。虽然目前针对电催化氨氧化反应开发了一些催化剂，但并没有关于铜锡双金属催化剂应用于电催化氨氧化的报道。Traditional noble metals (such as Pt, Ir) have low dAOR overpotential and high catalytic activity, but their high price and scarcity of resources limit their large-scale application. Therefore, the development of non-noble metal-based catalysts for electrocatalytic ammoxidation has become a research hotspot. Xuan Jiang et al. found that the Cu(OH) 2 catalyst exhibited a low ammonia removal rate when applied to electrocatalytic ammonia oxidation, and easily catalyzed ammonia oxidation to form peroxidation product-nitrate. Nitrate is also a wastewater pollutant. Although theoretical calculation studies have shown that Cu is considered to have a high dAOR activity among cheap transition metal elements, the deprotonation process of NH 3 molecules is hindered due to the weak adsorption capacity of Cu surface for NH 3 (The Journal of Physical Chemistry C , 2015.119(26), 14692-14701). And the concentration of ammonia nitrogen contained in the wastewater is low, generally 0.001-0.1mol/L. , so ammonia adsorption is also an important challenge in the field of electrocatalytic ammonia oxidation. Previous studies have shown that Sn-based materials have a strong adsorption capacity for NH 3 molecules (The Journal of Physical Chemistry C, 2011.115(46), 23050-23056). Although some catalysts have been developed for electrocatalytic ammoxidation, there is no report on the application of copper-tin bimetallic catalysts in electrocatalytic ammoxidation.

发明内容Contents of the invention

本发明的目的为克服上述不足，提供一种价格低廉且具有高效电催化氨氧化活性的铜锡双金属氢氧化物催化剂应用于电催化氨氧化制氮气领域。The object of the present invention is to overcome the above-mentioned shortcomings, and to provide a low-cost copper-tin double metal hydroxide catalyst with high-efficiency electrocatalytic ammoxidation activity for use in the field of electrocatalytic ammoxidation for nitrogen production.

本发明的技术方案如下：Technical scheme of the present invention is as follows:

一种铜锡双金属氢氧化物催化剂在电催化氨氧化制氮气中的应用，催化剂为CuSn(OH)6，应用方法如下：The application of a copper-tin double metal hydroxide catalyst in the production of nitrogen by electrocatalytic ammoxidation, the catalyst is CuSn(OH) 6 , and the application method is as follows:

(1)称取铜锡双金属氢氧化物催化剂(CuSn(OH)6)分散在易挥发溶剂中，并向其中加入萘酚溶液，超声得到均匀分散的分散液；(1) Weigh the copper-tin double metal hydroxide catalyst (CuSn(OH) 6 ) and disperse it in a volatile solvent, and add a naphthol solution therein, and obtain a uniformly dispersed dispersion by ultrasonication;

(2)取步骤(1)的电极分散液均匀滴涂在碳纸电极上；(2) Get the electrode dispersion liquid of step (1) and evenly drop-coat it on the carbon paper electrode;

(3)以Pt电极作为对电极，汞/***电极为参比电极，步骤(2)所制作的电极为工作电极，构成标准三电极体系，氨为底物，硫酸钾溶液为电解液，保持溶液pH为9～13进行电解测试，所得到氮气法拉第效率和分电流密度在最优电位下分别能达到70％和1mA·cm-2以上。(3) take Pt electrode as counter electrode, mercury/mercuric oxide electrode is reference electrode, the electrode that step (2) is made is working electrode, constitutes standard three-electrode system, and ammonia is substrate, and potassium sulfate solution is electrolyte, Keeping the pH of the solution at 9-13 for electrolysis test, the obtained nitrogen faradaic efficiency and partial current density can respectively reach 70% and above 1mA·cm -2 at the optimum potential.

优选条件：Preferred conditions:

易挥发性溶剂：N,N-二甲基甲酰胺、乙醇、异丙醇，优选为N,N-二甲基甲酰胺。Volatile solvent: N,N-dimethylformamide, ethanol, isopropanol, preferably N,N-dimethylformamide.

电极分散液中催化剂质量浓度为5～15mg/mL，优选为10mg/mL。The mass concentration of the catalyst in the electrode dispersion is 5-15 mg/mL, preferably 10 mg/mL.

萘酚溶液用量为25～75μL，优选为40～50μL。The dosage of naphthol solution is 25-75 μL, preferably 40-50 μL.

硫酸钾溶液浓度是0.1～1mol/L，优选为0.4～0.5mol/L。The concentration of the potassium sulfate solution is 0.1-1 mol/L, preferably 0.4-0.5 mol/L.

pH优选为11。The pH is preferably 11.

电解电压范围为0.8～2.0V vs.Hg/HgO。The electrolysis voltage range is 0.8～2.0V vs.Hg/HgO.

本发明催化剂制备方法根据文献(Journal of Materials Chemistry A,2019.7(13):p.7932-7938)并将文献中的锡盐换为可溶性氯化亚锡。前驱体溶液A与前驱体溶液B中可溶性锡盐和可溶性铜盐的摩尔量之比优选为4:1～1:2。The catalyst preparation method of the present invention is based on the literature (Journal of Materials Chemistry A, 2019.7 (13): p.7932-7938) and the tin salt in the literature is replaced by soluble stannous chloride. The molar ratio of the soluble tin salt and the soluble copper salt in the precursor solution A to the precursor solution B is preferably 4:1˜1:2.

称取可溶性锡盐溶于氢氧化钠溶液中形成前驱体溶液A；将可溶性铜盐溶于纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn双金属氢氧化物催化剂。Weigh soluble tin salt and dissolve in sodium hydroxide solution to form precursor solution A; dissolve soluble copper salt in pure water to form precursor solution B; slowly drop precursor solution B into precursor solution A while stirring, After the dropwise addition is completed, keep stirring; after the reaction is completed, separate, wash, and dry in a vacuum oven to obtain a CuSn double metal hydroxide catalyst.

本发明的显著优点：Significant advantage of the present invention:

(1)本发明催化剂应用于电催化氨氧化制氮气反应，具有优异的催化性能。同时，催化剂的应用过程简单，操作方便，且对环境友好，无二次污染，具有广阔的应用前景。(1) The catalyst of the present invention is applied to the electrocatalytic ammoxidation reaction to produce nitrogen, and has excellent catalytic performance. At the same time, the application process of the catalyst is simple, the operation is convenient, and it is friendly to the environment, without secondary pollution, and has broad application prospects.

(2)本发明的CuSn双金属氢氧化物催化剂应用于电催化氨氧化具有较低的氧化起峰电位(0.85V vs.Hg/HgO)，且具有较高的电催化氨氧化制氮气的法拉第效率(可达50％以上)。(2) The CuSn double metal hydroxide catalyst of the present invention has a lower oxidation peak potential (0.85V vs. Hg/HgO) when applied to the electrocatalytic ammoxidation, and has a higher Faraday for producing nitrogen from the electrocatalytic ammoxidation Efficiency (up to 50% or more).

附图说明Description of drawings

图1是实施例1、对比例1得到的CuSn(OH)6和Cu(OH)2催化剂电催化氨氧化电压-电流密度曲线图。Fig. 1 is the CuSn(OH) 6 and Cu(OH) 2 catalyst electrocatalytic ammoxidation voltage-current density graphs obtained in Example 1 and Comparative Example 1.

图2是实施例2、对比例1得到的CuSn(OH)6和Cu(OH)2催化剂电催化氨氧化制氮气法拉第电流效率曲线图。Fig. 2 is embodiment 2, comparative example 1 obtains CuSn (OH) 6 and Cu (OH) 2 Catalyst electrocatalytic ammoxidation produces nitrogen faradaic current efficiency curve.

图3是实施例2、对比例1得到的CuSn(OH)6和Cu(OH)2催化剂电催化氨氧化制氮气分电流密度曲线图。Fig. 3 is embodiment 2, comparative example 1 obtains CuSn (OH) 6 and Cu (OH) 2 Catalyst electrocatalytic ammoxidation produces nitrogen part electric current density curve.

图4是实施例9得到的CuSn(OH)6催化剂电催化氨氧化产物法拉第电流效率曲线图。Fig. 4 is the Faradaic current efficiency curve of CuSn(OH) 6 catalyst electrocatalytic ammoxidation product obtained in Example 9.

图5是实施例9得到的CuSn(OH)6催化剂电催化羟胺氧化产物法拉第电流效率曲线图。Fig. 5 is the Faradaic current efficiency curve of CuSn(OH) 6 catalyst electrocatalytic oxidation product of hydroxylamine obtained in Example 9.

图6是实施例10得到的CuSn(OH)6、Sn(OH)x和Cu(OH)2催化剂质谱-程序升温化学吸附曲线图。Fig. 6 is a mass spectrum-temperature-programmed chemical adsorption curve of CuSn(OH) 6 , Sn(OH)x and Cu(OH) 2 catalysts obtained in Example 10.

具体实施方案specific implementation plan

下面通过具体的实施例对本发明作进一步详细描述，但本发明的实施方法不限于此。The present invention will be further described in detail through specific examples below, but the implementation method of the present invention is not limited thereto.

实施例1Example 1

催化剂制备：称取2.2mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将4.4mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6。Catalyst preparation: take 2.2mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 4.4mmol copper sulfate in 50mL pure water to form precursor solution B; B is slowly dripped into the precursor solution A under stirring state, and keep stirring after the addition is completed; after the reaction is completed, separate, wash, and dry in a vacuum oven to obtain CuSn(OH) 6 .

(1)准确称取10mg CuSn(OH)6催化剂分散于1mL N,N-二甲基甲酰胺溶液中，将50μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 10 mg of CuSn(OH) 6 catalyst and disperse it in 1 mL of N,N-dimethylformamide solution, add 50 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+0.5mol硫酸钾为电解液。在pH为11条件下进行电催化氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.85V vs.Hg/HgO)，氮气分电流密度可达1.0mA/cm-2，氮气最大法拉第效率可达50％以上。(2) With the Pt sheet as the counter electrode, the mercury/mercury oxide (Hg/HgO) electrode as the reference electrode, the electrode prepared in step (1) as the working electrode, constitutes a standard three-electrode system, 10mmol NH 3 +0.5mol Potassium sulfate is the electrolyte. The electrocatalytic oxidation electrolytic activity test was carried out under the condition of pH 11. CuSn(OH) 6 shows a lower peak potential (0.85V vs. Hg/HgO), the current density of nitrogen gas can reach 1.0mA/cm -2 , and the maximum faradaic efficiency of nitrogen gas can reach more than 50%.

实施例2Example 2

催化剂制备：称取2.2mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将4.4mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6催化剂。Catalyst preparation: take 2.2mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 4.4mmol copper sulfate in 50mL pure water to form precursor solution B; B was slowly dripped into the precursor solution A under stirring, and kept stirring after the addition was completed; after the reaction, separated, washed, and dried in a vacuum oven to obtain a CuSn(OH) 6 catalyst.

(1)准确称取5mg CuSn(OH)6催化剂分散于0.5mL乙醇溶液中，将25μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 5 mg of CuSn(OH) 6 catalyst and disperse it in 0.5 mL of ethanol solution, add 25 μL of naphthol solution into the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+0.1mol硫酸钾为电解液。在pH为11条件下进行电催化氨氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.84V vs.Hg/HgO)，氮气分电流密度可达1.0mA/cm-2，氮气最大法拉第效率可达50％以上。(2) With the Pt sheet as the counter electrode, the mercury/mercury oxide (Hg/HgO) electrode as the reference electrode, and the electrode prepared in step (1) as the working electrode, a standard three-electrode system is formed, 10mmol NH 3 +0.1mol Potassium sulfate is the electrolyte. The electrolytic activity test of electrocatalytic ammoxidation was carried out under the condition of pH 11. CuSn(OH) 6 exhibits a lower peak potential (0.84V vs. Hg/HgO), the current density of nitrogen gas can reach 1.0mA/cm -2 , and the maximum faradaic efficiency of nitrogen gas can reach more than 50%.

实施例3Example 3

催化剂制备：称取2.2mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将4.4mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6催化剂。Catalyst preparation: take 2.2mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 4.4mmol copper sulfate in 50mL pure water to form precursor solution B; B is slowly dripped into the precursor solution A under stirring state, and keep stirring after the addition is completed; after the reaction is completed, separate, wash, and dry in a vacuum oven to obtain a CuSn(OH) 6 catalyst.

(1)准确称取10mg CuSn(OH)6催化剂分散于1mL N,N-二甲基甲酰胺溶液中，将40μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 10 mg of CuSn(OH) 6 catalyst and disperse it in 1 mL of N,N-dimethylformamide solution, add 40 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+0.4mol硫酸钾为电解液。在pH为11条件下进行电催化氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.85V vs.Hg/HgO)，氮气分电流密度可达1.1mA/cm-2，氮气最大法拉第效率可达50％以上。(2) With the Pt sheet as the counter electrode, the mercury/mercury oxide (Hg/HgO) electrode as the reference electrode, the electrode prepared in step (1) as the working electrode, constitutes a standard three-electrode system, 10mmol NH 3 +0.4mol Potassium sulfate is the electrolyte. The electrocatalytic oxidation electrolytic activity test was carried out under the condition of pH 11. CuSn(OH) 6 shows a lower peak potential (0.85V vs. Hg/HgO), the current density of nitrogen gas can reach 1.1mA/cm -2 , and the maximum faradaic efficiency of nitrogen gas can reach more than 50%.

实施例4Example 4

催化剂制备：称取2.2mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将4.4mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6催化剂。Catalyst preparation: take 2.2mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 4.4mmol copper sulfate in 50mL pure water to form precursor solution B; B was slowly dripped into the precursor solution A under stirring, and kept stirring after the addition was completed; after the reaction, separated, washed, and dried in a vacuum oven to obtain a CuSn(OH) 6 catalyst.

(1)准确称取10mg CuSn(OH)6催化剂分散于1mL N,N-二甲基甲酰胺溶液中，将50μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 10 mg of CuSn(OH) 6 catalyst and disperse it in 1 mL of N,N-dimethylformamide solution, add 50 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+0.5mol硫酸钾为电解液。在pH为13条件下进行电催化氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.85V vs.Hg/HgO)，氮气分电流密度可达1.3mA/cm-2，氮气最大法拉第效率可达50％以上。(2) With the Pt sheet as the counter electrode, the mercury/mercury oxide (Hg/HgO) electrode as the reference electrode, the electrode prepared in step (1) as the working electrode, constitutes a standard three-electrode system, 10mmol NH 3 +0.5mol Potassium sulfate is the electrolyte. The electrocatalytic oxidation electrolytic activity test was carried out under the condition of pH 13. CuSn(OH) 6 exhibits a lower peak potential (0.85V vs. Hg/HgO), the current density of nitrogen gas can reach 1.3mA/cm -2 , and the maximum faradaic efficiency of nitrogen gas can reach more than 50%.

实施例5Example 5

催化剂制备：称取2.2mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将4.4mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6催化剂。Catalyst preparation: take 2.2mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 4.4mmol copper sulfate in 50mL pure water to form precursor solution B; B was slowly dripped into the precursor solution A under stirring, and kept stirring after the addition was completed; after the reaction, separated, washed, and dried in a vacuum oven to obtain a CuSn(OH) 6 catalyst.

(1)准确称取10mg CuSn(OH)6催化剂分散于1mL N,N-二甲基甲酰胺溶液中，将50μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 10 mg of CuSn(OH) 6 catalyst and disperse it in 1 mL of N,N-dimethylformamide solution, add 50 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+1mol硫酸钾为电解液。在pH为9条件下进行电催化氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.86V vs.Hg/HgO)，氮气分电流密度可达1.0mA/cm-2，氮气最大法拉第效率可达50％以上。(2) With the Pt sheet as the counter electrode, the mercury/mercuric oxide (Hg/HgO) electrode as the reference electrode, and the electrode prepared in step (1) as the working electrode, a standard three-electrode system is formed, 10mmol NH 3 +1mol sulfuric acid Potassium is the electrolyte. The electrocatalytic oxidation electrolytic activity test was carried out under the condition of pH 9. CuSn(OH) 6 shows a lower peak potential (0.86V vs. Hg/HgO), the current density of nitrogen gas can reach 1.0mA/cm -2 , and the maximum faradaic efficiency of nitrogen gas can reach more than 50%.

对比例1Comparative example 1

(1)准确称取15mg Cu(OH)2催化剂分散于1.5mL异丙醇溶液中，将75μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 15 mg of Cu(OH) 2 catalyst and disperse it in 1.5 mL of isopropanol solution, add 75 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+0.5mol硫酸钾为电解液。在pH为11条件下进行电催化氨氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.84V vs.Hg/HgO)，氮气分电流密度为0.5mA/cm-2，氮气最大法拉第效率低于50％。(2) With the Pt sheet as the counter electrode, the mercury/mercury oxide (Hg/HgO) electrode as the reference electrode, the electrode prepared in step (1) as the working electrode, constitutes a standard three-electrode system, 10mmol NH 3 +0.5mol Potassium sulfate is the electrolyte. The electrolytic activity test of electrocatalytic ammoxidation was carried out under the condition of pH 11. CuSn(OH) 6 exhibits a lower onset potential (0.84V vs. Hg/HgO), a current density of 0.5mA/cm -2 in nitrogen, and a maximum Faradaic efficiency of less than 50% in nitrogen.

图1为实施例1和对比例1中CuSn(OH)6和Cu(OH)2催化剂的电压-电流密度曲线。从图中可以看出CuSn(OH)6具有较低的起峰电位，在0.85V vs.Hg/HgO开始起峰。CuSn(OH)6在较低电位1.2V vs.Hg/HgO出现一个峰值电流密度(0.85mA/cm-2)。Fig. 1 is the voltage-current density curve of CuSn(OH) 6 and Cu(OH) 2 catalyst in embodiment 1 and comparative example 1. It can be seen from the figure that CuSn(OH) 6 has a lower peak onset potential, and the peak starts at 0.85V vs. Hg/HgO. CuSn(OH) 6 exhibits a peak current density (0.85mA/cm -2 ) at a lower potential of 1.2V vs. Hg/HgO.

图2为实施例2、对比例1中CuSn(OH)6和Cu(OH)2催化剂电催化氨氧化制氮气法拉第效率图。从图中可以看出，随着所加电压的增加，氮气的法拉第效率都降低。这是由于所加电压越大，氨氧化的竞争反应-氧析出反应越严重。CuSn(OH)6催化剂具有较高的氮气法拉第效率，最高可达50％以上，最大电流密度可达1.2mA/cm-2。Fig. 2 is the Faradaic efficiency diagram of electrocatalytic ammonia oxidation of CuSn(OH) 6 and Cu(OH) 2 catalysts in Example 2 and Comparative Example 1 to nitrogen. It can be seen from the figure that as the applied voltage increases, the Faradaic efficiency of nitrogen decreases. This is because the greater the applied voltage, the more severe the competing reaction of ammonia oxidation—the oxygen evolution reaction. The CuSn(OH) 6 catalyst has a high nitrogen faradaic efficiency, up to over 50%, and a maximum current density of 1.2mA/cm -2 .

图3为实施例2、对比例1中CuSn(OH)6和Cu(OH)2催化剂电催化氨氧化制氮气分电流密度曲线图。图中主要描述了电压从1.0增加到1.4V vs.Hg/HgO，氮气分电流密度变化。从图中可以看出，在整个电解范围中，CuSn(OH)6都表现出较高的氮气分电流密度，最高电流密度可达1.2mA/cm-2。、Fig. 3 is the graph of the current density curve of nitrogen gas fraction produced by electrocatalytic ammoxidation of CuSn(OH) 6 and Cu(OH) 2 catalysts in Example 2 and Comparative Example 1. The figure mainly describes the change of the current density of nitrogen gas when the voltage increases from 1.0 to 1.4V vs. Hg/HgO. It can be seen from the figure that CuSn(OH) 6 exhibits a higher current density of nitrogen gas in the whole electrolytic range, and the highest current density can reach 1.2mA/cm -2 . ,

实施例6Example 6

催化剂制备：称取3.3mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将3.3mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6催化剂。Catalyst preparation: take 3.3mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 3.3mmol copper sulfate in 50mL pure water to form precursor solution B; B was slowly dripped into the precursor solution A under stirring, and kept stirring after the addition was completed; after the reaction, separated, washed, and dried in a vacuum oven to obtain a CuSn(OH) 6 catalyst.

(1)准确称取10mg CuSn(OH)6催化剂分散于1mL N,N-二甲基甲酰胺溶液中，将50μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 10 mg of CuSn(OH) 6 catalyst and disperse it in 1 mL of N,N-dimethylformamide solution, add 50 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+1mol硫酸钾为电解液。在pH为11条件下进行电催化氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.86V vs.Hg/HgO)，氮气分电流密度可达1.0mA/cm-2，氮气最大法拉第效率可达50％以上。(2) With the Pt sheet as the counter electrode, the mercury/mercuric oxide (Hg/HgO) electrode as the reference electrode, and the electrode prepared in step (1) as the working electrode, a standard three-electrode system is formed, 10mmol NH 3 +1mol sulfuric acid Potassium is the electrolyte. The electrocatalytic oxidation electrolytic activity test was carried out under the condition of pH 11. CuSn(OH) 6 shows a lower peak potential (0.86V vs. Hg/HgO), the current density of nitrogen gas can reach 1.0mA/cm -2 , and the maximum faradaic efficiency of nitrogen gas can reach more than 50%.

实施例7Example 7

催化剂制备：称取1.32mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将5.28mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6催化剂。Catalyst preparation: take 1.32mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 5.28mmol copper sulfate in 50mL pure water to form precursor solution B; B was slowly dripped into the precursor solution A under stirring, and kept stirring after the addition was completed; after the reaction, separated, washed, and dried in a vacuum oven to obtain a CuSn(OH) 6 catalyst.

(1)准确称取10mg CuSn(OH)6催化剂分散于1mL乙醇溶液中，将50μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 10 mg of CuSn(OH) 6 catalyst and disperse in 1 mL of ethanol solution, add 50 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+1mol硫酸钾为电解液。在pH为11条件下进行电催化氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.85V vs.Hg/HgO)，氮气分电流密度可达1.0mA/cm-2，氮气最大法拉第效率可达50％以上。(2) With the Pt sheet as the counter electrode, the mercury/mercuric oxide (Hg/HgO) electrode as the reference electrode, and the electrode prepared in step (1) as the working electrode, a standard three-electrode system is formed, 10mmol NH 3 +1mol sulfuric acid Potassium is the electrolyte. The electrocatalytic oxidation electrolytic activity test was carried out under the condition of pH 11. CuSn(OH) 6 shows a lower peak potential (0.85V vs. Hg/HgO), the current density of nitrogen gas can reach 1.0mA/cm -2 , and the maximum faradaic efficiency of nitrogen gas can reach more than 50%.

实施例8Example 8

催化剂制备：称取2.2mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将4.4mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6催化剂。Catalyst preparation: take 2.2mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 4.4mmol copper sulfate in 50mL pure water to form precursor solution B; B was slowly dripped into the precursor solution A under stirring, and kept stirring after the addition was completed; after the reaction, separated, washed, and dried in a vacuum oven to obtain a CuSn(OH) 6 catalyst.

(1)准确称取10mg CuSn(OH)6催化剂分散于1mL N,N-二甲基甲酰胺溶液中，将50μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 10 mg of CuSn(OH) 6 catalyst and disperse it in 1 mL of N,N-dimethylformamide solution, add 50 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系，10mmol NH3+1mol硫酸钾为电解液。在pH为11条件下进行电催化氧化电解活性测试。CuSn(OH)6表现出较低的起峰电位(0.87V vs.Hg/HgO)，氮气分电流密度可达1.0mA/cm-2，氮气最大法拉第效率可达50％以上。(2) With the Pt sheet as the counter electrode, the mercury/mercuric oxide (Hg/HgO) electrode as the reference electrode, and the electrode prepared in step (1) as the working electrode, a standard three-electrode system is formed, 10mmol NH 3 +1mol sulfuric acid Potassium is the electrolyte. The electrocatalytic oxidation electrolytic activity test was carried out under the condition of pH 11. CuSn(OH) 6 shows a lower peak potential (0.87V vs. Hg/HgO), the current density of nitrogen gas can reach 1.0mA/cm -2 , and the maximum faradaic efficiency of nitrogen gas can reach more than 50%.

实施例9Example 9

制备工作电极以及其在电催化羟胺氧化中的应用。具体实施步骤：Preparation of working electrode and its application in electrocatalytic oxidation of hydroxylamine. Specific implementation steps:

催化剂制备：称取2.2mmol氯化亚锡溶于100mL 2mol/L的氢氧化钠溶液中形成前驱体溶液A；将4.4mmol硫酸铜溶解于50mL纯水中形成前驱体溶液B；将前驱体溶液B在搅拌状态下缓慢滴入前驱体溶液A，待滴加结束，保持搅拌；反应结束后，分离，洗涤，置于真空烘箱中干燥，即得到CuSn(OH)6催化剂。Catalyst preparation: take 2.2mmol stannous chloride and dissolve in 100mL 2mol/L sodium hydroxide solution to form precursor solution A; dissolve 4.4mmol copper sulfate in 50mL pure water to form precursor solution B; B was slowly dripped into the precursor solution A under stirring, and kept stirring after the addition was completed; after the reaction, separated, washed, and dried in a vacuum oven to obtain a CuSn(OH) 6 catalyst.

(1)准确称取10mg CuSn(OH)6催化剂分散于1mL乙醇溶液中，将50μL的萘酚溶液加入到上述溶液中超声1h，得到电极分散液。取160μL电极分散液均匀滴涂在碳纸电极上，室温干燥备用。(1) Accurately weigh 10 mg of CuSn(OH) 6 catalyst and disperse in 1 mL of ethanol solution, add 50 μL of naphthol solution to the above solution and sonicate for 1 h to obtain an electrode dispersion. Take 160 μL of electrode dispersion and evenly drop-coat it on the carbon paper electrode, and dry it at room temperature for later use.

(2)以Pt片为对电极，汞/***(Hg/HgO)电极为参比电极，步骤(1)所制备的电极为工作电极，构成标准的三电极体系。分别在10mmol羟胺(HO-NH2)+0.5mol硫酸钾和10mmolNH3+0.5mol硫酸钾的电解液中，在pH为11条件下进行电催化氧化电解活性测试。(2) A Pt sheet is used as a counter electrode, a mercury/mercuric oxide (Hg/HgO) electrode is used as a reference electrode, and the electrode prepared in step (1) is used as a working electrode, forming a standard three-electrode system. The electrocatalytic oxidation electrolytic activity test was carried out under the condition of pH 11 in the electrolytes of 10 mmol hydroxylamine (HO-NH 2 ) + 0.5 mol potassium sulfate and 10 mmol NH 3 + 0.5 mol potassium sulfate respectively.

图4，5为实施例9中CuSn(OH)6分别对不同底物(NH3和HO-NH2)进行电催化氧化，所得到的各种产物的法拉第效率图。从图中可以看出CuSn(OH)6电催化氧化氨的主要产物为氮气，最大效可达75％以上，过氧化产物-硝酸盐的法拉第效率最大仅有19.6％，但是电催化氧化羟胺的主产物为硝酸盐，最大效率可达到75％以上，几乎没有氮气生成，说明HO-NH2中间体的形成会导致生成过氧化产物。Cu-Sn双金属位点可以减少HO-NH2中间体的形成。因此，说明CuSn(OH)6催化剂中Cu、Sn之间的协同效应促进电催化氨氧化生成氮气。4 and 5 are Faraday efficiency diagrams of various products obtained by electrocatalytic oxidation of different substrates (NH 3 and HO—NH 2 ) by CuSn(OH) 6 in Example 9. It can be seen from the figure that the main product of CuSn(OH) 6 electrocatalytic oxidation of ammonia is nitrogen, and the maximum efficiency can reach more than 75%. The maximum faradaic efficiency of peroxidation product-nitrate is only 19.6%. The main product is nitrate, the maximum efficiency can reach more than 75%, and almost no nitrogen gas is generated, indicating that the formation of HO- NH2 intermediates will lead to the generation of peroxidation products. Cu-Sn bimetallic sites can reduce the formation of HO- NH2 intermediates. Therefore, it is illustrated that the synergistic effect between Cu and Sn in the CuSn(OH) 6 catalyst promotes the electrocatalytic ammoxidation to nitrogen.

实施例10Example 10

测试催化剂对氨的吸附性能。具体实施步骤：The adsorption performance of the catalyst to ammonia was tested. Specific implementation steps:

(1)Sn(OH)x催化剂制备：将6.6mmol氯化亚锡溶解于50mL纯水中。然后在不断搅拌的条件下，将其缓慢滴加到100mL 2mol/L的氢氧化钠溶液中。滴加结束后，保持搅拌5h。反应结束后，用乙醇和超纯水洗涤三次后放入真空烘箱干燥，得到产物，记为Sn(OH)x。(1) Preparation of Sn(OH)x catalyst: 6.6 mmol of stannous chloride was dissolved in 50 mL of pure water. Then, it was slowly added dropwise to 100 mL of 2 mol/L sodium hydroxide solution under constant stirring. After the dropwise addition, keep stirring for 5h. After the reaction, it was washed three times with ethanol and ultrapure water, and then dried in a vacuum oven to obtain the product, which was denoted as Sn(OH) x .

(2)称取Cu2Sn1(OH)6、Sn(OH)x和Cu(OH)2催化剂在氨气氛围中进行质谱-程序升温化学吸附(MS-TPD)测试，测试催化剂对于氨的吸附性能。(2) The Cu2Sn1(OH) 6 , Sn(OH) x and Cu(OH) 2 catalysts were weighed and subjected to mass spectrometry-temperature-programmed chemical adsorption (MS-TPD) tests in an ammonia atmosphere to test the adsorption performance of the catalysts for ammonia.

图6为实施例10中Cu(OH)2，Sn(OH)x和CuSn(OH)6催化剂的MS-TPD曲线，Sn(OH)x在约100℃和395℃处的吸附峰分别对应于NH3的物理吸附和化学吸附。同时，CuSn(OH)6催化剂表现出两个NH3解吸峰，其位置与Sn(OH)x相似，且峰的强度更高。作为对比，Cu(OH)2仅表现出一个物理NH3吸附峰。以上结果表明，Sn元素的引入改善了CuSn(OH)6表面对NH3的吸附。Figure 6 is the MS-TPD curves of Cu(OH) 2 , Sn(OH) x and CuSn(OH) 6 catalysts in Example 10, and the adsorption peaks of Sn(OH)x at about 100°C and 395°C correspond to Physisorption and Chemisorption of NH3 . Meanwhile, the CuSn(OH) 6 catalyst exhibits two NH 3 desorption peaks, whose positions are similar to those of Sn(OH)x, and the intensity of the peaks is higher. For comparison, Cu(OH) 2 exhibits only one physical NH3 adsorption peak. The above results indicated that the introduction of Sn element improved the adsorption of NH 3 on the CuSn(OH) 6 surface.

本发明公开和提出的技术方案，本领域技术人员可通过借鉴本文内容，适当改变条件路线等环节实现，尽管本发明的方法和制备技术已通过较佳实施例子进行了描述，相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和技术路线进行改动或重新组合，来实现最终的制备技术。特别需要指出的是，所有相类似的替换和改动对本领域技术人员来说是显而易见的，他们都被视为包括在本发明精神、范围和内容中。The technical solutions disclosed and proposed by the present invention can be realized by those skilled in the art by referring to the content of this article and appropriately changing the conditions and routes. Although the method and preparation technology of the present invention have been described through preferred implementation examples, those skilled in the art can obviously The methods and technical routes described herein are modified or recombined without departing from the content, spirit and scope of the present invention to realize the final preparation technology. In particular, it should be pointed out that all similar substitutions and modifications will be obvious to those skilled in the art, and they are all considered to be included in the spirit, scope and content of the present invention.

Claims (5)

1. Application of copper-tin double-metal hydroxide catalyst in preparing nitrogen by electrocatalytic ammoxidation, wherein the copper-tin double-metal hydroxide catalyst is CuSn (OH) 6 The method comprises the steps of carrying out a first treatment on the surface of the The method comprises the following steps:
(1) Weighing copper-tin double-metal hydroxide catalyst CuSn (OH) 6 Dispersing in volatile solvent, adding naphthol solution, and ultrasonic treating to obtain homogeneously dispersed dispersion;
(2) Uniformly dripping the electrode dispersion liquid obtained in the step (1) on a carbon paper electrode;
(3) Taking a Pt electrode as a counter electrode, a mercury/mercury oxide electrode as a reference electrode, and the electrode manufactured in the step (2) as a working electrode to form a standard three-electrode system, taking ammonia as a substrate and a potassium sulfate solution as an electrolyte, and keeping the pH value of the solution to be 9-13 for electrolytic test to obtain nitrogen Faraday efficiency and current density reaching 70% and 1mA cm respectively under the optimal potential -2 The above;
wherein the mass concentration of the catalyst in the electrode dispersion liquid is 5-15 mg/mL, the dosage of naphthol solution is 25-75 mu L, the concentration of potassium sulfate solution is 0.1-1 mol/L, and the electrolysis voltage is 0.8-2.0V vs. Hg/HgO.
2. The use according to claim 1, wherein the volatile solvent is N, N-dimethylformamide, ethanol, isopropanol, or N, N-dimethylformamide.
3. The method according to claim 1, wherein the naphthol solution is used in an amount of 40 to 50. Mu.L.
4. The use according to claim 1, wherein the concentration of the potassium sulphate solution is 0.4 to 0.5mol/L.
5. The use according to claim 1, wherein the pH is 11.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108163886A (en) * 2017-12-11 2018-06-15 河南师范大学 The preparation method of hydroxyl stannate copper sunlight catalytic agent with ball shape structure
CN110523415A (en) * 2019-09-03 2019-12-03 浙江天地环保科技有限公司 Copper-iron layered double metal hydroxide, copper-iron layered double metal hydroxide/carbon matrix composite material and preparation method and application thereof
CN111701593A (en) * 2020-07-02 2020-09-25 济南大学 Preparation of a lithium iron layered double metal hydroxide catalyst and its application in electrocatalytic nitrogen reduction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108163886A (en) * 2017-12-11 2018-06-15 河南师范大学 The preparation method of hydroxyl stannate copper sunlight catalytic agent with ball shape structure
CN110523415A (en) * 2019-09-03 2019-12-03 浙江天地环保科技有限公司 Copper-iron layered double metal hydroxide, copper-iron layered double metal hydroxide/carbon matrix composite material and preparation method and application thereof
CN111701593A (en) * 2020-07-02 2020-09-25 济南大学 Preparation of a lithium iron layered double metal hydroxide catalyst and its application in electrocatalytic nitrogen reduction

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