CN114959771B - Nickel-based electrocatalyst and hydrogen production synergistic formaldehyde wastewater degradation electrolytic cell - Google Patents
Nickel-based electrocatalyst and hydrogen production synergistic formaldehyde wastewater degradation electrolytic cell Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 148
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 74
- 239000001257 hydrogen Substances 0.000 title claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 37
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 230000015556 catabolic process Effects 0.000 title claims abstract description 20
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 20
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229940116357 potassium thiocyanate Drugs 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 5
- 241000872198 Serjania polyphylla Species 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000002953 phosphate buffered saline Substances 0.000 claims 3
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 claims 1
- -1 that is Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
Description
技术领域Technical field
本发明涉及废水降解技术领域，尤其涉及一种镍基电催化剂及产氢协同降解甲醛废水电解池。The invention relates to the technical field of wastewater degradation, and in particular to a nickel-based electrocatalyst and a hydrogen-producing synergistic degradation formaldehyde wastewater electrolytic cell.
背景技术Background technique
化石燃料作为不可再生资源被大量消耗，造成了能源短缺和严重的环境污染。因此，迫切需要开发可再生、环保的能源，特别是氢这种高效清洁的能源。通过电催化分解水制氢是一种清洁和环保的方法，但其缓慢的阳极析氧反应仍然是限制其工业上的应用。Fossil fuels, as non-renewable resources, are consumed in large quantities, causing energy shortages and serious environmental pollution. Therefore, there is an urgent need to develop renewable and environmentally friendly energy, especially hydrogen, an efficient and clean energy source. Hydrogen production through electrocatalytic water splitting is a clean and environmentally friendly method, but its slow anodic oxygen evolution reaction still limits its industrial application.
研究表明，通过用其他氧化反应代替缓慢的阳极析氧反应，可以促进氢气的产生。其中，甲醛相较于水分子更容易被氧化，进而促进了阴极析氢反应。另一方面，甲醛的危害性众所周知，因此，本发明旨在直接利用甲醛废水作为电解液来提高制氢效率，同时电催化氧化废水中的甲醛。Studies have shown that hydrogen production can be promoted by replacing the slow anodic oxygen evolution reaction with other oxidation reactions. Among them, formaldehyde is more easily oxidized than water molecules, thereby promoting the cathode hydrogen evolution reaction. On the other hand, the harmfulness of formaldehyde is well known. Therefore, the present invention aims to directly use formaldehyde wastewater as electrolyte to improve hydrogen production efficiency and simultaneously electrocatalytically oxidize formaldehyde in the wastewater.
在已有报道中，韩卫清等人提供了一种处理含甲醛废水的装置及方法(CN202010339053.1)，该发明利用钛基二氧化钌电极，通过采用电催化氧化的方法处理废水中的甲醛，但造价较为高昂。李越湘等人提供了磷化钼在碱性甲醛溶液中催化制氢的应用(CN201710715999.1)，该发明用磷化钼在碱性甲醛溶液中催化制氢，但反应需要浓碱液和惰性气体保护，环境不友好。In existing reports, Han Weiqing and others provided a device and method for treating formaldehyde-containing wastewater (CN202010339053.1). This invention uses titanium-based ruthenium dioxide electrodes to treat formaldehyde in wastewater by electrocatalytic oxidation. But the cost is relatively high. Li Yuexiang and others provided the application of molybdenum phosphide in catalytic hydrogen production in alkaline formaldehyde solution (CN201710715999.1). This invention uses molybdenum phosphide to catalyze hydrogen production in alkaline formaldehyde solution, but the reaction requires concentrated alkali liquid and inert gas. Conservation, environmentally unfriendly.
因此，为了在降解甲醛的同时，明显降低电解池池电压，提高制氢效率，我们提出了以下方案。Therefore, in order to significantly reduce the voltage of the electrolytic cell and improve the hydrogen production efficiency while degrading formaldehyde, we proposed the following plan.
发明内容Contents of the invention
本发明公开一种镍基电催化剂及产氢协同降解甲醛废水电解池，旨在解决现有技术下对于产氢效率不高和甲醛溶液的降解效果不理想的技术问题。The invention discloses a nickel-based electrocatalyst and a hydrogen-generating synergistic degradation formaldehyde wastewater electrolytic cell, aiming to solve the technical problems of low hydrogen production efficiency and unsatisfactory degradation effect of formaldehyde solution under the existing technology.
为了实现上述目的，本发明采用了如下技术方案：In order to achieve the above objects, the present invention adopts the following technical solutions:
一种镍基电催化剂，包括以下具体步骤：A nickel-based electrocatalyst includes the following specific steps:
S11：材料混合：在容器中加入一定量的硝酸镍和硫***，并混合均匀；S11: Material mixing: add a certain amount of nickel nitrate and potassium thiocyanate into the container and mix evenly;
S12：恒温煅烧：将混合物放入在马弗炉中，在一定温度的恒温下进行煅烧；S12: Constant temperature calcination: Put the mixture into a muffle furnace and calcine at a certain constant temperature;
S13：自然冷却：恒温煅烧后，将混合物自然冷却至室温；S13: Natural cooling: After constant temperature calcination, the mixture is naturally cooled to room temperature;
S14：祛杂：用去离子水洗去多余的硫***；S14: Removal of impurities: wash away excess potassium thiocyanate with deionized water;
S15：干燥：干燥后即得所述的镍基电催化剂。S15: Drying: After drying, the nickel-based electrocatalyst is obtained.
化石燃料作为不可再生资源被大量消耗，造成了能源短缺和严重的环境污染，因此，迫切需要开发可再生、环保的能源，特别是氢这种高效清洁的能源，现有技术下，通过电催化分解水制氢是一种清洁和环保的方法，但其缓慢的阳极析氧反应仍然是限制其工业上的应用，研究表明，通过用其他氧化反应代替缓慢的阳极析氧反应，可以促进氢气的产生，其中，甲醛相较于水分子更容易被氧化，进而促进了阴极析氢反应，另一方面，甲醛的危害性众所周知，因此，本发明旨在直接利用甲醛废水作为电解液来提高制氢效率，同时电催化氧化废水中的甲醛，本发明通过使用NiSx作为电催化剂材料，在电解池电氧化甲醛废水的同时明显降低了电解池池电压，又提高了产氢效率，是一种环境友好、节能的制氢新策略，具有明显的实际应用价值。As a non-renewable resource, fossil fuels are consumed in large quantities, resulting in energy shortages and serious environmental pollution. Therefore, there is an urgent need to develop renewable and environmentally friendly energy, especially hydrogen, an efficient and clean energy. Under the existing technology, through electrocatalysis Splitting water to produce hydrogen is a clean and environmentally friendly method, but its slow anode oxygen evolution reaction still limits its industrial application. Studies have shown that by replacing the slow anode oxygen evolution reaction with other oxidation reactions, hydrogen production can be promoted. Among them, formaldehyde is more easily oxidized than water molecules, thereby promoting the cathode hydrogen evolution reaction. On the other hand, the harmfulness of formaldehyde is well known. Therefore, the present invention aims to directly use formaldehyde wastewater as the electrolyte to improve the hydrogen production efficiency. , while electrocatalytically oxidizing formaldehyde in wastewater. By using NiS , a new energy-saving hydrogen production strategy, which has obvious practical application value.
在一个优选的方案中，所述S12中，恒温煅烧的具体实施方式为控制马弗炉在450℃中恒温煅烧2小时；In a preferred solution, in S12, the specific implementation of constant temperature calcination is to control the muffle furnace to perform constant temperature calcination at 450°C for 2 hours;
一种产氢协同降解甲醛废水电解池，包括以下具体步骤：A hydrogen-producing synergistic degradation formaldehyde wastewater electrolytic cell includes the following specific steps:
S1：电催化剂制备：准备好镍基电催化剂备用；S1: Electrocatalyst preparation: Prepare the nickel-based electrocatalyst for later use;
S2：电解液制备：以PBS溶液制作电解液；S2: Preparation of electrolyte: use PBS solution to prepare electrolyte;
S3：电极制备：使用镍基电催化剂制作电极，构成二电极体系；S3: Electrode preparation: Use nickel-based electrocatalyst to make electrodes to form a two-electrode system;
S4：加入电催化物：加入一定量的电催化物进行电催化；S4: Add electrocatalyst: add a certain amount of electrocatalyst for electrocatalysis;
S5：施加电压：施加一定的电压，使电极制备中制备的电极对电催化物进行电解；S5: Apply voltage: Apply a certain voltage to cause the electrode prepared in the electrode preparation to electrolyze the electrocatalyst;
所述S2中，电解液制备中电解液中PBS的浓度为0.01M；In the S2, the concentration of PBS in the electrolyte during preparation of the electrolyte is 0.01M;
所述S4中，加入电催化物中的电催化物为一定量的HCHO，其中HCHO的浓度为2mg/L；In the S4, the electrocatalyst added to the electrocatalyst is a certain amount of HCHO, where the concentration of HCHO is 2 mg/L;
所述S3中，电极制备包括以下具体步骤：In the S3, electrode preparation includes the following specific steps:
S31：混合浆液制备：使用制备的电催化剂与一定量的其他材料混合，制成所需的混合浆液；S31: Preparation of mixed slurry: Use the prepared electrocatalyst to mix with a certain amount of other materials to make the required mixed slurry;
S32：浆液干燥：将浆液涂覆在介质上，并在室温下干燥24小时，得到NiSx电极；S32: Slurry drying: Coat the slurry on the medium and dry at room temperature for 24 hours to obtain NiS x electrode;
所述S31中，混合浆液制备的具体实施方式为将制得的镍基电催化剂和导电炭黑与聚偏氟乙烯以质量比为8：1：1混合，分散在1-甲基-2-吡咯烷酮中，在搅拌下形成均匀的浆液；In S31, the specific implementation method for preparing the mixed slurry is to mix the prepared nickel-based electrocatalyst and conductive carbon black with polyvinylidene fluoride at a mass ratio of 8:1:1, and disperse it in 1-methyl-2- In pyrrolidone, form a uniform slurry with stirring;
所述S32中，浆液干燥的具体实施方式为将制成的浆液涂覆在碳纤维布上，涂覆面积为0.5cm*0.5cm，干燥后得到NiSx电极。In S32, the specific implementation method of slurry drying is to coat the prepared slurry on carbon fiber cloth with a coating area of 0.5cm*0.5cm, and obtain a NiS x electrode after drying.
以下结合实施例对本发明作进一步的说明；The present invention will be further described below in conjunction with the examples;
实施例一：Example 1:
室温下，将1g的硝酸镍和10g的硫***加入容器中，混合均匀，再将混合物放入在马弗炉中，450℃恒温煅烧2小时，煅烧2小时后，自然冷却至室温，用去离子水洗去多余的硫***，干燥后即得所述的NiSx电催化剂；At room temperature, add 1g of nickel nitrate and 10g of potassium thiocyanate into the container, mix evenly, then put the mixture into a muffle furnace and calcine at a constant temperature of 450°C for 2 hours. After calcining for 2 hours, cool to room temperature naturally. Use deionized water to wash away excess potassium thiocyanate, and after drying, the NiS x electrocatalyst is obtained;
测试实例一：Test example one:
由图4可见，实施例一制备的产品的特征峰对应NiS和NiS2，实施例一制备产品为NiS和NiS2的复合物电催化剂；As can be seen from Figure 4, the characteristic peaks of the product prepared in Example 1 correspond to NiS and NiS 2 , and the product prepared in Example 1 is a composite electrocatalyst of NiS and NiS 2 ;
由图5可见，实施例一所制备的NiSx电催化剂由直径为2-10μm的大颗粒和直径为1μm的小颗粒的混合物组成；As can be seen from Figure 5, the NiS x electrocatalyst prepared in Example 1 is composed of a mixture of large particles with a diameter of 2-10 μm and small particles with a diameter of 1 μm;
由图6可见，相比传统的PBS电解池，甲醛/PBS电解池的池电压大幅降低了，并提高了阳极与阴极的电流密度；As can be seen from Figure 6, compared with the traditional PBS electrolytic cell, the cell voltage of the formaldehyde/PBS electrolytic cell is greatly reduced, and the current density of the anode and cathode is increased;
测试过程如下：The testing process is as follows:
将实施例一制得到的NiSx电催化剂和导电炭黑与聚偏氟乙烯以质量比为8：1：1混合，分散在1-甲基-2-吡咯烷酮中，在搅拌下形成均匀的浆液，再将浆料涂覆在碳纤维布上，然后在室温下干燥24小时，涂覆面积为0.5cm×0.5cm，得到NiSx电极；The NiS x electrocatalyst and conductive carbon black prepared in Example 1 were mixed with polyvinylidene fluoride at a mass ratio of 8:1:1, dispersed in 1-methyl-2-pyrrolidone, and formed into a uniform slurry under stirring. , then apply the slurry on the carbon fiber cloth, and then dry it at room temperature for 24 hours, with a coating area of 0.5cm×0.5cm, to obtain a NiS x electrode;
以上述制得的两片NiSx电极分别作阴、阳极，在此二电极体系，施加一定的电压，分别在0.01M PBS和0.01M PBS+2mg/L HCHO中进行电催化性能测试，由图3可见，HCHO的加入大幅降低了电解水的过电位，阴、阳极要达到10mA/cm2的电流密度时，PBS体系的池电压为3.55V，而PBS/HCHO体系的池电压仅为3.10V，池电压降低了0.45V，因为甲醛氧化反应代替缓慢的四电子水氧化半反应，进而减少了电解水的能耗，并促进产氢。The two NiS x electrodes prepared above were used as cathodes and anodes respectively. In this two-electrode system, a certain voltage was applied to conduct electrocatalytic performance tests in 0.01M PBS and 0.01M PBS+2mg/L HCHO respectively. As shown in the figure 3 It can be seen that the addition of HCHO greatly reduces the overpotential of electrolyzed water. When the cathode and anode reach a current density of 10mA/ cm2 , the cell voltage of the PBS system is 3.55V, while the cell voltage of the PBS/HCHO system is only 3.10V. , the cell voltage is reduced by 0.45V because the formaldehyde oxidation reaction replaces the slow four-electron water oxidation half-reaction, thereby reducing the energy consumption of electrolyzing water and promoting hydrogen production.
镍基电催化剂及产氢协同降解甲醛废水电解池应用步骤如下：The application steps of the nickel-based electrocatalyst and hydrogen production synergistic degradation of formaldehyde wastewater electrolytic cell are as follows:
1、电催化剂制备，在容器中加入一定量的硝酸镍和硫***，混合均匀，将混合物放入在马弗炉中，450℃恒温煅烧2小时，煅烧2小时后，自然冷却至室温，用去离子水洗去多余的硫***，干燥后即得所述的镍基电催化剂；1. Preparation of the electrocatalyst. Add a certain amount of nickel nitrate and potassium thiocyanate into the container, mix evenly, put the mixture into a muffle furnace, and calcine at a constant temperature of 450°C for 2 hours. After calcining for 2 hours, cool to room temperature naturally. , wash away excess potassium thiocyanate with deionized water, and dry to obtain the nickel-based electrocatalyst;
2、电解液制备，选择合适的电解液备用；2. Prepare the electrolyte and select the appropriate electrolyte for later use;
3、电极制备，制得到的NiSx电催化剂和导电炭黑与聚偏氟乙烯以质量比为8：1：1混合，分散在1-甲基-2-吡咯烷酮中，在搅拌下形成均匀的浆液，将浆料涂覆在碳纤维布上，然后在室温下干燥24小时，涂覆面积为0.5cm×0.5cm，得到NiSx电极；3. Electrode preparation. The prepared NiS x electrocatalyst and conductive carbon black are mixed with polyvinylidene fluoride at a mass ratio of 8:1:1, dispersed in 1-methyl-2-pyrrolidone, and formed into a uniform layer under stirring. Slurry, apply the slurry on the carbon fiber cloth, and then dry it at room temperature for 24 hours, with a coating area of 0.5cm×0.5cm, to obtain a NiS x electrode;
上述制得的两片NiSx电极分别作阴、阳极，在此二电极体系，施加一定的电压，并添加一定量的PBS和HCHO进行电催化性能测试，其中HCHO的加入大幅降低了电解水的过电位，因为甲醛氧化反应代替缓慢的四电子水氧化半反应，进而减少了电解水的能耗，并促进产氢。The two NiS x electrodes prepared above are used as cathodes and anodes respectively. In this two-electrode system, a certain voltage is applied, and a certain amount of PBS and HCHO are added for electrocatalytic performance testing. The addition of HCHO greatly reduces the electrolysis of water. overpotential, because the formaldehyde oxidation reaction replaces the slow four-electron water oxidation half-reaction, thereby reducing the energy consumption of electrolyzing water and promoting hydrogen production.
通过使用镍基电催化剂作为电极材料，并构成二电极电解池，再通过加入一定量的PBS和HCHO，采用HCHO/PBS电解***，相比传统电解水***，有效降低了池电压，高效电解水，并氧化降解了甲醛污染物。By using a nickel-based electrocatalyst as the electrode material and forming a two-electrode electrolytic cell, and then adding a certain amount of PBS and HCHO, the HCHO/PBS electrolysis system is used. Compared with the traditional water electrolysis system, the cell voltage is effectively reduced and the water is electrolyzed efficiently. , and oxidatively degrades formaldehyde pollutants.
由上可知，一种镍基电催化剂，包括以下具体步骤：It can be seen from the above that a nickel-based electrocatalyst includes the following specific steps:
S11：材料混合：在容器中加入一定量的硝酸镍和硫***，并混合均匀；S11: Material mixing: add a certain amount of nickel nitrate and potassium thiocyanate into the container and mix evenly;
S12：恒温煅烧：将混合物放入在马弗炉中，在一定温度的恒温下进行煅烧；S12: Constant temperature calcination: Put the mixture into a muffle furnace and calcine at a certain constant temperature;
S13：自然冷却：恒温煅烧后，将混合物自然冷却至室温；S13: Natural cooling: After constant temperature calcination, the mixture is naturally cooled to room temperature;
S14：祛杂：用去离子水洗去多余的硫***；S14: Removal of impurities: wash away excess potassium thiocyanate with deionized water;
S15：干燥：干燥后即得所述的镍基电催化剂。本发明提供的镍基电催化剂及产氢协同降解甲醛废水电解池具有在电解池电氧化甲醛废水的同时又提高了产氢效率的技术效果。S15: Drying: After drying, the nickel-based electrocatalyst is obtained. The nickel-based electrocatalyst and hydrogen-producing synergistic degradation of formaldehyde wastewater electrolytic cell provided by the present invention have the technical effect of electrolyzing formaldehyde wastewater in the electrolytic cell while improving the hydrogen production efficiency.
附图说明Description of the drawings
图1为本发明提出的一种镍基电催化剂及产氢协同降解甲醛废水电解池的整体流程图。Figure 1 is an overall flow chart of a nickel-based electrocatalyst and a hydrogen-producing synergistic degradation formaldehyde wastewater electrolytic cell proposed by the present invention.
图2为本发明提出的一种镍基电催化剂及产氢协同降解甲醛废水电解池的电催化剂制备流程图。Figure 2 is a flow chart for the preparation of a nickel-based electrocatalyst and an electrocatalyst for a hydrogen-producing synergistic degradation of formaldehyde wastewater electrolytic cell proposed by the present invention.
图3为本发明提出的一种镍基电催化剂及产氢协同降解甲醛废水电解池的电极制备流程图。Figure 3 is a flow chart for electrode preparation of a nickel-based electrocatalyst and hydrogen production synergistic degradation of formaldehyde wastewater electrolytic cell proposed by the present invention.
图4为本发明提出的一种镍基电催化剂及产氢协同降解甲醛废水电解池的实施例一制备的镍基电催化剂NiSx的X射线衍射(XRD)图。Figure 4 is an X-ray diffraction (XRD) pattern of a nickel-based electrocatalyst and a nickel-based electrocatalyst NiS x prepared in Example 1 of the hydrogen-producing synergistic degradation of formaldehyde wastewater electrolytic cell proposed by the present invention.
图5为本发明提出的一种镍基电催化剂及产氢协同降解甲醛废水电解池的实施例一制备的NiSx电催化剂的扫描电子显微镜(SEM)图。Figure 5 is a scanning electron microscope (SEM) image of a NiS x electrocatalyst prepared in Example 1 of a nickel-based electrocatalyst proposed by the present invention and a hydrogen-producing synergistic degradation of formaldehyde wastewater electrolytic cell.
图6为本发明提出的一种镍基电催化剂及产氢协同降解甲醛废水电解池的实施例一制备的NiSx电催化剂分别在0.01M PBS和0.01M PBS+2mg/L HCHO中的电催化性能测试图。Figure 6 shows the electrocatalysis of a NiS x electrocatalyst prepared in Example 1 of a nickel-based electrocatalyst proposed by the present invention and a hydrogen-producing synergistic degradation of formaldehyde wastewater electrolytic cell in 0.01M PBS and 0.01M PBS+2mg/L HCHO respectively. Performance test chart.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments.
本发明公开的一种镍基电催化剂及产氢协同降解甲醛废水电解池主要应用于废水电解的场景。The invention discloses a nickel-based electrocatalyst and a hydrogen-producing synergistic degradation formaldehyde wastewater electrolytic cell mainly used in wastewater electrolysis scenarios.
参照图2，一种镍基电催化剂，包括以下具体步骤：Referring to Figure 2, a nickel-based electrocatalyst includes the following specific steps:
S11：材料混合：在容器中加入一定量的硝酸镍和硫***，并混合均匀；S11: Material mixing: add a certain amount of nickel nitrate and potassium thiocyanate into the container and mix evenly;
S12：恒温煅烧：将混合物放入在马弗炉中，在一定温度的恒温下进行煅烧；S12: Constant temperature calcination: Put the mixture into a muffle furnace and calcine at a certain constant temperature;
S13：自然冷却：恒温煅烧后，将混合物自然冷却至室温；S13: Natural cooling: After constant temperature calcination, the mixture is naturally cooled to room temperature;
S14：祛杂：用去离子水洗去多余的硫***；S14: Removal of impurities: wash away excess potassium thiocyanate with deionized water;
S15：干燥：干燥后即得所述的镍基电催化剂。S15: Drying: After drying, the nickel-based electrocatalyst is obtained.
参照图2，在一个优选的实施方式中，S12中，恒温煅烧的具体实施方式为控制马弗炉在450℃中恒温煅烧2小时。Referring to Figure 2, in a preferred embodiment, in S12, the specific implementation of constant temperature calcination is to control the muffle furnace to perform constant temperature calcination at 450°C for 2 hours.
参照图1，一种产氢协同降解甲醛废水电解池，包括以下具体步骤：Referring to Figure 1, a hydrogen production synergistic degradation of formaldehyde wastewater electrolysis cell includes the following specific steps:
S1：电催化剂制备：准备好镍基电催化剂备用；S1: Electrocatalyst preparation: Prepare the nickel-based electrocatalyst for later use;
S2：电解液制备：以PBS为基液制作电解液；S2: Electrolyte preparation: use PBS as the base liquid to prepare the electrolyte;
S3：电极制备：使用镍基电催化剂制作电极，构成二电极体系；S3: Electrode preparation: Use nickel-based electrocatalyst to make electrodes to form a two-electrode system;
S4：加入电催化物：加入一定量的电催化物进行电催化；S4: Add electrocatalyst: add a certain amount of electrocatalyst for electrocatalysis;
S5：施加电压：施加一定的电压，使电极制备中制备的电极对电催化物进行电解。S5: Apply voltage: Apply a certain voltage to cause the electrode prepared in the electrode preparation to electrolyze the electrocatalyst.
参照图1，在一个优选的实施方式中，S2中，电解液制备中电解液中PBS的浓度为0.01M。Referring to Figure 1, in a preferred embodiment, in S2, the concentration of PBS in the electrolyte solution during preparation of the electrolyte solution is 0.01M.
参照图1，在一个优选的实施方式中，S4中，加入电催化物中的电催化物为一定量的HCHO，其中HCHO的浓度为2mg/L。Referring to Figure 1, in a preferred embodiment, in S4, the electrocatalyst added to the electrocatalyst is a certain amount of HCHO, where the concentration of HCHO is 2 mg/L.
参照图3，在一个优选的实施方式中，S3中，电极制备包括以下具体步骤：Referring to Figure 3, in a preferred embodiment, in S3, electrode preparation includes the following specific steps:
S31：混合浆液制备：使用制备的电催化剂与一定量的其他材料混合，制成所需的混合浆液；S31: Preparation of mixed slurry: Use the prepared electrocatalyst to mix with a certain amount of other materials to make the required mixed slurry;
S32：浆液干燥：将浆液涂覆在介质上，并在室温下干燥24小时，得到NiSx电极。S32: Slurry drying: Coat the slurry on the medium and dry at room temperature for 24 hours to obtain NiS x electrode.
参照图3，在一个优选的实施方式中，S31中，混合浆液制备的具体实施方式为将制得的镍基电催化剂和导电炭黑与聚偏氟乙烯以质量比为8：1：1混合，分散在1-甲基-2-吡咯烷酮中，在搅拌下形成均匀的浆液。Referring to Figure 3, in a preferred embodiment, in S31, the specific implementation method of preparing the mixed slurry is to mix the prepared nickel-based electrocatalyst and conductive carbon black with polyvinylidene fluoride in a mass ratio of 8:1:1 , dispersed in 1-methyl-2-pyrrolidone, forming a uniform slurry under stirring.
参照图3，在一个优选的实施方式中，S32中，浆液干燥的具体实施方式为将制成的浆液涂覆在碳纤维布上，涂覆面积为0.5cm*0.5cm，干燥后得到NiSx电极。Referring to Figure 3, in a preferred embodiment, in S32, the specific implementation of slurry drying is to coat the prepared slurry on carbon fiber cloth with a coating area of 0.5cm*0.5cm. After drying, a NiS x electrode is obtained .
以下结合实施例对本发明作进一步的说明。The present invention will be further described below in conjunction with the examples.
实施例一：Example 1:
室温下，将1g的硝酸镍和10g的硫***加入容器中，混合均匀，再将混合物放入在马弗炉中，450℃恒温煅烧2小时，煅烧2小时后，自然冷却至室温，用去离子水洗去多余的硫***，干燥后即得所述的NiSx电催化剂；At room temperature, add 1g of nickel nitrate and 10g of potassium thiocyanate into the container, mix evenly, then put the mixture into a muffle furnace and calcine at a constant temperature of 450°C for 2 hours. After calcining for 2 hours, cool to room temperature naturally. Use deionized water to wash away excess potassium thiocyanate, and after drying, the NiS x electrocatalyst is obtained;
测试实例一：Test example one:
由图4可见，实施例一制备的产品的特征峰对应NiS和NiS2，实施例一制备产品为NiS和NiS2的复合物电催化剂；456As can be seen from Figure 4, the characteristic peaks of the product prepared in Example 1 correspond to NiS and NiS 2 , and the product prepared in Example 1 is a composite electrocatalyst of NiS and NiS 2 ; 456
由图5可见，实施例一所制备的NiSx电催化剂由直径为2-10μm的大颗粒和直径为1μm的小颗粒的混合物组成；As can be seen from Figure 5, the NiS x electrocatalyst prepared in Example 1 is composed of a mixture of large particles with a diameter of 2-10 μm and small particles with a diameter of 1 μm;
由图6可见，NiSx电催化剂在甲醛/PBS二电极电解池，相比传统的PBS电解池，大幅降低了池电压，并提高了阳极与阴极的电流密度；As can be seen from Figure 6, the NiS x electrocatalyst in the formaldehyde/PBS two-electrode electrolytic cell significantly reduces the cell voltage and increases the current density of the anode and cathode compared to the traditional PBS electrolytic cell;
测试过程如下：The testing process is as follows:
将实施例一制得到的NiSx电催化剂和导电炭黑与聚偏氟乙烯以质量比为8：1：1混合，分散在1-甲基-2-吡咯烷酮中，在搅拌下形成均匀的浆液，再将浆料涂覆在碳纤维布上，然后在室温下干燥24小时，涂覆面积为0.5cm×0.5cm，得到NiSx电极；The NiS x electrocatalyst and conductive carbon black prepared in Example 1 were mixed with polyvinylidene fluoride at a mass ratio of 8:1:1, dispersed in 1-methyl-2-pyrrolidone, and formed into a uniform slurry under stirring. , then apply the slurry on the carbon fiber cloth, and then dry it at room temperature for 24 hours, with a coating area of 0.5cm×0.5cm, to obtain a NiS x electrode;
以上述制得的两片NiSx电极分别作阴、阳极，在此二电极体系，施加一定的电压，分别在0.01M PBS和0.01M PBS+2mg/L HCHO中进行电催化性能测试，由图3可见，HCHO的加入大幅降低了电解水的过电位，阴、阳极要达到10mA/cm2的电流密度时，PBS体系的池电压为3.55V，而PBS/HCHO体系的池电压仅为3.10V，池电压降低了0.45V，因为甲醛氧化反应代替缓慢的四电子水氧化半反应，进而减少了电解水的能耗，并促进产氢，因此，我们的设计是节能的，在低压高效电解水的同时，并降解了污染物。The two NiS x electrodes prepared above were used as cathodes and anodes respectively. In this two-electrode system, a certain voltage was applied to conduct electrocatalytic performance tests in 0.01M PBS and 0.01M PBS+2mg/L HCHO respectively. As shown in the figure 3 It can be seen that the addition of HCHO greatly reduces the overpotential of electrolyzed water. When the cathode and anode reach a current density of 10mA/ cm2 , the cell voltage of the PBS system is 3.55V, while the cell voltage of the PBS/HCHO system is only 3.10V. , the cell voltage is reduced by 0.45V, because the formaldehyde oxidation reaction replaces the slow four-electron water oxidation half-reaction, thereby reducing the energy consumption of electrolyzing water and promoting hydrogen production. Therefore, our design is energy-saving and efficient in low-voltage electrolysis of water. At the same time, pollutants are degraded.
工作原理：镍基电催化剂及产氢协同降解甲醛废水电解池应用步骤如下：Working principle: The application steps of the nickel-based electrocatalyst and hydrogen production synergistic degradation of formaldehyde wastewater electrolytic cell are as follows:
4、电催化剂制备，在容器中加入一定量的硝酸镍和硫***，混合均匀，将混合物放入在马弗炉中，450℃恒温煅烧2小时，煅烧2小时后，自然冷却至室温，用去离子水洗去多余的硫***，干燥后即得所述的镍基电催化剂；4. Preparation of the electrocatalyst. Add a certain amount of nickel nitrate and potassium thiocyanate into the container, mix evenly, put the mixture into a muffle furnace, and calcine at a constant temperature of 450°C for 2 hours. After calcining for 2 hours, cool to room temperature naturally. , wash away excess potassium thiocyanate with deionized water, and dry to obtain the nickel-based electrocatalyst;
5、电解液制备，选择合适的电解质备用；5. Prepare the electrolyte and select the appropriate electrolyte for later use;
6、电极制备，制得到的NiSx电催化剂和导电炭黑与聚偏氟乙烯以质量比为8：1：1混合，分散在1-甲基-2-吡咯烷酮中，在搅拌下形成均匀的浆液，将浆料涂覆在碳纤维布上，然后在室温下干燥24小时，涂覆面积为0.5cm×0.5cm，得到NiSx电极；6. Electrode preparation. The prepared NiS x electrocatalyst and conductive carbon black are mixed with polyvinylidene fluoride at a mass ratio of 8:1:1, dispersed in 1-methyl-2-pyrrolidone, and formed into a uniform layer under stirring. Slurry, apply the slurry on the carbon fiber cloth, and then dry it at room temperature for 24 hours, with a coating area of 0.5cm×0.5cm, to obtain a NiS x electrode;
7、上述制得的两片NiSx电极分别作阴、阳极，在此二电极体系，施加一定的电压，并添加一定量的PBS和HCHO进行电催化性能测试，其中HCHO的加入大幅降低了电解水的过电位，因为甲醛氧化反应代替缓慢的四电子水氧化半反应，进而减少了电解水的能耗，并促进产氢，因此，我们的设计是节能的，在低压高效电解水的同时，提高了产氢效率，并降解了污染物。7. The two NiS x electrodes prepared above are used as cathodes and anodes respectively. In this two-electrode system, a certain voltage is applied, and a certain amount of PBS and HCHO are added for electrocatalytic performance testing. The addition of HCHO greatly reduces the electrolysis The overpotential of water, because the formaldehyde oxidation reaction replaces the slow four-electron water oxidation half-reaction, thereby reducing the energy consumption of electrolyzing water and promoting hydrogen production. Therefore, our design is energy-saving, while electrolyzing water efficiently at low pressure, The hydrogen production efficiency is improved and pollutants are degraded.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person familiar with the technical field can, within the technical scope disclosed in the present invention, implement the technical solutions of the present invention. Equivalent substitutions or changes of the inventive concept thereof shall be included in the protection scope of the present invention.
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