CN105970265B - A kind of preparation method for decomposing the Ni-Fe hydroxide nano film catalysts of the doping sulphur of water oxygen - Google Patents
A kind of preparation method for decomposing the Ni-Fe hydroxide nano film catalysts of the doping sulphur of water oxygen Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 34
- 229910003271 Ni-Fe Inorganic materials 0.000 title claims abstract description 33
- 239000002120 nanofilm Substances 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 239000005864 Sulphur Substances 0.000 title abstract 3
- 238000004070 electrodeposition Methods 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000006260 foam Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000002484 cyclic voltammetry Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000006262 metallic foam Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 abstract 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 abstract 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- 229950009789 cetomacrogol 1000 Drugs 0.000 abstract 1
- 239000002659 electrodeposit Substances 0.000 abstract 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
Description
技术领域technical field
本发明属于电解水制备氧气催化电极材料技术领域，具体涉及一种用于分解水制氧的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂的制备方法。The invention belongs to the technical field of preparing oxygen catalytic electrode materials by electrolyzing water, and in particular relates to a preparation method of a sulfur-doped Ni-Fe hydroxide nano-film catalyst for decomposing water to produce oxygen.
背景技术Background technique
目前，低成本、高纯度制备氧气最有效的方法就是通过电催化或者光催化水分解。水氧化反应是催化水分解重要反应，这一步反应涉及到四个电子转移过程，最终生成氧-氧键。但是，在这个反应过程中反应速率非常缓慢，需要使用催化剂降低活化能，加快反应速率。工业上电催化水分解电极使用氧化钌或氧化铱为阳极，但是贵金属储量小和成本高限制了其在电解水工业中的规模化使用。为此近年来大量的科研人员集中研究价格低廉且储量丰富的非贵金属，如Fe、Co、Ni、Mn、Mo等元素的合金及其化合物，主要由Ni、Fe、Co等氧化物、磷化物、硫化物、氢氧化物、碳化物等，以及复合氢氧化物，层状(LDH)氧化物等对催化析氧反应有比较高的催化活性。其中，镍基催化剂首先被用于碱性溶液中催化水氧化，效果良好，科研人员发现把铁元素加入的镍基催化剂中可以明显降低析氧过电势。这一发现引起人们对镍铁复合组分催化剂大量研究。现有镍铁复合组分催化剂的制备方法主要有水热法和溶胶凝胶法，而关于用电化学方法制备掺杂硫的Ni-Fe氢氧化物材料以及用于电解水催化电极材料的研究未见报道。At present, the most effective way to produce oxygen with low cost and high purity is through electrocatalytic or photocatalytic water splitting. Water oxidation reaction is an important reaction to catalyze water splitting, and this step involves four electron transfer processes, which eventually generate oxygen-oxygen bonds. However, the reaction rate is very slow in this reaction process, and it is necessary to use a catalyst to reduce the activation energy and speed up the reaction rate. Industrially, ruthenium oxide or iridium oxide is used as the anode for electrocatalytic water splitting electrodes, but the small reserves and high cost of precious metals limit their large-scale use in the electrolytic water industry. For this reason, in recent years, a large number of scientific researchers have focused on the research of low-cost and abundant non-noble metals, such as alloys and compounds of Fe, Co, Ni, Mn, Mo and other elements, mainly composed of Ni, Fe, Co and other oxides, phosphides, etc. , sulfides, hydroxides, carbides, etc., as well as composite hydroxides, layered (LDH) oxides, etc. have relatively high catalytic activity for catalyzing oxygen evolution reactions. Among them, nickel-based catalysts were first used to catalyze water oxidation in alkaline solutions, and the effect was good. Researchers found that adding iron to the nickel-based catalysts could significantly reduce the oxygen evolution overpotential. This discovery has led to a lot of research on nickel-iron composite component catalysts. The existing preparation methods of nickel-iron composite component catalysts mainly include hydrothermal method and sol-gel method, and the research on the preparation of sulfur-doped Ni-Fe hydroxide materials by electrochemical methods and the catalytic electrode materials for electrolysis of water None reported.
发明内容Contents of the invention
本发明所要解决的技术问题在于提供一种通过循环伏安电沉积法制备具有良好的降低电解水析氧反应过电势的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂的方法。The technical problem to be solved by the present invention is to provide a method for preparing a sulfur-doped Ni-Fe hydroxide nano-film catalyst with a good ability to reduce the overpotential of the electrolytic water oxygen evolution reaction by cyclic voltammetric electrodeposition.
解决上述技术问题所采用的技术方案由下述步骤组成：The technical solution adopted to solve the above technical problems consists of the following steps:
1、将下述质量百分配比的原料混合均匀，制备成电沉积液：1. Mix the raw materials in the following mass percentage proportions evenly to prepare an electrodeposition solution:
2、以金属条或泡沫金属基板为工作电极、碳棒为对电极、Ag/AgCl电极作为参比电极，放入步骤1制备的电沉积液中，通过循环伏安法电沉积，扫描范围为-1.4～0.3V，扫描速率为2～15mV/s，循环次数为5～50次，在金属条或泡沫金属基板上沉积掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂。2. Put the metal strip or metal foam substrate as the working electrode, the carbon rod as the counter electrode, and the Ag/AgCl electrode as the reference electrode, put it into the electrodeposition solution prepared in step 1, and conduct electrodeposition by cyclic voltammetry. The scanning range is -1.4-0.3V, the scan rate is 2-15mV/s, the number of cycles is 5-50 times, and the sulfur-doped Ni-Fe hydroxide nano-film catalyst is deposited on the metal strip or foam metal substrate.
本发明优选将下述质量百分配比的原料混合均匀，制备成电沉积液：In the present invention, the raw materials with the following mass percentage ratios are preferably mixed uniformly to prepare the electrodeposition solution:
本发明进一步优选将下述质量百分配比的原料混合均匀，制备成电沉积液：In the present invention, it is further preferred to mix the raw materials in the following mass percentage proportions uniformly to prepare the electrodeposition solution:
上述的金属条为铜条或镍条，泡沫金属为泡沫铜或泡沫镍。The metal strips mentioned above are copper strips or nickel strips, and the foamed metals are copper foams or nickel foams.
上述步骤2中，优选扫描范围为-1.2～0.2V，扫描速率为5mV/s，循环次数为25次。In the above step 2, the preferred scanning range is -1.2-0.2V, the scanning rate is 5mV/s, and the number of cycles is 25 times.
本发明以含有NiCl2、FeCl2、硫脲和聚乙二醇的水溶液为电沉积液，通过循环伏安电沉积法，在一定的沉积条件下得到具有纳米片状结构的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂。本发明制备的催化剂未经过交联剂粘到基板表面，而是采用电沉积的方法直接沉积在基板表面，并且催化剂中的各种组分与沉积薄膜的厚度可以调节，催化剂有效组分均匀地生长在基板表面，而且制备的催化剂保持了金属基板原有的柔韧性，用于电分解水析氧反应过程中，在较大电流密度下所需要的过电势较低，在高浓度的KOH溶液中，经过大电流密度长时间分解水，催化效果良好，且催化剂组分不易从基板表面脱落。采用本发明方法制备催化剂的操作设备、方法简单，成本低廉，拟代替目前价格昂贵的IrO2、RuO2等贵金属催化剂，可望规模化应用。In the present invention, the aqueous solution containing NiCl 2 , FeCl 2 , thiourea and polyethylene glycol is used as the electrodeposition solution, and the sulfur-doped Ni with nano-sheet structure is obtained under certain deposition conditions through the cyclic voltammetry electrodeposition method. -Fe hydroxide nanometer film catalyst. The catalyst prepared by the present invention does not stick to the surface of the substrate through a crosslinking agent, but is directly deposited on the surface of the substrate by electrodeposition, and the thickness of various components in the catalyst and the deposition film can be adjusted, and the effective components of the catalyst are evenly distributed. It grows on the surface of the substrate, and the prepared catalyst maintains the original flexibility of the metal substrate. It is used in the process of electrolysis of water for oxygen evolution reaction. The overpotential required at a large current density is low. In a high-concentration KOH solution Among them, after a long time of high current density to decompose water, the catalytic effect is good, and the catalyst components are not easy to fall off from the substrate surface. The operation equipment and method for preparing the catalyst by the method of the invention are simple and low in cost, and it is intended to replace the current expensive IrO 2 , RuO 2 and other noble metal catalysts, and is expected to be applied on a large scale.
附图说明Description of drawings
图1是实施例1制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂中Ni的XPS图。Fig. 1 is the XPS figure of Ni in the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 1.
图2是实施例1制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂中Fe的XPS图。Fig. 2 is the XPS figure of Fe in the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 1.
图3是实施例1制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂中S的XPS图。3 is an XPS diagram of S in the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 1.
图4是实施例1制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂中O的XPS图。4 is an XPS diagram of O in the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 1.
图5是实施例1制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂的扫描电镜图。5 is a scanning electron micrograph of the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 1.
图6是实施例1制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂的透射电镜图。6 is a transmission electron microscope image of the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 1.
图7是实施例1制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂催化水分解制氧的效果图。7 is an effect diagram of the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 1 to catalyze water splitting to produce oxygen.
图8是实施例2制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂催化水分解制氧的效果图。8 is an effect diagram of the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 2 to catalyze water splitting to produce oxygen.
图9是实施例3制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂催化水分解制氧的效果图。9 is an effect diagram of the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 3 to catalyze water splitting to produce oxygen.
图10是实施例4制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂催化水分解制氧的效果图。10 is an effect diagram of the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 4 to catalyze water splitting to produce oxygen.
图11是实施例5制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂催化水分解制氧的效果图。11 is an effect diagram of the sulfur-doped Ni-Fe hydroxide nano-film catalyst prepared in Example 5 to catalyze water splitting to produce oxygen.
具体实施方式Detailed ways
下面结合附图和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments, but the protection scope of the present invention is not limited to these embodiments.
实施例1Example 1
1、将下述原料混合均匀，制备成电沉积液：1. Mix the following raw materials evenly to prepare electrodeposition solution:
2、以泡沫镍基板为工作电极、碳棒为对电极，Ag/AgCl电极(3mol/L KCl)作为参比电极，放入步骤1制备的电沉积液中，通过循环伏安法电沉积，扫描范围为-1.2～0.2V，扫描速率为5mV/s，循环25次，直接在泡沫镍基板表面沉积掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂。由图1～4可知，沉积在泡沫镍表面的纳米薄膜中含有Ni、Fe、S和O元素，XPS图谱通过C1s(284.8eV)标准校准，其中Ni和Fe主要是以二价形式存在，而S主要是硫脲分解形成硫酸根与硫，证明制备的纳米薄膜是掺杂硫的Ni-Fe氢氧化物。从图5～6中可以看出，沉积在泡沫镍表面的掺杂硫的Ni-Fe氢氧化物是由带有褶皱的纳米片状构成，纳米片状的掺杂硫的Ni-Fe氢氧化物在泡沫镍表面堆积成三维纳米多孔结构。2. Take the nickel foam substrate as the working electrode, the carbon rod as the counter electrode, and the Ag/AgCl electrode (3mol/L KCl) as the reference electrode, put it into the electrodeposition solution prepared in step 1, and conduct electrodeposition by cyclic voltammetry. The scanning range is -1.2～0.2V, the scanning rate is 5mV/s, and the cycle is 25 times, and the sulfur-doped Ni-Fe hydroxide nano-film catalyst is directly deposited on the surface of the nickel foam substrate. It can be seen from Figures 1 to 4 that the nano-film deposited on the surface of nickel foam contains Ni, Fe, S and O elements, and the XPS spectrum is calibrated by the C1s (284.8eV) standard, in which Ni and Fe mainly exist in divalent form, while S is mainly decomposed from thiourea to form sulfate and sulfur, which proves that the prepared nano-film is Ni-Fe hydroxide doped with sulfur. It can be seen from Figures 5 to 6 that the sulfur-doped Ni-Fe hydroxide deposited on the surface of nickel foam is composed of nano-sheets with wrinkles, and the nano-sheet-shaped sulfur-doped Ni-Fe hydroxide The substances accumulate on the surface of nickel foam to form a three-dimensional nanoporous structure.
实施例2Example 2
1、将下述原料混合均匀，制备成电沉积液：1. Mix the following raw materials evenly to prepare electrodeposition solution:
2、以泡沫镍基板为工作电极、碳棒为对电极，Ag/AgCl电极(3mol/L KCl)作为参比电极，放入步骤1制备的电沉积液中，通过循环伏安法电沉积，扫描范围为-1.4～0V，扫描速率为10mV/s，循环40次，直接在泡沫镍基板表面沉积掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂。2. Take the nickel foam substrate as the working electrode, the carbon rod as the counter electrode, and the Ag/AgCl electrode (3mol/L KCl) as the reference electrode, put it into the electrodeposition solution prepared in step 1, and conduct electrodeposition by cyclic voltammetry. The scanning range is -1.4～0V, the scanning rate is 10mV/s, and the cycle is 40 times, and the sulfur-doped Ni-Fe hydroxide nano-film catalyst is directly deposited on the surface of the nickel foam substrate.
实施例3Example 3
1、将下述原料混合均匀，制备成电沉积液：1. Mix the following raw materials evenly to prepare electrodeposition solution:
2、以泡沫镍基板为工作电极、碳棒为对电极，Ag/AgCl电极(3mol/L KCl)作为参比电极，放入步骤1制备的电沉积液中，通过循环伏安法电沉积，扫描范围为-1～0.3V，扫描速率为15mV/s，循环50次，直接在泡沫镍基板表面沉积掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂。2. Take the nickel foam substrate as the working electrode, the carbon rod as the counter electrode, and the Ag/AgCl electrode (3mol/L KCl) as the reference electrode, put it into the electrodeposition solution prepared in step 1, and conduct electrodeposition by cyclic voltammetry. The scanning range is -1 to 0.3V, the scanning rate is 15mV/s, and the cycle is 50 times, and the sulfur-doped Ni-Fe hydroxide nano-film catalyst is directly deposited on the surface of the nickel foam substrate.
实施例4Example 4
1、将下述原料混合均匀，制备成电沉积液：1. Mix the following raw materials evenly to prepare electrodeposition solution:
2、以泡沫镍基板为工作电极、碳棒为对电极，Ag/AgCl电极(3mol/L KCl)作为参比电极，放入步骤1制备的电沉积液中，通过循环伏安法电沉积，扫描范围为-1.3～0V，扫描速率为3mV/s，循环10次，直接在泡沫镍基板表面沉积掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂。2. Take the nickel foam substrate as the working electrode, the carbon rod as the counter electrode, and the Ag/AgCl electrode (3mol/L KCl) as the reference electrode, put it into the electrodeposition solution prepared in step 1, and conduct electrodeposition by cyclic voltammetry. The scanning range is -1.3～0V, the scanning rate is 3mV/s, and the cycle is 10 times, and the sulfur-doped Ni-Fe hydroxide nano-film catalyst is directly deposited on the surface of the nickel foam substrate.
实施例5Example 5
1、将下述原料混合均匀，制备成电沉积液：1. Mix the following raw materials evenly to prepare electrodeposition solution:
2、以泡沫镍基板为工作电极、碳棒为对电极，Ag/AgCl电极(3mol/L KCl)作为参比电极，放入步骤1制备的电沉积液中，通过循环伏安法电沉积，扫描范围为-1～0.2V，扫描速率为15mV/s，循环20次，直接在泡沫镍基板表面沉积掺杂硫的Ni-Fe氢氧化物纳米薄膜催化剂。2. Take the nickel foam substrate as the working electrode, the carbon rod as the counter electrode, and the Ag/AgCl electrode (3mol/L KCl) as the reference electrode, put it into the electrodeposition solution prepared in step 1, and conduct electrodeposition by cyclic voltammetry. The scanning range is -1 to 0.2V, the scanning rate is 15mV/s, and the cycle is 20 times, and the sulfur-doped Ni-Fe hydroxide nano-film catalyst is directly deposited on the surface of the nickel foam substrate.
为了证明本发明的有益效果，发明人采用实施例1～5中沉积掺杂硫的Ni-Fe氢氧化物纳米薄膜的泡沫镍基板作为工作电极、碳棒为对电极，Ag/AgCl电极(3mol/L KCl)作为参比电极，通过采用线性扫描伏安法以5mV s-1的扫描速度在1mol/L的KOH水溶液里检测其对水分解的析氧催化性能，所有的检测试验都在室温下进行，测得的电势按照ERHE＝EAg/AgCl+0.197V+0.059pH进行校正，最后测得结果都是相对于标准氢电极电势。测试结果见图7～11和表1。In order to prove the beneficial effect of the present invention, the inventor adopts the foamed nickel substrate of the Ni-Fe hydroxide nano-film deposited in the embodiment 1～5 as the working electrode, the carbon rod as the counter electrode, and the Ag/AgCl electrode (3mol /L KCl) as a reference electrode, by using linear sweep voltammetry with a scan rate of 5mV s -1 in a 1mol/L KOH aqueous solution to detect its oxygen evolution catalytic performance for water splitting, all detection tests were performed at room temperature The measured potential is corrected according to E RHE =E Ag/AgCl +0.197V+0.059pH, and the final measured results are all relative to the potential of the standard hydrogen electrode. The test results are shown in Figures 7-11 and Table 1.
表1Table 1
由图7～11和表1可见，采用本发明方法制备的掺杂硫的Ni-Fe氢氧化物纳米薄膜作为分解水析氧催化剂，其催化过电势很小，而且电流密度大。It can be seen from Figures 7 to 11 and Table 1 that the sulfur-doped Ni-Fe hydroxide nano-film prepared by the method of the present invention is used as a catalyst for water decomposition and oxygen evolution, and its catalytic overpotential is small and the current density is large.
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| CN110624568B (en) * | 2019-10-14 | 2022-05-17 | 青岛科技大学 | Preparation method of sulfur-doped nickel, iron and cobalt ternary hydroxide high-performance oxygen evolution catalyst with stepped three-dimensional structure |
| AU2021265075A1 (en) * | 2020-04-28 | 2022-11-24 | University Of Houston System | Fast ambient-temperature synthesis of OER catalysts for water electrolysis |
| CN111437838B (en) * | 2020-05-11 | 2023-06-09 | 苏州大学 | A kind of biomass carbon oxygen evolution electrocatalyst and preparation method thereof |
| CN112237927B (en) * | 2020-09-27 | 2024-03-29 | 东莞理工学院 | Catalyst for electrocatalytic reduction of nitrate as well as preparation method and application thereof |
| CN112695340B (en) * | 2021-01-03 | 2022-01-04 | 山东海氢能源科技有限公司 | A kind of preparation method of S-La-Ni/foamed nickel cathode material |
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