CN108321388A - The synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate - Google Patents
The synthetic method of nickel doping ferrous disulfide nanowire array structure in titanium sheet substrate Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 110
- 239000002070 nanowire Substances 0.000 title claims abstract description 85
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 84
- 239000000758 substrate Substances 0.000 title claims abstract description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 45
- 229910052759 nickel Inorganic materials 0.000 title claims description 22
- 229940095991 ferrous disulfide Drugs 0.000 title claims 13
- 238000010189 synthetic method Methods 0.000 title claims 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 20
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 229910052786 argon Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 229910002588 FeOOH Inorganic materials 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 3
- 239000005864 Sulphur Substances 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 2
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 abstract description 35
- 229910000339 iron disulfide Inorganic materials 0.000 abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000001257 hydrogen Substances 0.000 abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 24
- 238000003491 array Methods 0.000 abstract description 15
- 150000002505 iron Chemical class 0.000 abstract description 10
- 238000004073 vulcanization Methods 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 10
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 7
- 238000004832 voltammetry Methods 0.000 description 7
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 229910052976 metal sulfide Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001453 impedance spectrum Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052960 marcasite Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003944 fast scan cyclic voltammetry Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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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Abstract
本发明涉及钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成方法，配制含铁盐、镍盐、硫酸钠及尿素的混合水溶液，投入干净钛片，经水热反应得到了原位生长于钛片基底表面的镍掺杂氢氧化氧铁纳米线阵列；将前驱体置于管式炉中进行高温气相硫化利用氩气进行气氛保护，得到了组装于钛片基底的镍掺杂二硫化铁纳米线阵列。本发明方法操作简便、重复性好，得到的产物结构稳定，能够均匀且坚固地分布在钛片表面，可以直接作为二维电极材料应用于电化学设备中，同时经电解水测试，发现镍的掺杂大幅度提升了二硫化铁的电催化产氢活性及稳定性，而且有望进一步促进其在储能、光催化等领域的性能提升，扩展其应用范围。
The invention relates to a method for synthesizing a nickel-doped iron disulfide nanowire array structure on a titanium sheet substrate. A mixed aqueous solution containing iron salt, nickel salt, sodium sulfate and urea is prepared, a clean titanium sheet is put in, and the in-situ nanowire structure is obtained through hydrothermal reaction. Nickel-doped ferric oxyhydroxide nanowire arrays grown on the surface of the titanium sheet substrate; the precursor was placed in a tube furnace for high-temperature gas-phase vulcanization, and the atmosphere was protected with argon, and the nickel-doped iron oxide hydroxide nanowire array assembled on the titanium sheet substrate was obtained. Iron sulfide nanowire arrays. The method of the invention is easy to operate and has good repeatability, and the obtained product has a stable structure and can be evenly and firmly distributed on the surface of the titanium sheet, and can be directly used as a two-dimensional electrode material in electrochemical equipment. Doping greatly improves the electrocatalytic hydrogen production activity and stability of iron disulfide, and is expected to further promote its performance in energy storage, photocatalysis and other fields, and expand its application range.
Description
技术领域technical field
本发明涉及一种掺杂型过渡金属硫化物的合成方法，尤其是涉及一种钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成方法。The invention relates to a method for synthesizing a doped transition metal sulfide, in particular to a method for synthesizing a nickel-doped iron disulfide nanowire array structure on a titanium substrate.
背景技术Background technique
目前随着社会的发展，各行业对于能源的需求也在不断加大，因此设计并研发出高性能、低成本、成效高的纳米能源材料则成为科学工作者们重点关注的方向。特别是在电催化及电化学储能领域，纳米电极材料的性能局限性问题丞待解决。金属硫化物中的硫元素，其最外层电子结构为3S23P4，具有的空3d轨道和3s、3p轨道能级接近，因此d轨道在一定条件下具有多种成键方式，使得金属硫化物的结构具有多样性，表现出丰富的性质，具有广泛的应用范围。例如二硫化钴、二硫化铁、二硫化镍等等可以应用于电解水产氢产氧、超级电容器及锂离子电池领域。为了进一步提升金属硫化物在电化学方面的性能，越来越多类型的材料被发明，如多相复合型材料、合金型材料、掺杂型材料等。其中，杂元素的掺杂因具有操作简便、选择性广、性能提升明显而成为一项研究热点。如在二硫化钴纳米材料里面进行镍元素的掺杂，或者对二硫化钼进行硒掺杂，均使得电催化产氢性能得到了明显的提升。At present, with the development of society, the demand for energy in various industries is also increasing. Therefore, the design and development of high-performance, low-cost, and high-efficiency nano energy materials have become the focus of scientific workers. Especially in the field of electrocatalysis and electrochemical energy storage, the performance limitations of nano-electrode materials have yet to be resolved. The sulfur element in metal sulfides has the outermost electronic structure of 3S 2 3P 4 , and its empty 3d orbital is close to the energy levels of 3s and 3p orbitals. Therefore, the d orbital has a variety of bonding methods under certain conditions, making the metal Sulfides have diverse structures, exhibit rich properties, and have a wide range of applications. For example, cobalt disulfide, iron disulfide, nickel disulfide, etc. can be used in the fields of electrolyzing water to produce hydrogen and oxygen, supercapacitors and lithium-ion batteries. In order to further improve the electrochemical performance of metal sulfides, more and more types of materials have been invented, such as multi-phase composite materials, alloy materials, doped materials, etc. Among them, the doping of heteroelements has become a research hotspot because of its simple operation, wide selectivity, and obvious performance improvement. For example, the doping of nickel element in cobalt disulfide nanomaterials, or the doping of selenium in molybdenum disulfide can significantly improve the performance of electrocatalytic hydrogen production.
金属硫化物中的黄铁矿型二硫化铁，属立方晶系，其地表储量丰富、成本低廉，禁带宽度为0.95eV，为一种应用较广泛的半导体材料。纳米级别的二硫化铁可作为具有潜力的电极材料普遍应用于光电催化、电化学储能等领域。目前已有工作报道，在二硫化铁材料中进行钴离子的掺杂，同时与碳纳米管复合，其电解水产氢性能相对于纯相二硫化铁与碳纳米管复合材料有了明显的提升。因此，杂原子的掺杂对于二硫化铁材料在产氢方面的提升起到了很大的贡献作用，同时也有望提升其在储能方面的性能，具有一定的研究意义。同时于导电基底上组装的纳米材料可直接作为能源器件，构建高效的电化学能源装置，具有操作简便、活性面积大、电荷易传输等优势。但是目前掺杂型的金属硫化物由于制备方法繁琐、导电性不够优良，而且在酸性电解液中产氢稳定性较差，从而使其应用受到了一定的限制。基于上述存在的问题，我们发展了钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成方法，制备步骤简便易操作，产物形貌均匀，重复性好，结构较稳定，而且镍的掺杂使得材料在0.5M H2SO4电解液中表现出了明显优于纯二硫化铁纳米线阵列的产氢催化活性及长效稳定性，并且有望广泛应用于储能、光催化、全电解水等领域。The pyrite-type iron disulfide in the metal sulfide belongs to the cubic crystal system. It has abundant surface reserves, low cost, and a band gap of 0.95eV. It is a widely used semiconductor material. Nano-scale iron disulfide can be widely used as a potential electrode material in photoelectrocatalysis, electrochemical energy storage and other fields. At present, it has been reported that the doping of cobalt ions in iron disulfide materials and compounding with carbon nanotubes at the same time can significantly improve the hydrogen production performance of electrolyzed water compared with pure phase iron disulfide and carbon nanotube composite materials. Therefore, the doping of heteroatoms has greatly contributed to the improvement of hydrogen production of iron disulfide materials, and it is also expected to improve its performance in energy storage, which has certain research significance. At the same time, nanomaterials assembled on conductive substrates can be directly used as energy devices to construct efficient electrochemical energy devices, which have the advantages of easy operation, large active area, and easy charge transfer. However, the current doped metal sulfides are limited in application due to tedious preparation methods, poor electrical conductivity, and poor hydrogen production stability in acidic electrolytes. Based on the above problems, we developed a synthesis method of nickel-doped iron disulfide nanowire array structure on the titanium substrate. The dopant makes the material show significantly better hydrogen production catalytic activity and long-term stability than pure iron disulfide nanowire array in 0.5MH 2 SO 4 electrolyte, and it is expected to be widely used in energy storage, photocatalysis, and full electrolysis of water. and other fields.
发明内容Contents of the invention
本发明的目的就是为了克服上述二硫化铁材料在电化学性能方面的局限性，发展了一种钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成方法。The object of the present invention is to develop a synthesis method of a nickel-doped iron disulfide nanowire array structure on a titanium sheet substrate in order to overcome the limitations of the above-mentioned iron disulfide materials in terms of electrochemical performance.
本发明的目的可以通过以下技术方案来实现：The purpose of the present invention can be achieved through the following technical solutions:
钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成方法，包括以下步骤：A method for synthesizing a nickel-doped iron disulfide nanowire array structure on a titanium sheet substrate, comprising the following steps:
(1)钛片基底上原位生长的镍掺杂氢氧化氧铁纳米线阵列的合成：将铁盐、镍盐、硫酸钠和尿素溶于去离子水中得到反应溶液，投入经超声处理过的干净裸钛片后置于高温下反应，反应结束后取出钛片，依次用乙醇和去离子水冲洗干净，于80℃烘干，得到原位生长的镍掺杂氢氧化氧铁纳米线阵列(Ni-FeOOH/Ti)；(1) Synthesis of nickel-doped iron oxyhydroxide nanowire arrays grown in situ on a titanium substrate: dissolving iron salts, nickel salts, sodium sulfate and urea in deionized water to obtain a reaction solution, and putting it into ultrasonically treated Clean the bare titanium sheet and put it under high temperature to react. After the reaction, take out the titanium sheet, rinse it with ethanol and deionized water successively, and dry it at 80°C to obtain the nickel-doped iron oxyhydroxide nanowire array grown in situ ( Ni-FeOOH/Ti);
(2)钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成：取步骤(1)制得的镍掺杂氢氧化氧铁纳米线阵列置于管式炉中，并称取足量的硫粉置于管式炉的气源端口，将管式炉用氩气进行反复冲洗从而排净空气，在一定流速的氩气气氛保护下，进行高温气相硫化，反应结束后待反应装置自然冷却至室温，取出组装于钛片基底的镍掺杂二硫化铁纳米线阵列，用乙醇和去离子水依次清洗，于80℃烘干，即制备得到镍掺杂二硫化铁纳米线阵列结构。(2) Synthesis of nickel-doped iron disulfide nanowire array structure on titanium substrate: take the nickel-doped iron oxyhydroxide nanowire array prepared in step (1) and place it in a tube furnace, and weigh a sufficient amount The sulfur powder is placed at the gas source port of the tube furnace, and the tube furnace is repeatedly flushed with argon to remove the air. Under the protection of argon atmosphere at a certain flow rate, high-temperature gas-phase vulcanization is carried out. After the reaction, the reaction device is naturally Cool to room temperature, take out the nickel-doped iron disulfide nanowire array assembled on the titanium sheet substrate, wash with ethanol and deionized water in sequence, and dry at 80°C to prepare the nickel-doped iron disulfide nanowire array structure.
步骤(1)中所述的铁盐为六水合三氯化铁，所述的镍盐为六水合二氯化镍，所述的硫酸钠为无水硫酸钠。反应溶液中铁盐的浓度为20～30mM，镍盐的浓度为0～30mM但不为0，硫酸钠的浓度为40～60mM，尿素的浓度为0～50mM但不为0。高温反应的温度为110～130℃，反应时间为6～12h。The iron salt described in step (1) is ferric trichloride hexahydrate, the described nickel salt is nickel dichloride hexahydrate, and the described sodium sulfate is anhydrous sodium sulfate. The concentration of iron salt in the reaction solution is 20-30mM, the concentration of nickel salt is 0-30mM but not 0, the concentration of sodium sulfate is 40-60mM, and the concentration of urea is 0-50mM but not 0. The temperature of the high-temperature reaction is 110-130° C., and the reaction time is 6-12 hours.
步骤(2)中加入的硫粉与镍掺杂氢氧化氧铁纳米线阵列的比例关系为1～2g/1～2cm2。高温气相硫化的反应温度为350～450℃，反应时间为1～3h。氩气流速为25sccm。The ratio of the sulfur powder added in step (2) to the nickel-doped iron oxyhydroxide nanowire array is 1-2g/1-2cm 2 . The reaction temperature of high temperature vapor phase vulcanization is 350-450°C, and the reaction time is 1-3h. The argon flow rate was 25 sccm.
制备得到的镍掺杂二硫化铁纳米线阵列均匀坚固地分布于钛片表面，纳米线的平均长度为200～250nm，平均直径为30～50nm。The prepared nickel-doped iron disulfide nanowire array is uniformly and firmly distributed on the surface of the titanium sheet, the average length of the nanowires is 200-250nm, and the average diameter is 30-50nm.
上述制备工艺参数中，合成前驱体Ni-FeOOH纳米线的原料配比量，以及气相硫化反应的温度、时间，对最终产物的形貌、结构稳定性和产物尺寸具有决定性的影响。原料配比量对Ni-FeOOH纳米线的形貌以及组装于钛片基底的结构稳定性具有决定性的作用，如果配比量超出合适的范围，材料的形貌会发生一定程度的变化，于基底上原位生长的结构稳定性也会相应变差；气相硫化反应的温度和时间，对最终产物Ni-FeS2纳米线的性能和结构稳定性会有影响，温度过低及时间过短，会导致产物硫化不充分，物相不纯，从而使其性能可能会变差，温度过高会使得产物结构稳定性变差，同样可能会使得性能受到影响。Among the above-mentioned preparation process parameters, the raw material ratio of the synthetic precursor Ni-FeOOH nanowires, as well as the temperature and time of the gas-phase vulcanization reaction have a decisive impact on the morphology, structural stability and product size of the final product. The proportion of raw materials has a decisive effect on the morphology of Ni-FeOOH nanowires and the structural stability assembled on the titanium sheet substrate. If the proportion exceeds the appropriate range, the morphology of the material will change to a certain extent. The structural stability of the in-situ growth will also be correspondingly worse; the temperature and time of the gas-phase vulcanization reaction will have an impact on the performance and structural stability of the final product Ni-FeS 2 nanowires. If the temperature is too low and the time is too short, it will Insufficient vulcanization of the product and impure phase may result in poor performance. Excessively high temperature will deteriorate the structural stability of the product and may also affect the performance.
本发明的反应体系不依赖于精确的pH值，产物在基底表面均匀分布，结构稳固，只需将负载着产物的钛片进行简单的浸润清洗即可，而且气相反应单纯，副产物少，成功率高。同时材料直接组装于钛片基底表面，在进行锂电池封装以及电催化测试时可直接作为工作电极使用，无需粘接剂的辅助以及拌料、涂膜等一系列繁琐的电极制备流程，避免了导电性的降低，具有操作简便、活性面积大等优势。The reaction system of the present invention does not depend on the precise pH value, the product is evenly distributed on the substrate surface, and the structure is stable. It only needs to carry out simple immersion cleaning on the titanium sheet loaded with the product, and the gas phase reaction is simple, with few by-products, successfully The rate is high. At the same time, the material is directly assembled on the surface of the titanium sheet substrate, and can be used directly as a working electrode when performing lithium battery packaging and electrocatalytic testing, without the aid of adhesives and a series of cumbersome electrode preparation processes such as mixing materials and coating films, which avoids the The reduction of conductivity has the advantages of easy operation and large active area.
与现有技术相比，本发明采用的方法合成的钛片基底上镍掺杂二硫化铁纳米线阵列，其形貌均一，分散均匀，能够致密、坚固地分布于钛片基底表面，而且重复性好，合成方法简便易行。镍的掺杂有望进一步提升二硫化铁纳米线阵列在电催化产氢、锂离子电池方面的性能表现，具有良好的应用前景。Compared with the prior art, the nickel-doped iron disulfide nanowire array on the titanium sheet substrate synthesized by the method adopted in the present invention has uniform appearance and uniform dispersion, and can be densely and firmly distributed on the surface of the titanium sheet substrate, and repeated Good properties, simple synthesis method. Nickel doping is expected to further improve the performance of iron disulfide nanowire arrays in electrocatalytic hydrogen production and lithium-ion batteries, and has a good application prospect.
附图说明Description of drawings
图1中a，b分别为实施例1、2制备的钛片基底上原位生长的FeOOH纳米线阵列及Ni-FeOOH纳米线阵列的扫描电子显微镜照片；Among Fig. 1, a, b are the scanning electron micrographs of FeOOH nanowire array and Ni-FeOOH nanowire array grown in situ on the titanium sheet substrate prepared by embodiment 1 and 2 respectively;
图2中a，b分别为实施例3、4制备的钛片基底上组装的FeS2纳米线阵列及Ni-FeS2纳米线阵列的扫描电子显微镜照片；Among Fig. 2, a, b are the scanning electron micrographs of FeS2nanowire arrays and Ni-FeS2nanowire arrays assembled on the titanium sheet substrate prepared by embodiment 3 and 4 respectively;
图3为实施例4制备的钛片基底上组装的Ni-FeS2纳米线阵列的X射线衍射图谱；Fig. 3 is the Ni-FeS assembled on the titanium sheet substrate that embodiment 4 prepares The X-ray diffraction pattern of nanowire array;
图4为实施例6得到的钛片基底上组装的FeS2及Ni-FeS2纳米线阵列，以及裸钛片三者的线性伏安产氢曲线；Fig. 4 is FeS assembled on the titanium sheet substrate that embodiment 6 obtains and Ni-FeS Nanowire array, and the three linear voltammetry hydrogen production curves of the bare titanium sheet;
图5为实施例6得到的钛片基底上组装的Ni-FeS2纳米线阵列(图5a)及FeS2纳米线阵列(图5b)的产氢循环稳定性测试图；Fig. 5 is the Ni-FeS assembled on the titanium sheet substrate that embodiment 6 obtains 2 nanowire arrays (Fig. 5a) and FeS2 nanowire arrays (Fig. 5b) hydrogen production cycle stability test figure;
图6为实施例6得到的钛片基底上组装的FeS2及Ni-FeS2纳米线阵列的电化学阻抗谱图。Fig. 6 is the electrochemical impedance spectrum of FeS 2 and Ni-FeS 2 nanowire arrays assembled on the titanium sheet substrate obtained in Example 6.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
实施例1Example 1
钛片基底上原位生长的FeOOH纳米线阵列的合成Synthesis of In Situ FeOOH Nanowire Arrays Grown on Titanium Sheet Substrates
将六水合三氯化铁和硫酸钠溶于去离子水中得到反应溶液，反应溶液中铁盐的浓度为25mM，硫酸钠的浓度为50mM，并转入反应釜中，向反应体系中投入经超声处理过的干净裸钛片，封装釜，并置于120℃下反应12小时。反应结束后取出钛片，依次用乙醇和去离子水冲洗干净，于80℃烘干，得到原位生长的FeOOH纳米线阵列。所得到的样品如图1(a)所示，扫描电镜显示FeOOH为均匀生长在钛片基底上的纳米线阵列结构，单根纳米线的直径范围约为50～80nm。Dissolve ferric chloride hexahydrate and sodium sulfate in deionized water to obtain a reaction solution, the concentration of iron salt in the reaction solution is 25mM, the concentration of sodium sulfate is 50mM, and transfer to the reaction kettle, put into the reaction system and undergo ultrasonic treatment The cleaned bare titanium sheet was cleaned, sealed in the kettle, and placed at 120°C for 12 hours to react. After the reaction, the titanium sheet was taken out, rinsed with ethanol and deionized water in sequence, and dried at 80° C. to obtain FeOOH nanowire arrays grown in situ. The obtained sample is shown in Figure 1(a). The scanning electron microscope showed that FeOOH was a nanowire array structure uniformly grown on the titanium sheet substrate, and the diameter of a single nanowire ranged from about 50 to 80nm.
实施例2Example 2
钛片基底上原位生长的Ni-FeOOH纳米线阵列的合成Synthesis of Ni-FeOOH Nanowire Arrays Grown in Situ on Titanium Sheet Substrate
将六水合三氯化铁、六水合二氯化镍、硫酸钠和尿素溶于去离子水中得到反应溶液，反应溶液中铁盐的浓度为25mM，镍盐的浓度为25mM，硫酸钠的浓度为50mM，尿素的浓度为50mM，并转入反应釜中，向反应体系中投入经超声处理过的干净裸钛片，封装釜，并置于120℃下反应12小时。反应结束后取出钛片，依次用乙醇和去离子水冲洗干净，于80℃烘干，得到原位生长的Ni-FeOOH纳米线阵列。所得到的样品如图1(b)所示，扫描电镜显示Ni-FeOOH均匀生长在钛片基底上，并为纳米线阵列结构，单根纳米线的直径范围约为40～60nm。Ferric chloride hexahydrate, nickel dichloride hexahydrate, sodium sulfate and urea were dissolved in deionized water to obtain a reaction solution, the concentration of iron salt in the reaction solution was 25mM, the concentration of nickel salt was 25mM, and the concentration of sodium sulfate was 50mM , the concentration of urea was 50mM, and it was transferred into a reaction kettle, and a clean bare titanium sheet that had been ultrasonically treated was put into the reaction system, sealed in the kettle, and placed at 120° C. for 12 hours to react. After the reaction, the titanium sheet was taken out, rinsed with ethanol and deionized water in sequence, and dried at 80°C to obtain an in-situ grown Ni-FeOOH nanowire array. The obtained sample is shown in Figure 1(b). Scanning electron microscopy shows that Ni-FeOOH grows uniformly on the titanium sheet substrate, and has a nanowire array structure. The diameter of a single nanowire ranges from about 40 to 60nm.
实施例3Example 3
钛片基底上FeS2纳米线阵列结构的合成Synthesis of FeS 2 Nanowire Array Structure on Titanium Sheet Substrate
将六水合三氯化铁和硫酸钠溶于去离子水中得到反应溶液，反应溶液中铁盐的浓度为25mM，硫酸钠的浓度为50mM，并转入反应釜中，向反应体系中投入经超声处理过的干净裸钛片，封装釜，并置于120℃下反应12小时。反应结束后取出钛片，依次用乙醇和去离子水冲洗干净，于80℃烘干，得到原位生长的FeOOH纳米线阵列。然后将制得的FeOOH/Ti剪切为2cm2，置于管式炉中，并称取2g硫粉置于管式炉的气源端口，将管式炉用氩气进行反复冲洗从而排净空气，在25sccm流速的氩气气氛保护下，450℃硫化3h，待反应装置自然冷却至室温，取出组装于钛片基底的镍掺杂二硫化铁纳米线阵列，用乙醇和去离子水依次清洗，于80℃烘干，保存。所得到的样品如图2(a)所示，扫描电镜显示FeS2为均匀生长在钛片基底上的纳米线阵列结构，单根纳米线的直径范围约为40～70nm。Dissolve ferric chloride hexahydrate and sodium sulfate in deionized water to obtain a reaction solution, the concentration of iron salt in the reaction solution is 25mM, the concentration of sodium sulfate is 50mM, and transfer to the reaction kettle, put into the reaction system and undergo ultrasonic treatment The cleaned bare titanium sheet was cleaned, sealed in the kettle, and placed at 120°C for 12 hours to react. After the reaction, the titanium sheet was taken out, rinsed with ethanol and deionized water in sequence, and dried at 80° C. to obtain FeOOH nanowire arrays grown in situ. Then cut the obtained FeOOH/Ti into 2cm 2 , put it in a tube furnace, weigh 2g of sulfur powder and place it at the gas source port of the tube furnace, and repeatedly flush the tube furnace with argon to discharge it. Air, under the protection of an argon atmosphere with a flow rate of 25 sccm, vulcanize at 450 ° C for 3 h, wait for the reaction device to cool naturally to room temperature, take out the nickel-doped iron disulfide nanowire array assembled on the titanium substrate, and wash it with ethanol and deionized water in sequence , dried at 80°C and stored. The obtained sample is shown in Figure 2(a). The scanning electron microscope shows that FeS 2 is a nanowire array structure uniformly grown on the titanium sheet substrate, and the diameter of a single nanowire ranges from about 40 to 70nm.
实施例4Example 4
钛片基底上Ni-FeS2纳米线阵列结构的合成Synthesis of Ni-FeS 2 Nanowire Array Structure on Titanium Sheet Substrate
将六水合三氯化铁、六水合二氯化镍、硫酸钠和尿素溶于去离子水中得到反应溶液，反应溶液中铁盐的浓度为25mM，镍盐的浓度为25mM，硫酸钠的浓度为50mM，尿素的浓度为50mM，并转入反应釜中，向反应体系中投入经超声处理过的干净裸钛片，封装釜，并置于120℃下反应12小时。反应结束后取出钛片，依次用乙醇和去离子水冲洗干净，于80℃烘干，得到原位生长的Ni-FeOOH纳米线阵列。然后将制得的Ni-FeOOH/Ti剪切为2cm2，置于管式炉中，并称取2g硫粉置于管式炉的气源端口，将管式炉用氩气进行反复冲洗从而排净空气，在25sccm流速的氩气气氛保护下，450℃硫化3h，待反应装置自然冷却至室温，取出组装于钛片基底的镍掺杂二硫化铁纳米线阵列，用乙醇和去离子水依次清洗，于80℃烘干，保存。所得到的样品如图2(b)所示，扫描电镜显示Ni-FeS2为均匀生长在钛片基底上的纳米线阵列结构，纳米线的平均长度为250nm，平均直径为50nm。Ferric chloride hexahydrate, nickel dichloride hexahydrate, sodium sulfate and urea were dissolved in deionized water to obtain a reaction solution, the concentration of iron salt in the reaction solution was 25mM, the concentration of nickel salt was 25mM, and the concentration of sodium sulfate was 50mM , the concentration of urea was 50mM, and it was transferred into a reaction kettle, and a clean bare titanium sheet that had been ultrasonically treated was put into the reaction system, sealed in the kettle, and placed at 120° C. for 12 hours to react. After the reaction, the titanium sheet was taken out, rinsed with ethanol and deionized water in sequence, and dried at 80°C to obtain an in-situ grown Ni-FeOOH nanowire array. Then the prepared Ni-FeOOH/Ti was cut into 2cm 2 , placed in a tube furnace, and 2g of sulfur powder was weighed and placed at the gas source port of the tube furnace, and the tube furnace was repeatedly flushed with argon to thereby Exhaust the air, under the protection of an argon atmosphere with a flow rate of 25sccm, vulcanize at 450°C for 3h, wait for the reaction device to cool naturally to room temperature, take out the nickel-doped iron disulfide nanowire array assembled on the titanium sheet substrate, wash with ethanol and deionized water Wash sequentially, dry at 80°C, and store. The obtained sample is shown in Figure 2(b). The scanning electron microscope shows that Ni-FeS 2 is a nanowire array structure uniformly grown on the titanium sheet substrate. The average length of the nanowires is 250nm and the average diameter is 50nm.
实施例5Example 5
钛片基底上Ni-FeS2纳米线阵列结构的合成Synthesis of Ni-FeS 2 Nanowire Array Structure on Titanium Sheet Substrate
将六水合三氯化铁、六水合二氯化镍、硫酸钠和尿素溶于去离子水中得到反应溶液，反应溶液中铁盐的浓度为25mM，镍盐的浓度为25mM，硫酸钠的浓度为50mM，尿素的浓度为50mM，并转入反应釜中，向反应体系中投入经超声处理过的干净裸钛片，封装釜，并置于110℃下反应6小时。反应结束后取出钛片，依次用乙醇和去离子水冲洗干净，于80℃烘干，得到原位生长的Ni-FeOOH纳米线阵列。然后将制得的Ni-FeOOH/Ti剪切为1cm2，置于管式炉中，并称取1g硫粉置于管式炉的气源端口，将管式炉用氩气进行反复冲洗从而排净空气，在25sccm流速的氩气气氛保护下，350℃硫化1h，待反应装置自然冷却至室温，取出组装于钛片基底的镍掺杂二硫化铁纳米线阵列，用乙醇和去离子水依次清洗，于80℃烘干，保存。纳米线的平均长度为200nm，平均直径为30nm。Ferric chloride hexahydrate, nickel dichloride hexahydrate, sodium sulfate and urea were dissolved in deionized water to obtain a reaction solution, the concentration of iron salt in the reaction solution was 25mM, the concentration of nickel salt was 25mM, and the concentration of sodium sulfate was 50mM , the concentration of urea was 50mM, and transferred to the reaction kettle, put into the reaction system a clean bare titanium sheet that had been ultrasonically treated, sealed the kettle, and placed it at 110°C for 6 hours. After the reaction, the titanium sheet was taken out, rinsed with ethanol and deionized water in sequence, and dried at 80°C to obtain an in-situ grown Ni-FeOOH nanowire array. Then the prepared Ni-FeOOH/Ti was cut into 1cm 2 , placed in a tube furnace, and 1g of sulfur powder was weighed and placed at the gas source port of the tube furnace, and the tube furnace was repeatedly flushed with argon to thereby Exhaust the air, under the protection of an argon atmosphere with a flow rate of 25sccm, vulcanize at 350°C for 1h, wait for the reaction device to cool naturally to room temperature, take out the nickel-doped iron disulfide nanowire array assembled on the titanium sheet substrate, wash with ethanol and deionized water Wash sequentially, dry at 80°C, and store. The nanowires have an average length of 200 nm and an average diameter of 30 nm.
实施例6Example 6
钛片基底上镍掺杂二硫化铁纳米线阵列结构的电解水产氢实验。Electrolyzed water hydrogen production experiments with nickel-doped iron disulfide nanowire array structure on titanium sheet substrate.
实验仪器：CHI 660E电化学工作站。Experimental equipment: CHI 660E electrochemical workstation.
三电极体系：饱和甘汞电极(参比电极)、石墨棒电极(对电极)、Ni-FeS2/Ti(工作电极)、FeS2/Ti(工作电极)、裸钛片(工作电极)。Three-electrode system: saturated calomel electrode (reference electrode), graphite rod electrode (counter electrode), Ni-FeS 2 /Ti (working electrode), FeS 2 /Ti (working electrode), bare titanium sheet (working electrode).
产氢电解液：配制0.5M H2SO4溶液，并用酸度计测试其pH值。Electrolyte for hydrogen production: Prepare a 0.5M H 2 SO 4 solution and test its pH value with a pH meter.
产氢测试方法：线性伏安法、循环伏安法、电化学阻抗法。Hydrogen production test methods: linear voltammetry, cyclic voltammetry, electrochemical impedance method.
工作电极的构建：Construction of the working electrode:
(1)镍掺杂二硫化铁纳米线阵列(Ni-FeS2纳米线阵列)：(1) Nickel-doped iron disulfide nanowire array (Ni-FeS 2 nanowire array):
用剪刀剪取一定面积的负载着催化剂材料的钛片基底，并刮掉多余部位的材料，将钛片基底直接作为工作电极，通过铂片电极夹与电化学工作站相连接；Use scissors to cut a certain area of the titanium sheet substrate loaded with catalyst materials, and scrape off the excess material, use the titanium sheet substrate directly as the working electrode, and connect it to the electrochemical workstation through the platinum sheet electrode clip;
(2)二硫化铁纳米线阵列(Ni-FeS2纳米线阵列)：(2) Iron disulfide nanowire array (Ni-FeS 2 nanowire array):
用剪刀剪取一定面积的负载着催化剂材料的钛片基底，并刮掉多余部位的材料，将钛片基底直接作为工作电极，通过铂片电极夹与电化学工作站相连接；Use scissors to cut a certain area of the titanium sheet substrate loaded with catalyst materials, and scrape off the excess material, use the titanium sheet substrate directly as the working electrode, and connect it to the electrochemical workstation through the platinum sheet electrode clip;
(3)对比工作电极：(3) Contrast working electrode:
将一定面积的裸钛片作为工作电极用于对比，并用绝缘胶带粘住裸钛片的多余部位，以确保电极的产氢面积为固定值。A certain area of bare titanium sheet was used as the working electrode for comparison, and the excess part of the bare titanium sheet was stuck with insulating tape to ensure that the hydrogen production area of the electrode was a fixed value.
实验步骤：Experimental steps:
(1)取适量0.5M H2SO4溶液于电解槽中，通氮气约20min，然后搭建三电极装置，分别测试Ni-FeS2/Ti、FeS2/Ti、裸钛片的线性伏安曲线(扫速2mV/s)；(1) Take an appropriate amount of 0.5M H 2 SO 4 solution in the electrolytic cell, pass nitrogen gas for about 20 minutes, then build a three-electrode device, and test the linear voltammetry curves of Ni-FeS 2 /Ti, FeS 2 /Ti, and bare titanium sheet respectively ( Sweep speed 2mV/s);
(2)取适量0.5M H2SO4溶液于电解槽中，通氮气约20min，然后搭建三电极装置，分别测试Ni-FeS2/Ti、FeS2/Ti的首次线性伏安曲线(扫速2mV/s)，及在经2000次快速循环伏安(扫速100mV/s)之后的线性伏安曲线(扫速2mV/s)；(2) Take an appropriate amount of 0.5M H 2 SO 4 solution in the electrolytic cell, pass nitrogen gas for about 20 minutes, then build a three-electrode device, and test the first linear voltammetry curves of Ni-FeS 2 /Ti and FeS 2 /Ti respectively (sweep rate 2mV /s), and the linear voltammetry curve (sweep rate 2mV/s) after 2000 fast cyclic voltammetry (sweep rate 100mV/s);
(3)取适量0.5M H2SO4溶液于电解槽中，通氮气约20min，然后搭建三电极装置，分别测试Ni-FeS2/Ti、FeS2/Ti的电化学阻抗谱图，测试电压为-440mV，频率范围为0.1Hz～105Hz，电压振幅为5mV。(3) Take an appropriate amount of 0.5M H 2 SO 4 solution in the electrolytic cell, pass nitrogen gas for about 20 minutes, then build a three-electrode device, and test the electrochemical impedance spectra of Ni-FeS 2 /Ti and FeS 2 /Ti respectively. The test voltage is -440mV, the frequency range is 0.1Hz～10 5 Hz, and the voltage amplitude is 5mV.
每次测试之前，电解液均要通氮气20min使饱和，除掉溶解的多余氧气。线性伏安曲线均经手动欧姆补偿处理。测试电势通过如下公式校正为可逆氢电极：E(RHE)＝E(SCE)+0.242+0.059pH。Before each test, the electrolyte was saturated with nitrogen gas for 20 minutes to remove excess dissolved oxygen. All linear voltammetry curves are manually ohmic compensated. The test potential was corrected for a reversible hydrogen electrode by the following formula: E(RHE)=E(SCE)+0.242+0.059pH.
结果分析：Result analysis:
(1)图4为经测试得到的Ni-FeS2/Ti、FeS2/Ti及及裸钛片的线性伏安曲线，经对比可发现，经镍掺杂得到的Ni-FeS2/Ti表现出了优于纯相FeS2/Ti的产氢活性，具有较低的产氢过电势及相同电压下的较高电流密度；(1) Figure 4 shows the linear voltammetry curves of Ni-FeS 2 /Ti, FeS 2 /Ti and bare titanium sheets obtained through testing. After comparison, it can be found that the performance of Ni-FeS 2 /Ti obtained by nickel doping It has better hydrogen production activity than pure phase FeS 2 /Ti, has lower hydrogen production overpotential and higher current density at the same voltage;
(2)图5为Ni-FeS2/Ti、FeS2/Ti两者的循环稳定性，图5a表明了Ni-FeS2/Ti在经过2000次快速循环测试之后仍具有和首次产氢线性伏安曲线相比较高的重复性，展现出较好的催化稳定性，而图5b则显示出FeS2/Ti具有较差的催化稳定性，2000次循环之后的产氢曲线相对于首次产氢曲线而活性明显衰减，产氢过电势明显升高，因此图5可表明镍的掺杂不仅有助于提升FeS2的产氢催化活性，降低产氢过电势，同时明显提升其产氢催化稳定性。(2) Figure 5 shows the cycle stability of both Ni-FeS 2 /Ti and FeS 2 /Ti. Figure 5a shows that Ni-FeS 2 /Ti still has the same linear volt rate as the first hydrogen production after 2000 rapid cycle tests. The Ann curve has a higher repeatability, showing better catalytic stability, while Figure 5b shows that FeS 2 /Ti has poor catalytic stability, and the hydrogen production curve after 2000 cycles is compared with the first hydrogen production curve However, the activity is obviously attenuated, and the hydrogen production overpotential is obviously increased. Therefore, Figure 5 shows that the doping of nickel not only helps to improve the hydrogen production catalytic activity of FeS2 , but also reduces the hydrogen production overpotential, and at the same time significantly improves its hydrogen production catalytic stability. .
(3)图6为Ni-FeS2/Ti、FeS2/Ti两者的的电化学阻抗谱图，能够发现在相同电压下，Ni-FeS2/Ti具有更加良好的导电性。(3) Fig. 6 is the electrochemical impedance spectrum of Ni-FeS 2 /Ti and FeS 2 /Ti. It can be found that under the same voltage, Ni-FeS 2 /Ti has better conductivity.
上述性能测试的结果进一步证明，镍的掺杂明显提升了二硫化铁材料的产氢催化性能，包括产氢活性的优化、导电性的增加及催化稳定性的增强。The results of the above performance tests further prove that the doping of nickel significantly improves the hydrogen production catalytic performance of iron disulfide materials, including the optimization of hydrogen production activity, the increase of electrical conductivity and the enhancement of catalytic stability.
实施例7Example 7
钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成方法，包括以下步骤：A method for synthesizing a nickel-doped iron disulfide nanowire array structure on a titanium sheet substrate, comprising the following steps:
(1)钛片基底上原位生长的镍掺杂氢氧化氧铁纳米线阵列的合成：将六水合三氯化铁、六水合二氯化镍、硫酸钠和尿素溶于去离子水中得到反应溶液，反应溶液中铁盐的浓度为30mM，镍盐的浓度为30mM，硫酸钠的浓度为60mM，尿素的浓度为50mM，并转入反应釜中，投入经超声处理过的干净裸钛片后,封装釜,置于130℃反应6h，反应结束后取出钛片，依次用乙醇和去离子水冲洗干净，于80℃烘干，得到原位生长的镍掺杂氢氧化氧铁纳米线阵列(Ni-FeOOH/Ti)；(1) Synthesis of nickel-doped ferric oxyhydroxide nanowire arrays grown in situ on a titanium substrate: ferric chloride hexahydrate, nickel dichloride hexahydrate, sodium sulfate and urea were dissolved in deionized water to obtain a reaction solution, the concentration of iron salt in the reaction solution is 30mM, the concentration of nickel salt is 30mM, the concentration of sodium sulfate is 60mM, and the concentration of urea is 50mM, and transfer it to the reaction kettle, drop into the clean bare titanium sheet after ultrasonic treatment, Seal the kettle and place it at 130°C for 6 hours. After the reaction, take out the titanium sheet, rinse it with ethanol and deionized water in turn, and dry it at 80°C to obtain an in-situ grown nickel-doped iron oxyhydroxide nanowire array (Ni -FeOOH/Ti);
(2)钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成：取步骤(1)制得的镍掺杂氢氧化氧铁纳米线阵列置于管式炉中，并称取足量的硫粉置于管式炉的气源端口，加入的硫粉与镍掺杂氢氧化氧铁纳米线阵列的比例关系为2g/1cm2，将管式炉用氩气进行反复冲洗从而排净空气，在流速为25sccm的氩气气氛保护下，进行高温气相硫化，反应温度为450℃，反应时间为1h，反应结束后待反应装置自然冷却至室温，取出组装于钛片基底的镍掺杂二硫化铁纳米线阵列，用乙醇和去离子水依次清洗，于80℃烘干，即制备得到镍掺杂二硫化铁纳米线阵列结构，纳米线的平均长度为200nm，平均直径为50nm。(2) Synthesis of nickel-doped iron disulfide nanowire array structure on titanium substrate: take the nickel-doped iron oxyhydroxide nanowire array prepared in step (1) and place it in a tube furnace, and weigh a sufficient amount The sulfur powder is placed at the gas source port of the tube furnace, and the ratio of the added sulfur powder to the nickel-doped iron oxyhydroxide nanowire array is 2g/1cm 2 , and the tube furnace is repeatedly flushed with argon to discharge Air, under the protection of an argon gas atmosphere with a flow rate of 25 sccm, high-temperature gas-phase vulcanization is carried out, the reaction temperature is 450 ° C, and the reaction time is 1 h. The iron disulfide nanowire array is washed sequentially with ethanol and deionized water, and dried at 80°C to prepare a nickel-doped iron disulfide nanowire array structure. The average length of the nanowires is 200nm and the average diameter is 50nm.
实施例8Example 8
钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成方法，包括以下步骤：A method for synthesizing a nickel-doped iron disulfide nanowire array structure on a titanium sheet substrate, comprising the following steps:
(1)钛片基底上原位生长的镍掺杂氢氧化氧铁纳米线阵列的合成：将六水合三氯化铁、六水合二氯化镍、硫酸钠和尿素溶于去离子水中得到反应溶液，反应溶液中铁盐的浓度为20mM，镍盐的浓度为0.1mM，硫酸钠的浓度为40mM，尿素的浓度为0.1mM，并转入反应釜中，投入经超声处理过的干净裸钛片后,封装釜,置于110℃反应12h，反应结束后取出钛片，依次用乙醇和去离子水冲洗干净，于80℃烘干，得到原位生长的镍掺杂氢氧化氧铁纳米线阵列(Ni-FeOOH/Ti)；(1) Synthesis of nickel-doped ferric oxyhydroxide nanowire arrays grown in situ on a titanium substrate: ferric chloride hexahydrate, nickel dichloride hexahydrate, sodium sulfate and urea were dissolved in deionized water to obtain a reaction Solution, the concentration of iron salt in the reaction solution is 20mM, the concentration of nickel salt is 0.1mM, the concentration of sodium sulfate is 40mM, and the concentration of urea is 0.1mM, and it is transferred to the reaction kettle, and the clean bare titanium sheet that has been put into the ultrasonic treatment Finally, seal the kettle and place it at 110 ° C for 12 hours. After the reaction, take out the titanium sheet, rinse it with ethanol and deionized water in turn, and dry it at 80 ° C to obtain the nickel-doped iron oxyhydroxide nanowire array grown in situ. (Ni-FeOOH/Ti);
(2)钛片基底上镍掺杂二硫化铁纳米线阵列结构的合成：取步骤(1)制得的镍掺杂氢氧化氧铁纳米线阵列置于管式炉中，并称取足量的硫粉置于管式炉的气源端口，加入的硫粉与镍掺杂氢氧化氧铁纳米线阵列的比例关系为1g/2cm2，将管式炉用氩气进行反复冲洗从而排净空气，在流速为25sccm的氩气气氛保护下，进行高温气相硫化，反应温度为350℃，反应时间为3h，反应结束后待反应装置自然冷却至室温，取出组装于钛片基底的镍掺杂二硫化铁纳米线阵列，用乙醇和去离子水依次清洗，于80℃烘干，即制备得到镍掺杂二硫化铁纳米线阵列结构，纳米线的平均长度为250nm，平均直径为30nm。(2) Synthesis of nickel-doped iron disulfide nanowire array structure on titanium substrate: take the nickel-doped iron oxyhydroxide nanowire array prepared in step (1) and place it in a tube furnace, and weigh a sufficient amount Place the sulfur powder at the gas source port of the tube furnace, and the ratio of the added sulfur powder to the nickel-doped ferric oxyhydroxide nanowire array is 1g/2cm 2 , and the tube furnace is repeatedly flushed with argon to drain Air, under the protection of an argon atmosphere with a flow rate of 25 sccm, high-temperature gas-phase vulcanization is carried out, the reaction temperature is 350 ° C, and the reaction time is 3 hours. The iron disulfide nanowire array is washed sequentially with ethanol and deionized water, and dried at 80°C to prepare a nickel-doped iron disulfide nanowire array structure. The average length of the nanowires is 250nm and the average diameter is 30nm.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art may make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention.
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