CN108374179A - A kind of preparation method and application of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping - Google Patents
A kind of preparation method and application of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 7
- -1 cobaltous selenide Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 title description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title 1
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007772 electrode material Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004917 carbon fiber Substances 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 239000011669 selenium Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910021094 Co(NO3)2-6H2O Inorganic materials 0.000 claims description 3
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 3
- 238000011068 loading method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013112 stability test Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- 229910001447 ferric ion Inorganic materials 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000000992 sputter etching Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
本发明公开了一种铁掺杂二硒化钴复合氮掺杂碳材料的制备方法及应用。该方法以金属有机骨架ZIF‑67为前驱体，利用三价铁离子刻蚀得到铁修饰的Fe‑ZIF‑67，将Fe‑ZIF‑67在高温下用硒蒸汽进行炭化和硒化，得到氮掺杂多孔碳负载的铁掺杂二硒化钴(Fe‑CoSe2@NC)粉末状电极材料。将Fe‑CoSe2@NC粉末制成浆料刷涂在导电碳纤维纸上制成Fe‑CoSe2@NC/CFP电极。Fe‑CoSe2@NC/CFP电极的电化学催化产氢性能指标为：Tafel斜率为40.9mV/decade；达到10mA/cm2电流密度的过电势为‑0.143V(vs RHE)。同时，该组装电极具有优良的电化学稳定性，在48小时恒电流稳定性测试中，没有出现明显的电压波动。该复合电极合成方法简单高效、绿色环保，原料和合成成本低，适合电化学分解水产氢的工业应用，具有广泛的科学意义。
The invention discloses a preparation method and application of an iron-doped cobalt diselenide composite nitrogen-doped carbon material. The method uses metal-organic framework ZIF-67 as a precursor, and uses ferric ion etching to obtain iron-modified Fe-ZIF-67, and carbonizes and selenizes Fe-ZIF-67 with selenium vapor at high temperature to obtain nitrogen Doped porous carbon-supported iron-doped cobalt diselenide (Fe‑ CoSe2 @NC) powder electrode material. Fe-CoSe 2 @NC powder was made into slurry and brushed on conductive carbon fiber paper to make Fe-CoSe 2 @NC/CFP electrode. The electrochemical catalytic hydrogen production performance index of Fe‑CoSe 2 @NC/CFP electrode is: the Tafel slope is 40.9mV/decade; the overpotential to reach a current density of 10mA/cm 2 is ‑0.143V (vs RHE). At the same time, the assembled electrode has excellent electrochemical stability, and there is no obvious voltage fluctuation in the 48-hour constant current stability test. The composite electrode synthesis method is simple, efficient, green and environmentally friendly, and has low raw material and synthesis costs, and is suitable for industrial applications in electrochemically decomposing water to produce hydrogen, and has extensive scientific significance.
Description
技术领域technical field
本发明涉及一种电催化分解水复合电极，尤其涉及一种高效电催化分解水产氢复合电极的制备方法与应用，属于电解水制氢领域。The invention relates to an electrocatalytic water splitting composite electrode, in particular to a preparation method and application of a high-efficiency electrocatalytic splitting water hydrogen production composite electrode, which belongs to the field of electrolytic water hydrogen production.
背景技术Background technique
随着全球煤、石油等化石能源消耗量的日益增长，严重的环境污染和未来能源危机是人类必须面临的问题。开发高效的、可再生的清洁能源,如太阳能、风能、水能、生物质能以及由此衍生的电能，提高其在整个能源结构中的比例迫在眉睫。在众多的新型能源中，如何实现新能源的存储和连续供应是一个非常关键的问题，其中将其转化为化学能是一个主要的途径，例如电分解水制氢。研制高效的电解水产氢催化剂对于提高电解水制氢过程中能源的利用效率至关重要，迄今为止，最高效的产氢催化剂是贵金属铂，但是其高成本和稀缺性限制了其在电解水制氢反应中的大规模应用。而基于过渡金属(铁、钴、镍等)的化合物在电解水产氢领域展现了不错的潜能，其低廉的价格和相对高的催化活性引起了研究人员的广泛关注。因此，用一种简单的方法制备廉价、高效、稳定的过渡金属化合物来替代贵金属铂作为电极催化产氢材料，是目前具有重要研究意义的一项工作。With the increasing consumption of fossil energy such as coal and oil in the world, serious environmental pollution and future energy crisis are problems that human beings must face. It is imminent to develop efficient, renewable and clean energy, such as solar energy, wind energy, water energy, biomass energy and the derived electric energy, and increase its proportion in the entire energy structure. Among the many new energy sources, how to realize the storage and continuous supply of new energy is a very critical issue, among which converting it into chemical energy is a main way, such as electrolysis of water to produce hydrogen. The development of efficient catalysts for hydrogen production by electrolysis of water is crucial to improving the efficiency of energy utilization in the process of hydrogen production by electrolysis of water. So far, the most efficient catalyst for hydrogen production is the noble metal platinum, but its high cost and scarcity limit its use in electrolysis of water. Large-scale applications in hydrogen reactions. Compounds based on transition metals (iron, cobalt, nickel, etc.) have shown good potential in the field of electrolyzing water to produce hydrogen, and their low price and relatively high catalytic activity have attracted widespread attention of researchers. Therefore, using a simple method to prepare cheap, efficient, and stable transition metal compounds to replace noble metal platinum as an electrode catalyst for hydrogen production is a work of great research significance at present.
发明内容Contents of the invention
本发明所要解决的问题就是提供一种采用简单温和的制备方法，合成高效、成本低、稳定性好的电解水催化产氢电极材料。The problem to be solved by the present invention is to provide a simple and mild preparation method, which is highly efficient, low in cost, and good in stability for electrolyzing water to catalyze hydrogen production electrode materials.
本发明的另一目的在于提供电解水产氢复合催化电极材料的制备方法。Another object of the present invention is to provide a method for preparing a composite catalytic electrode material for electrolyzing water to produce hydrogen.
本发明再有一目的在于提供粉末电极材料在酸性电解水产氢中的应用方法。Another object of the present invention is to provide an application method of the powder electrode material in acidic electrolysis of water for hydrogen production.
本发明主要采用如下技术方案实现：The present invention mainly adopts following technical scheme to realize:
一种铁掺杂二硒化钴复合氮掺杂碳材料的制备方法,包括如下步骤：A method for preparing an iron-doped cobalt diselenide composite nitrogen-doped carbon material, comprising the steps of:
1)ZIF-67制备：将Co(NO3)2·6H2O和2-甲基咪唑分别溶解在甲醇溶剂中，室温条件下混合搅拌反应，生成紫色的沉淀，即为产物ZIF-67，将ZIF-67沉淀反复洗涤直至得到澄清无色的上清液，将沉淀物离心分离，干燥备用；1) Preparation of ZIF-67: Dissolve Co(NO 3 ) 2 6H 2 O and 2-methylimidazole in methanol solvent respectively, mix and stir the reaction at room temperature, and form a purple precipitate, which is the product ZIF-67. The ZIF-67 precipitate was repeatedly washed until a clear and colorless supernatant was obtained, and the precipitate was centrifuged and dried for later use;
2)Fe-ZIF-67制备：将Fe(NO3)3·9H2O溶解于乙醇或水中得到含有硝酸铁的乙醇溶液或含有硝酸铁的水溶液；取步骤1)中得到的产物ZIF-67均匀分散在乙醇或水中，缓慢加入含有硝酸铁的乙醇溶液或含有硝酸铁的水溶液，并搅拌，利用Fe3+水解产生的氢质子刻蚀ZIF-67释放出Co2+,随着氢质子的消耗，Fe3+和Co2+发生共沉淀在ZIF-67颗粒上，得到铁修饰的Fe-ZIF-67；2) Preparation of Fe-ZIF-67: dissolving Fe(NO 3 ) 3 9H 2 O in ethanol or water to obtain an ethanol solution containing ferric nitrate or an aqueous solution containing ferric nitrate; take the product ZIF-67 obtained in step 1) Uniformly disperse in ethanol or water, slowly add ethanol solution containing ferric nitrate or aqueous solution containing ferric nitrate, and stir, use hydrogen protons produced by Fe 3+ hydrolysis to etch ZIF-67 to release Co 2+ , with the hydrogen protons Consumption, Fe 3+ and Co 2+ co-precipitate on ZIF-67 particles to obtain iron-modified Fe-ZIF-67;
3)Fe-CoSe2@NC制备:将步骤2)中得到的Fe-ZIF-67粉末利用硒蒸汽在350-500℃条件下进行炭化和硒化，得到黑色粉末状的氮掺杂多孔碳负载的铁掺杂二硒化钴复合电极材料，即Fe-CoSe2@NC电极材料。3) Preparation of Fe-CoSe 2 @NC: The Fe-ZIF-67 powder obtained in step 2) was carbonized and selenized at 350-500°C with selenium vapor to obtain a black powdery nitrogen-doped porous carbon support Iron-doped cobalt diselenide composite electrode material, that is, Fe-CoSe 2 @NC electrode material.
优选的，所述步骤1)中，Co(NO3)2·6H2O和2-甲基咪唑的摩尔比范围为1:1-1:16，反应时间为6-24小时。Preferably, in the step 1), the molar ratio of Co(NO 3 ) 2 ·6H 2 O to 2-methylimidazole is in the range of 1:1-1:16, and the reaction time is 6-24 hours.
优选的，所述的ZIF-67和Fe(NO3)3·9H2O的质量比为2:1-8:1。Preferably, the mass ratio of ZIF-67 to Fe(NO 3 ) 3 ·9H 2 O is 2:1-8:1.
优选的，所述步骤3)中，炭化和硒化在管式炉中进行，硒化炭化以惰性气体为载气，硒化炭化条件为400℃反应1-4小时。Preferably, in the step 3), the carbonization and selenization are carried out in a tube furnace, the selenization carbonization uses an inert gas as a carrier gas, and the selenization carbonization condition is 400° C. for 1-4 hours.
本发明还公开了一种Fe-CoSe2@NC/CFP电极的制备方法，将制备的Fe-CoSe2@NC电极材料混合导电炭黑、聚偏氟乙烯分散制成浆料，将浆料均匀刷涂在导电碳纤维纸上，干燥得到Fe-CoSe2@NC/CFP电极。The invention also discloses a preparation method of Fe-CoSe 2 @NC/CFP electrode. The prepared Fe-CoSe 2 @NC electrode material is mixed with conductive carbon black and polyvinylidene fluoride to form a slurry, and the slurry is uniformly Brush coated on conductive carbon fiber paper and dry to obtain Fe-CoSe 2 @NC/CFP electrode.
优选的，Fe-CoSe2@NC粉末材料与导电炭黑、聚偏氟乙烯按照质量比1:(0.125-1):(0.125-0.5)混合，CFP上Fe-CoSe2@NC有效活性成分负载量为0.2-1mg/cm2。Preferably, Fe-CoSe 2 @NC powder material is mixed with conductive carbon black and polyvinylidene fluoride in a mass ratio of 1:(0.125-1):(0.125-0.5), and the effective active ingredient of Fe-CoSe 2 @NC is loaded on CFP The amount is 0.2-1 mg/cm 2 .
优选的，所述干燥过程在50℃条件下进行，干燥时间为12小时。Preferably, the drying process is carried out at 50° C., and the drying time is 12 hours.
本发明还公开了Fe-CoSe2@NC/CFP电极在电解水产氢中的应用。在0.5MH2SO4电解液中进行的电化学产氢测试结果表明，Fe-CoSe2@NC/CFP复合催化电极具有高的产氢活性，其催化产生10mA/cm2的电流密度仅需要-0.143V(vs.RHE)的过电势，且在48小时恒电流测试过程中展现出优异的稳定性。The invention also discloses the application of the Fe-CoSe 2 @NC/CFP electrode in electrolyzing water to produce hydrogen. The electrochemical hydrogen production test results in 0.5MH 2 SO 4 electrolyte showed that the Fe-CoSe 2 @NC/CFP composite catalytic electrode has high hydrogen production activity, and its catalytic current density of 10mA/cm 2 only needs- 0.143V (vs.RHE) overpotential, and exhibited excellent stability during the 48-hour galvanostatic test.
相对于现有技术，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
1.Fe-CoSe2@NC/CFP电解水制氢过电势低，10mA/cm2过电势仅为-143mV。1. Fe-CoSe 2 @NC/CFP electrolyzed water has a low overpotential for hydrogen production, and the overpotential at 10mA/cm 2 is only -143mV.
2.Fe-CoSe2@NC/CFP电解水制氢Tafel斜率低，仅为40.9mV/dec，略高于贵金属铂(30mV/dec)，越低的Tafel斜率说明材料可以更低的过电势下驱动产生更大的电流，从而产生更多的氢气，提高能源的利用效率。2. The Tafel slope of Fe-CoSe 2 @NC/CFP electrolyzed water for hydrogen production is low, only 40.9mV/dec, which is slightly higher than that of noble metal platinum (30mV/dec). The lower the Tafel slope, the lower the overpotential of the material can be The drive generates a larger current, thereby generating more hydrogen and improving energy utilization efficiency.
3.电极材料合成工艺简单，反应条件温和，催化剂Fe-CoSe2@NC可以通过制成浆料刷涂在导电基底上制成电极使用，工艺流程简单可控，利于工业化操作。3. The synthesis process of the electrode material is simple, and the reaction conditions are mild. The catalyst Fe-CoSe 2 @NC can be used as an electrode by making a slurry and brushing it on a conductive substrate. The process flow is simple and controllable, which is conducive to industrial operation.
附图说明Description of drawings
图1示出实施例2通过扫描电镜观察的ZIF-67形貌图；Fig. 1 shows the ZIF-67 morphology figure observed by scanning electron microscope of embodiment 2;
图2示出实施例2通过扫描电镜观察的Fe-ZIF-67形貌图；Fig. 2 shows the Fe-ZIF-67 morphology figure that embodiment 2 observes by scanning electron microscope;
图3示出实施例2通过扫描电镜观察的Fe-CoSe2@NC形貌图；Fig. 3 shows the Fe-CoSe 2 @NC topography diagram observed by scanning electron microscope in embodiment 2;
图4示出实施例2中ZIF-67、Fe-CoSe2@NC和CoSe2@NC的结晶状态和晶型结构表征；Fig. 4 shows the crystalline state and crystal structure characterization of ZIF-67, Fe-CoSe 2 @NC and CoSe 2 @NC in Example 2;
图5示出实施例4中的Fe-CoSe2@NC/CFP和CoSe2@NC/CFP电极线性扫描伏安曲线；Fig. 5 shows Fe-CoSe 2 @NC/CFP and CoSe 2 @NC/CFP electrode linear sweep voltammetry curve in embodiment 4;
图6示出实施例4中的Fe-CoSe2@NC/CFP和CoSe2@NC/CFP电极的Tafel曲线；Fig. 6 shows the Tafel curve of Fe-CoSe 2 @NC/CFP and CoSe 2 @NC/CFP electrode in embodiment 4;
图7示出实施例4中的Fe-CoSe2@NC/CFP电极稳定性测试的电流-时间曲线；Fig. 7 shows the current-time curve of Fe-CoSe 2 @NC/CFP electrode stability test in embodiment 4;
图8示出实施例5中氢气实际产量和理论产量随时间的变化曲线。Fig. 8 shows the variation curve of the actual hydrogen production and the theoretical production with time in Example 5.
具体实施方式Detailed ways
实施例1Example 1
将几何面积为2平方厘米的碳纤维纸，依次用去稀盐酸、乙醇、去离子水超声清洗30分钟，除去表面的金属离子和有机物等杂质。放置在烘箱中，50℃干燥12小时，备用。The carbon fiber paper with a geometric area of 2 square centimeters was ultrasonically cleaned with dediluted hydrochloric acid, ethanol, and deionized water for 30 minutes in order to remove impurities such as metal ions and organic substances on the surface. Place in an oven, dry at 50°C for 12 hours, and set aside.
实施例2Example 2
首先采用溶液沉淀法制备ZIF-67，将8mmol 2-甲基咪唑和2mmol六水合硝酸钴分别溶解在50ml甲醇溶液中溶解得到澄清溶液，然后将两种溶液混合室温搅拌反应24小时。随后将反应产物离心、洗涤、干燥，得到固体紫色粉末ZIF-67,ZIF-67的形貌图片如图1所示，呈现出标准的菱形十二面体结构。取40mg ZIF-67粉末均匀分散在20ml乙醇溶液中，加入5ml硝酸铁乙醇溶液(2mg/ml),室温条件下搅拌反应两小时，ZIF-67在Fe3+水解产生的氢离子的刻蚀作用释放出Co2+,随着氢质子的消耗，Fe3+和Co2+共沉淀在ZIF-67颗粒上，得到铁修饰的Fe-ZIF-67，然后将反应产物离心、洗涤、干燥得到紫色的固体粉末Fe-ZIF-67，形貌图片如图2所示，Fe-ZIF-67保持了菱形十二面体结构，颗粒表面在刻蚀后变的粗糙。然后将Fe-ZIF-67均匀铺散在瓷舟中，放入管式炉，以100sccm氩气为载气，以硒蒸汽为反应气，在400℃条件下进行高温硒化两个小时，得到Fe-CoSe2@NC电极材料，形貌图片如图3所示，单个的Fe-CoSe2@NC颗粒仍然维持了菱形十二面体结构，表面变的更加粗糙。作为对比，将没有刻蚀过的ZIF-67粉末进行同样的硒化处理，直接在400℃条件下高温硒化两个小时，得到CoSe2@NC电极材料跟Fe-CoSe2@NC具有相似的形貌。ZIF-67、Fe-CoSe2@NC和CoSe2@NC的结晶状态和晶型结构如图4所示，其中Fe-CoSe2@NC和CoSe2@NC中均含有结晶度良好的斜立方相二硒化钴晶体。First, ZIF-67 was prepared by solution precipitation method. 8 mmol 2-methylimidazole and 2 mmol cobalt nitrate hexahydrate were dissolved in 50 ml methanol solution to obtain a clear solution, and then the two solutions were mixed and stirred at room temperature for 24 hours. Subsequently, the reaction product was centrifuged, washed, and dried to obtain solid purple powder ZIF-67. The morphology picture of ZIF-67 is shown in Figure 1, showing a standard rhombic dodecahedral structure. Take 40mg of ZIF-67 powder and evenly disperse in 20ml of ethanol solution, add 5ml of ferric nitrate ethanol solution (2mg/ml), stir and react at room temperature for two hours, the etching effect of ZIF-67 on the hydrogen ions generated by Fe 3+ hydrolysis Co 2+ is released, and with the consumption of hydrogen protons, Fe 3+ and Co 2+ co-precipitate on ZIF-67 particles to obtain iron-modified Fe-ZIF-67, and then the reaction product is centrifuged, washed, and dried to obtain a purple color The solid powder Fe-ZIF-67, as shown in Figure 2, Fe-ZIF-67 maintains a rhombic dodecahedron structure, and the surface of the particles becomes rough after etching. Then spread Fe-ZIF-67 evenly in a porcelain boat, put it into a tube furnace, use 100 sccm argon as the carrier gas, and use selenium vapor as the reaction gas, and carry out high-temperature selenization at 400 ° C for two hours to obtain Fe -CoSe 2 @NC electrode material, the morphology picture is shown in Figure 3, a single Fe-CoSe 2 @NC particle still maintains a rhombic dodecahedron structure, and the surface becomes rougher. As a comparison, the unetched ZIF-67 powder was subjected to the same selenization treatment, and directly selenized at 400°C for two hours at a high temperature, and the obtained CoSe 2 @NC electrode material had similar properties to Fe-CoSe 2 @NC shape. The crystalline state and crystal structure of ZIF-67, Fe-CoSe 2 @NC and CoSe 2 @NC are shown in Fig. 4, in which both Fe-CoSe 2 @NC and CoSe 2 @NC contain a rhombic cubic phase with good crystallinity Cobalt diselenide crystals.
实施例3Example 3
将制备好的上述Fe-CoSe2@NC粉末材料与导电炭黑、聚偏氟乙烯按照质量比5:4:1混合，用乙醇调和制成浆料刷涂在CFP上制成Fe-CoSe2@NC/CFP电极，在50℃条件下干燥12小时。将CoSe2@NC电极材料按照同样的比例和刷涂方法负载到CFP上，制备CoSe2@NC/CFP电极。其中Fe-CoSe2@NC和CoSe2@NC活性成分在CFP上的负载量均为0.5mg/cm2。Mix the prepared Fe-CoSe 2 @NC powder material with conductive carbon black and polyvinylidene fluoride at a mass ratio of 5:4:1, and use ethanol to make a slurry and brush it on CFP to make Fe-CoSe 2 @NC/CFP electrode, dried at 50°C for 12 hours. CoSe 2 @NC electrode material was loaded on CFP according to the same ratio and brushing method to prepare CoSe 2 @NC/CFP electrode. The loads of Fe-CoSe 2 @NC and CoSe 2 @NC active ingredients on CFP are both 0.5mg/cm 2 .
实施例4Example 4
采用三电极体系的电化学工作站,将如实施例3所述制备的Fe-CoSe2@NC/CFP电极和CoSe2@NC/CFP电极作为工作电极，石墨棒为对电极，Ag/AgCl电极为参比电极，电解液为0.5M H2SO4溶液。极化曲线扫描区间为0到-0.6V(vs.Ag/AgCl),扫描速率为3mV/s,不同电极的极化结果如图5所示，由极化曲线计算得出的Tafel曲线如图6所示，图中的产氢测试结果表明，Fe-CoSe2@NC/CFP电极达到10mA/cm2的电流密度仅需要-0.143V(vs.RHE)，而未掺杂的CoSe2@NC/CFP电极达到10mA/cm2的电流密度需要-0.173V(vs.RHE)，Fe-CoSe2@NC/CFP电极和CoSe2@NC/CFP电极的产氢Tafel斜率分别为40.9mV/dec和69.2mV/dec，因此，Fe-CoSe2@NC/CFP电极的产氢性能相比于CoSe2@NC/CFP电极有明显的提升。Fe-CoSe2@NC/CFP电极在10mA/cm2条件下恒电流稳定性测试数据如图7所示，在48小时恒电流测试过程中，Fe-CoSe2@NC/CFP电极的过电势没有明显的波动，显示出良好的电化学稳定性。根据DFT理论计算分析，Fe-CoSe2晶体与CoSe2晶体的产氢活性位点主要为Co原子，而Fe-CoSe2晶体中Co位点的活性氢吸附自由能要比CoSe2晶体中的Co位点更接近零，因此可以加快电解水产氢中的过渡态氢的吸脱附过程，因此Fe-CoSe2具有更高的催化活性。实施例5Using an electrochemical workstation with a three-electrode system, the Fe-CoSe 2 @NC/CFP electrode and the CoSe 2 @NC/CFP electrode prepared as described in Example 3 were used as the working electrode, the graphite rod was the counter electrode, and the Ag/AgCl electrode was Reference electrode, the electrolyte is 0.5MH 2 SO 4 solution. The scanning interval of the polarization curve is 0 to -0.6V (vs.Ag/AgCl), and the scanning rate is 3mV/s. The polarization results of different electrodes are shown in Figure 5, and the Tafel curve calculated from the polarization curve is shown in Figure 5. 6, the hydrogen production test results in the figure show that the Fe-CoSe 2 @NC/CFP electrode needs only -0.143V (vs.RHE) to achieve a current density of 10mA/cm 2 , while the undoped CoSe 2 @NC /CFP electrode needs -0.173V(vs.RHE) to achieve a current density of 10mA/cm 2 , and the hydrogen production Tafel slopes of Fe-CoSe 2 @NC/CFP electrode and CoSe 2 @NC/CFP electrode are 40.9mV/dec and 69.2mV/dec, therefore, the hydrogen production performance of Fe-CoSe 2 @NC/CFP electrode is significantly improved compared with CoSe 2 @NC/CFP electrode. The galvanostatic stability test data of the Fe-CoSe 2 @NC/CFP electrode under the condition of 10mA/cm 2 is shown in Figure 7. During the 48-hour galvanostatic test, the overpotential of the Fe-CoSe 2 @NC/CFP electrode did not Obvious fluctuations, showing good electrochemical stability. According to DFT theoretical calculation and analysis, the hydrogen-producing active sites of Fe-CoSe 2 crystals and CoSe 2 crystals are mainly Co atoms, and the active hydrogen adsorption free energy of Co sites in Fe-CoSe 2 crystals is higher than that of Co atoms in CoSe 2 crystals. The site is closer to zero, so the adsorption and desorption process of transition state hydrogen in the electrolysis of water for hydrogen production can be accelerated, so Fe-CoSe 2 has higher catalytic activity. Example 5
如实施例4所述，采用三电极体系的电化学工作站,Fe-CoSe2@NC/CFP电极作为工作电极，石墨棒为对电极，Ag/AgCl电极为参比电极，电解液为0.5M H2SO4溶液。电解液持续曝入30分钟N2排除体系中的氧气，测试过程中持续通入氮气。施加10mA恒电流，每隔30分钟取一次气体，用气相色谱测试密闭体系中氢气产量。氢气的产量随时间变化的曲线如图8，其测得的实际氢气产量基本等同于理论计算产量，说明电解水产氢过程中基本没有其他副反应发生，Fe-CoSe2@NC/CFP电极电解水产氢的电流效率接近100％。As described in Example 4, an electrochemical workstation with a three-electrode system is used, the Fe-CoSe 2 @NC/CFP electrode is used as the working electrode, the graphite rod is used as the counter electrode, the Ag/AgCl electrode is used as the reference electrode, and the electrolyte is 0.5MH 2 SO4 solution. The electrolyte was continuously exposed to N2 for 30 minutes to eliminate the oxygen in the system, and nitrogen gas was continuously introduced during the test. A constant current of 10mA was applied, the gas was taken every 30 minutes, and the hydrogen production in the closed system was tested by gas chromatography. The curve of hydrogen production versus time is shown in Figure 8. The measured actual hydrogen production is basically equal to the theoretical calculation production, indicating that there are basically no other side reactions in the process of electrolyzing water to produce hydrogen. Fe-CoSe 2 @NC/CFP electrode electrolyzes water production The current efficiency of hydrogen is close to 100%.
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