CN114377682B - 一种自支撑电催化材料及其制备方法 - Google Patents
一种自支撑电催化材料及其制备方法 Download PDFInfo
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- CN114377682B CN114377682B CN202111160250.8A CN202111160250A CN114377682B CN 114377682 B CN114377682 B CN 114377682B CN 202111160250 A CN202111160250 A CN 202111160250A CN 114377682 B CN114377682 B CN 114377682B
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 226
- 229910052802 copper Inorganic materials 0.000 claims abstract description 98
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000006260 foam Substances 0.000 claims abstract description 71
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- 229910002640 NiOOH Inorganic materials 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 239000010937 tungsten Substances 0.000 claims description 13
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 7
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 6
- XKGMHABTFTUWDV-UHFFFAOYSA-N [W+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [W+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] XKGMHABTFTUWDV-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- VNYOIRCILMCTHO-UHFFFAOYSA-L nickel(2+);oxalate;dihydrate Chemical compound O.O.[Ni+2].[O-]C(=O)C([O-])=O VNYOIRCILMCTHO-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 150000004687 hexahydrates Chemical class 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 41
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- -1 polytetrafluoroethylene Polymers 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001027 hydrothermal synthesis Methods 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
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- 239000003054 catalyst Substances 0.000 description 8
- 238000000643 oven drying Methods 0.000 description 8
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 7
- 239000002070 nanowire Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
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- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 238000004729 solvothermal method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 239000007777 multifunctional material Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- 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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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明涉及一种自支撑电催化材料及其制备方法,所述自支撑电催化材料为Cu2O/WO3/CF自支撑电催化材料,该Cu2O/WO3/CF自支撑电催化材料包括:泡沫铜基材,以及原位生长在泡沫铜基材中的Cu2O和WO3。
Description
技术领域
本发明涉及一种自支撑电催化材料,具体涉及Cu2O/WO3/CF自支撑电催化材料和NiOOH/Cu2O/WO3/CF自支撑电催化材料及其制备方法,属于复合材料技术领域。
背景技术
将水电化学分解成氢和氧是一种从根本上实现可再生能源转换和存储的战略,解决全球能源和环境问题的有效方法。在此过程中,转换效率受到高的过电位的限制。目前,贵金属Pt基材料被认为是最有效的HER电催化剂,Ir/Ru及其氧化物被认为在酸性和碱性电解液中均表现出优异的OER电催化剂。然而,由于这些贵金属材料在地壳中含量较少,而且成本较高,其商业化大规模应用受到了限制。开发新型具有低成本和高效益的可持续非贵金属电催化材料是关键。
WO3属于n型半导体,其由正八面体的钙钛矿单元组成,具有独特的光学、电子以及化学性质,近年来被广泛应用于传感器、催化、电致变色等领域。WO3材料具有快速的电子转移速度(12cm2V-1s-1)、合适的空穴扩散长度(150nm)和较宽的光吸收范围(12%),因此,WO3是一种具有发展前景的光电催化材料。然而,目前研究制备得到的WO3纳米材料存在比表面积小、催化活性位点少、产氢和产氧过电势较高且不稳定等缺点,使得其催化活性受到限制。金属氧化物中的氧缺陷作为活性位点可以改善电导率并有利于水分子或中间反应物质的吸附和解吸(例如,HER中的·H;OER中得·OH和·OOH),由此进一步说明在WO3材料中引入氧缺陷有望提升WO3材料的电催化性能。同时,通过复合等工艺,调整WO3电子结构,可以有效提升氧缺陷含量,从而增加电催化活性位点,优化电催化性能。
目前,铜基材料用于析氧催化剂被广泛关注,铜基材料具有储量丰富、成本低、其化合物合成简单等优点。Cu基金属氧化物是很好的电极材料。然而,尽管氧化亚铜(Cu2O)材料被用于光催化材料,但其用于电催化的研究相对较少。因此,有必要进一步研究和探索Cu2O电催化材料。另外,为了避免在制备工作电极期间粘合剂对催化剂的导电性和活性面积的影响,在导电基底上直接合成WO3纳米结构催化剂可以有效地提高电催化性能。具有高丰度和较低价格的泡沫铜引起了广泛关注,其因较大的比表面积,较高的电子传导性和理想的3D开孔结构而被广泛用作电极材料的支撑体系。
泡沫铜是一种在铜基体中均匀分布着大量连通或不连通孔洞的新型多功能材料。泡沫铜的导电性和延展性好,且制备成本比泡沫镍低,导电性能比泡沫镍更好,是一种制备电池负极材料、催化剂和电磁屏蔽材料的潜在多维载体。与金属材料相比,利用高导电性的碳材料(如碳纤维、碳布、碳纸等)作为载体具有很多优点,例如它们重量轻、化学性能稳定、环境友好等等。然而,正由于其良好的化学惰性,碳材料与各种无机材料之间的兼容性较差,因此很难直接有效地在其表面生长活性物质。因此,发展一种有效的方法直接在泡沫铜导电基底上生长具有高活性的复合材料,并将其直接用于电催化产氢具有重大意义。
发明内容
针对上述问题,本发明提供了一种全新的自支撑电催化材料及其制备方法。本发明的目的是采用多步法合成高效HER电催化材料,且所制备合成的自支撑电催化材料结构可控,产物同时存在纳米线(WO3)正四面体(Cu2O)和超小纳米颗粒(NiOOH)结构,且纳米线、正四面体和超小纳米颗粒结构均匀分布。所制备材料在中性溶液中表现出较好的电催化性能。
第一方面,本发明提供了一种所述Cu2O/WO3/CF自支撑电催化材料包括:泡沫铜基材,以及原位生长在泡沫铜基材中的Cu2O和WO3。
本发明中,首次以泡沫铜为铜源,通过一步法原位在泡沫铜基材表面生长出Cu2O四面体结构和WO3纳米线结构,既避免了在制备工作电极期间粘合剂对催化剂的导电性和活性的影响,又可以有效地提高电催化性能。
较佳的,所述Cu2O、WO3的总担载量为0.5~4mg/cm2。
较佳的,所述WO3和Cu2O摩尔比为1:(0.5~1)。
第二方面,本发明提供了一种Cu2O/WO3/CF自支撑电催化材料,所述Cu2O/WO3/CF自支撑电催化材料还包括原位生长在泡沫铜基材中的NiOOH,计为NiOOH/Cu2O/WO3/CF自支撑电催化材料。也就是说,所述NiOOH/Cu2O/WO3/CF自支撑电催化材料包括:泡沫铜基材,以及生长在泡沫铜基材中的NiOOH、Cu2O和WO3。其中,在Cu2O和WO3中都分布NiOOH纳米颗粒。
在本发明中,泡沫铜基材(CF)由于其具有高比表面,高电子传导性和3D开孔结构可以提高产物活性位点的暴露,有利于电催化性能的提高。因此,本发明首次以泡沫铜为铜源原位生长出Cu2O四面体结构,同时再将NiOOH和WO3直接生长在泡沫铜基材(CF)上,利用协同作用,既避免了在制备工作电极期间粘合剂对催化剂的导电性和活性的影响,又可以有效地提高电催化性能。
较佳的,所述Cu2O、WO3和NiOOH的总担载量为0.5~4mg/cm2。
较佳的,所述WO3、Cu2O和NiOOH摩尔比为1:(0.5~1):(0.01~0.05)。
第三方面,本发明还提供了一种上述的Cu2O/WO3/CF自支撑电催化材料的制备方法,包括:
(1)将钨源溶于无水乙醇中,得到溶液B;
(2)将泡沫铜浸渍于含有溶液B的高压反应釜中,然后在100~200℃下反应1~36h,再经离心、洗涤和干燥,得到所述Cu2O/WO3/CF自支撑电催化材料。
较佳的,所述钨源选自钨酸铵(NH4)6W7O24·6H2O、仲钨酸铵(NH4)10[H2W12O42]、偏钨酸铵(NH4)6H2W12O40和异丙醇钨W(OCH(CH3)2)6、六氯化钨WCl6中的至少一种;所述溶液B中钨源的浓度为0.01~5mol/L。
较佳的,所述含有溶液B的高压反应釜的体积填充比为20~60%。
第四方面,本发明还提供了一种上述的NiOOH/Cu2O/WO3/CF自支撑电催化材料的制备方法,包括:
(1)将钨源溶于无水乙醇中,得到溶液B;
(2)将生长有NiOOH和Cu2O的泡沫铜浸渍于含有溶液B的高压反应釜中,然后在100~200℃下反应1~36h,再经离心、洗涤和干燥,得到生长有NiOOH/Cu2O/WO3的泡沫铜,即NiOOH/Cu2O/WO3/CF自支撑电催化材料。在此过程中,产物晶体结构发生过重结晶,基于溶剂热过程加热,动力学增加NiOOH重新分布,使得其在Cu2O和WO3中同时分布。
较佳的,所述溶液B中钨源的浓度为0.01~5mol/L。
较佳的,所述钨源选自钨酸铵(NH4)6W7O24·6H2O、仲钨酸铵(NH4)10[H2W12O42]、偏钨酸铵(NH4)6H2W12O40和异丙醇钨W(OCH(CH3)2)6、六氯化钨WCl6中的至少一种。
较佳的,所述含有溶液B的高压反应釜的体积填充比为20~60%。
较佳的,所述生长有NiOOH和Cu2O的泡沫铜的制备方法包括:
(1)将镍源溶于水中,得到溶液A;
(2)将泡沫铜浸渍于含有溶液A的高压反应釜中,然后在160~200℃下反应6~12h,再经洗涤和干燥,得到生长有NiOOH和Cu2O的泡沫铜,即NiOOH/Cu2O/CF。
又,较佳的,所述镍源选自乙酸镍Ni(CH3COO)2、二水合草酸镍NiC2O4·2H2O、六水合氯化镍NiCl2·6H2O和六水合硝酸镍NiN2O6·6H2O中的至少一种所述镍源的浓度为0.01~5mol/L。
较佳的,所述含有溶液A的高压反应釜的体积填充比为20~80%。
有益效果:
(1)本发明通过两步法合成NiOOH/Cu2O/WO3复合材料,Cu2O为以泡沫铜为原料原位合成,且此复合材料直接生长在泡沫铜基体上;同时,本发明通过一步法直接在泡沫铜上原位生长Cu2O和WO3;
(2)本发明的反应条件温和,易于实现,过程易控;
(3)本发明制备的复合材料存在大量氧缺陷;
(4)本发明制得的NiOOH/Cu2O/WO3自支撑电催化材料,在中性电解液中表现出较好的电催化性能。
附图说明
图1为实施例1、对比例1和实施例5条件下所制备的NiOOH/Cu2O/WO3/CF、Cu2O/WO3/CF和NiOOH/Cu2O/CF的XRD图谱,其中横坐标为2θ,纵坐标为强度(Intensity);
图2为对比例1和实施例5条件下所制备的(a-b)NiOOH/Cu2O/CF和(c-d)Cu2O/WO3/CF的SEM照片;
图3为实施例1条件下所制备的NiOOH/Cu2O/WO3/CF的SEM照片;
图4为实施例1条件下所制备的NiOOH/Cu2O/WO3/CF的TEM和HRTEM照片;
图5为实施例1条件下所制备的NiOOH/Cu2O/WO3/CF的对应元素分布图;
图6为实施例1、对比例1和实施例5条件下所制备的NiOOH/Cu2O/WO3/CF、Cu2O/WO3/CF和NiOOH/Cu2O/CF的O1s图谱,其中横坐标为结合能(Binding Energy),纵坐标为强度(Intensity);
图7为实施例1、对比例1和实施例5条件下所制备的NiOOH/Cu2O/WO3/CF、Cu2O/WO3/CF、NiOOH/Cu2O/CF和CF在不同电流密度下的电催化产氢过电势对比图;
图8为实施例1条件下所制备的NiOOH/CuO2/WO3/CF的拉曼光谱图(其中横坐标为拉曼位移(Raman shift),纵坐标为强度(Intensity)),从图中可知,在474cm-1和554cm-1处的峰与NiOOH的Ni-O键振动有关,结合TEM分析,进一步证实了产物中NiOOH的存在。
具体实施方式
以下通过下述实施方式进一步说明本发明,应理解,下述实施方式仅用于说明本发明,而非限制本发明。
在本公开中,首次NiOOH、Cu2O和WO3复合,通过两步法直接生长在泡沫铜,制备得到富含氧缺陷的NiOOH/Cu2O/WO3/CF自支撑电催化材料。其中,NiOOH/Cu2O/WO3的最佳总担载量为0.5~4mg/cm2。所述WO3、Cu2O和NiOOH摩尔比为1:(0.5~1):(0.01~0.05)。
以下示例性地说明NiOOH/Cu2O/WO3/CF自支撑电催化材料的制备方法。
泡沫铜基材的清洗。取50mL的烧杯,将长为3~7cm,宽为1~2cm的泡沫铜依次完全浸入丙酮、2~6mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理15~30min。
生长有NiOOH/Cu2O的泡沫铜的制备。本发明中所选的镍源种类、浓度和反应温度至关重要,选择不适所制备的目标产物物相无法合成,产物担载量过大或者过小,使得后续复合合成阶段产物不易在泡沫铜上直接生长或造成复合产物从泡沫铜上脱落。
将分析纯乙酸镍Ni(CH3COO)2作为镍源加入到20~80mL的去离子水中,并搅拌20~60min,形成均匀混合的溶液A。其中,镍源还可选自乙酸镍Ni(CH3COO)2、二水合草酸镍NiC2O4·2H2O、六水合氯化镍NiCl2·6H2O和六水合硝酸镍NiN2O6·6H2O等。溶液A中Ni源的浓度可为0.01~5mol/L。
将泡沫铜浸渍于含有溶液A的聚四氟乙烯内衬的高压反应釜中并进行密封,保持体积填充比在20%~80%之间。将密封好的高压反应釜放入均相水热反应仪中,设置温度参数可为160~200℃,反应时间可为6~12h。
反应结束后冷却至室温,再经离心、洗涤和干燥,得到表面生长有NiOOH/Cu2O的泡沫铜。其中,洗涤包括:用去离子水洗涤3~5次。其中,干燥包括:将洗涤后的泡沫铜放入50~70℃真空烘箱中干燥5~8h,或者放入-40~-60℃的冷冻干燥箱中干燥5~8h。
将分析纯钨酸铵(NH4)6W7O24·6H2O作为钨源溶于加入到20~80mL的无水乙醇中,并搅拌20~60min,形成均匀混合的溶液B。其中,钨源还可选自钨酸铵(NH4)6W7O24·6H2O、仲钨酸铵(NH4)10[H2W12O42]xH2O、偏钨酸铵(NH4)6H2W12O40·XH2O和异丙醇钨W(OCH(CH3)2)6、六氯化钨WCl6等中的一种。溶液B中钨源的浓度可为0.01~5mol/L。
将生长有NiOOH/Cu2O的泡沫铜或纯泡沫铜浸渍于含有溶液B的聚四氟乙烯内衬的高压反应釜中并进行密封,保持体积填充比在20%~60%之间。将密封好的高压反应釜放入均相水热反应仪中,设置温度参数可为100~200℃,反应时间可为1~36小时。
反应结束后冷却至室温,再经离心、洗涤和干燥,得到生长有NiOOH/Cu2O/WO3的泡沫铜或生长有Cu2O/WO3的泡沫铜。其中,洗涤包括:用去离子水洗涤3~5次。其中,干燥包括:将洗涤后的泡沫铜放入50~70℃真空烘箱中干燥5~8h,或者放入-40~-60℃的冷冻干燥箱中干燥5~8h。
下面进一步例举实施例以详细说明本发明。同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例,即本领域技术人员可以通过本文的说明做合适的范围内选择,而并非要限定于下文示例的具体数值。
实施例1:
(1)配制浓度为0.05mol/L的乙酸镍Ni(CH3COO)2·4H2O溶液A。具体来说,将Ni(CH3COO)2·4H2O加入到40mL的去离子水中,并搅拌30min,形成均匀混合的溶液A;
(2)将溶液A装入聚四氟乙烯内衬高压反应釜中,保持体积填充比在40%。
(3)取50mL的烧杯,将长为6cm,宽为1cm的泡沫铜依次完全浸入丙酮、3mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理30min。将处理好的泡沫铜放入含有溶液A的聚四氟乙烯反应釜中;将密封好的反应釜放入均相水热反应仪中,设置温度参数为160℃,反应时间为12h;
(4)反应结束后冷却至室温,将反应后的泡沫铜取出分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥6h,得到生长有NiOOH/Cu2O的泡沫铜;
(5)配制浓度为0.05mol/L的六氯化钨WCl6溶液B。具体来说,将WCl6加入到40mL的去离子水中,并搅拌30min,形成均匀混合的溶液B;
(6)将生长NiOOH/Cu2O的泡沫铜浸渍于含有溶液B的聚四氟乙烯内衬的高压反应釜中并进行密封,保持体积填充比在40%。将密封好的高压反应釜放入均相水热反应仪中,设置温度参数为160℃,反应时间为12h;
(7)反应结束后冷却至室温,将反应后的泡沫铜取出分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥6h,得到NiOOH/Cu2O/WO3/CF自支撑电催化材料。其中NiOOH/Cu2O/WO3的总担载量为0.86mg/cm2。所述WO3和Cu2O的摩尔比为1:0.5。所述WO3、Cu2O和NiOOH摩尔比为1:0.5:0.01。
实施例2
(1)配制浓度为1mol/L的乙酸镍Ni(CH3COO)2·4H2O溶液A。具体来说,将Ni(CH3COO)2·4H2O加入到60mL的去离子水中,并搅拌30min,形成均匀混合的溶液A;
(2)将溶液A装入聚四氟乙烯内衬高压反应釜中,保持体积填充比在60%;
(3)取50mL的烧杯,将长为6cm,宽为2cm的泡沫铜依次完全浸入丙酮、4mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理30min。将处理好的泡沫铜放入含有溶液A的聚四氟乙烯反应釜中;将密封好的反应釜放入均相水热反应仪中,设置温度参数为200℃,反应时间为12h;
(4)反应结束后冷却至室温,将反应后的泡沫铜取出分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥6h,得到生长有NiOOH/Cu2O的泡沫铜;
(5)配制浓度为1mol/L的钨酸铵(NH4)6W7O24·6H2O溶液B。具体来说,将(NH4)6W7O24·6H2O加入到40mL的去离子水中,并搅拌30min,形成均匀混合的溶液B;
(6)将生长有NiOOH/Cu2O的泡沫铜浸渍于含有溶液B的聚四氟乙烯内衬的高压反应釜中并进行密封,保持体积填充比在40%。将密封好的高压反应釜放入均相水热反应仪中,设置温度参数为140℃,反应时间为24h;
(7)反应结束后冷却至室温,将反应后的泡沫铜取出分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥6h,得到NiOOH/Cu2O/WO3/CF自支撑电催化材料。所得NiOOH/Cu2O/WO3/CF自支撑电催化材料中NiOOH/Cu2O/WO3的总担载量为1.5mg/cm2。所述WO3、Cu2O和NiOOH摩尔比为1:0.3:0.03。
实施例3:
(1)配制浓度为3mol/L的二水合草酸镍NiC2O4·2H2O溶液A。具体来说,将NiC2O4·2H2O加入到50mL的去离子水中,并搅拌30min,形成均匀混合的溶液A;
(2)将溶液A装入聚四氟乙烯内衬高压反应釜中,保持体积填充比在50%;
(3)取50mL的烧杯,将长为7cm,宽为1cm的泡沫铜依次完全浸入丙酮、3mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理30min。将处理好的泡沫铜放入含有溶液A的聚四氟乙烯反应釜中;将密封好的反应釜放入均相水热反应仪中,设置温度参数为180℃,反应时间为18h;
(4)反应结束后冷却至室温,将反应后的泡沫铜取出分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥6h,得到生长有NiOOH/Cu2O的泡沫铜;
(5)配制浓度为4mol/L的六氯化钨WCl6溶液B。具体来说,将WCl6加入到60mL的去离子水中,并搅拌30min,形成均匀混合的溶液B;
(6)将生长有NiOOH/Cu2O的泡沫铜浸渍于含有溶液B的聚四氟乙烯内衬的高压反应釜中并进行密封,保持体积填充比在60%。将密封好的高压反应釜放入均相水热反应仪中,设置温度参数为140℃,反应时间为30h;
(7)反应结束后冷却至室温,将反应后的泡沫铜取出分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥6h,得到NiOOH/Cu2O/WO3/CF自支撑电催化材料。所述NiOOH/Cu2O/WO3的总担载量为3mg/cm2。所述WO3、Cu2O和NiOOH摩尔比为1:0.6:0.05。
实施例4:
(1)配制浓度为4mol/L的六水合硝酸镍NiN2O6·6H2O溶液A。具体来说,将NiN2O6·6H2O加入到80mL的去离子水中,并搅拌30min,形成均匀混合的溶液A;
(2)将溶液A装入聚四氟乙烯内衬高压反应釜中,保持体积填充比在80%;
(3)取50mL的烧杯,将长为5cm,宽为2cm的泡沫铜依次完全浸入丙酮、6mol/L的HCl溶液、去离子水、无水乙醇中,并分别超声处理30min。将处理好的泡沫铜放入含有溶液A的聚四氟乙烯反应釜中;将密封好的反应釜放入均相水热反应仪中,设置温度参数为160℃,反应时间为6h;
(4)反应结束后冷却至室温,将反应后的泡沫铜取出分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥6h,得到生长有NiOOH/Cu2O的泡沫铜;
(5)配制浓度为2mol/L的异丙醇钨W(OCH(CH3)2)6溶液B。具体来说,将W(OCH(CH3)2)6加入到40mL的去离子水中,并搅拌30min,形成均匀混合的溶液B;
(6)将生长有NiOOH/Cu2O的泡沫铜浸渍于含有溶液B的聚四氟乙烯内衬的高压反应釜中并进行密封,保持体积填充比在40%。将密封好的高压反应釜放入均相水热反应仪中,设置温度参数为160℃,反应时间为24h;
(7)反应结束后冷却至室温,将反应后的泡沫铜取出分别用无水乙醇和去离子水洗涤3次。放入60℃真空烘箱或者冷冻干燥箱中干燥6h,得到NiOOH/Cu2O/WO3/CF自支撑电催化材料。其中,NiOOH/Cu2O/WO3的总担载量为2.8mg/cm2。所述WO3、Cu2O和NiOOH摩尔比为1:0.55:0.03。
实施例5
本实施例5中Cu2O/WO3/CF电催化材料的制备过程参见实施例1,区别在于:只通过一步溶剂热法得到生长有Cu2O/WO3的泡沫铜,即只进行实施例1中的5-7步骤,且在步骤6中加入的是未生长有任何东西的泡沫铜。所得Cu2O/WO3/CF自支撑电催化材料中,Cu2O/WO3的担载量为0.7mg/cm2,WO3和Cu2O的摩尔比为1:0.5。
对比例1
本对比例1中NiOOH/Cu2O/CF自支撑电催化材料的制备过程参见实施例1,区别在于:只通过一步水热法得到生长有NiOOH/Cu2O的泡沫铜,即只进行实施例1中的1-4步骤,未进行5-7的溶剂热反应过程。所得NiOOH/Cu2O/CF自支撑电催化材料中,NiOOH/Cu2O的担载量为0.28mg/cm2。其中NiOOH和Cu2O的摩尔比为0.02:1。
图1为实施例1、对比例1和实施例5条件下所制备的NiOOH/Cu2O/WO3/CF、Cu2O/WO3/CF和NiOOH/Cu2O/CF的XRD图谱,从图中可知本发明所合成的物相中无其他杂相存在;
图2为对比例1和实施例5条件下所制备的NiOOH/Cu2O/CF和Cu2O/WO3/CF的SEM照片,可以看出对比例1中的NiOOH/Cu2O为由许多小纳米颗粒团聚生成的大颗粒分散在粗糙的表面结构中。实施例5中的Cu2O/WO3为由WO3纳米线和Cu2O四面体均匀分散的复合结构。这些四面体大小相同,同时被相互交织的纳米线结构缠绕;
图3-5分别为实施例1条件下所制备的NiOOH/Cu2O/WO3/CF的SEM照片,以及NiOOH/Cu2O/WO3/CF结构中四面体和纳米线结构分别的元素分布。可以看出NiOOH/Cu2O/WO3在泡沫铜中生长的微观结构与Cu2O/WO3相似(图3),四面体主要元素为Cu和O,由此结合XRD进一步证明,四面体结构为Cu2O,纳米线结构为WO3(图5);此外,从图4中进一步看出材料中还均匀分散着NiOOH和Cu2O纳米粒子。这种WO3/Cu2O/NiOOH多级结构所形成的异质结面对于电催化性能的提高至关重要。
图6为实施例1、对比例1和实施例5条件下所制备的NiOOH/Cu2O/WO3/CF、Cu2O/WO3/CF和NiOOH/Cu2O/CF的O1s图谱,可以发现,将NiOOH、氧化亚铜和氧化钨通过两步法原位生长在泡沫铜上,产物中的氧缺陷明显增加,比较Cu2O/WO3/CF和NiOOH/Cu2O/WO3/CF复合材料,也进一步证明了NiOOH对于氧缺陷含量的增加至关重要;
图7为实施例1、对比例1和实施例5条件下所制备的NiOOH/Cu2O/WO3/CF、Cu2O/WO3/CF、NiOOH/Cu2O/CF和CF在不同电流密度下的电催化产氢过电势对比。所得电催化材料分别置于中性电解液(1M KH2PO4+1M K2HPO4)中进行电催化测试。可以看出本专利所制备的氧缺陷丰富的NiOOH/Cu2O/WO3/CF电催化复合材料其过电势不同电流密度下最小,表面其产氢性能最好。其在100、200、300、400和500mA/cm2的大电流密度下,其过电势分别为294、386、464、533和589mV。
Claims (10)
1.一种Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述Cu2O/WO3/CF自支撑电催化材料包括:泡沫铜基材,以及原位生长在泡沫铜基材中的Cu2O和WO3;所述Cu2O/WO3/CF自支撑电催化材料的制备方法包括:
(1)将钨源溶于无水乙醇中,得到溶液B;
(2)将泡沫铜浸渍于含有溶液B的高压反应釜中,然后在100~200 ℃下反应1~36 h,再经离心、洗涤和干燥,得到所述Cu2O/WO3/CF自支撑电催化材料。
2. 根据权利要求1所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述Cu2O和WO3的总担载量为0.5~4 mg/cm2。
3.根据权利要求1所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述WO3和Cu2O的摩尔比为1:(0.5~1)。
4.根据权利要求1所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述Cu2O/WO3/CF自支撑电催化材料还包括原位生长在泡沫铜基材中的NiOOH;所述Cu2O/WO3/CF自支撑电催化材料的制备方法包括:
(1)将钨源溶于无水乙醇中,得到溶液B;
(2)将生长有NiOOH和Cu2O的泡沫铜浸渍于含有溶液B的高压反应釜中,然后在100~200℃下反应1~36 h,再经离心、洗涤和干燥,得到NiOOH/Cu2O/WO3/CF自支撑电催化材料。
5. 根据权利要求4所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述Cu2O/WO3/CF自支撑电催化材料中NiOOH、Cu2O和WO3的总担载量为0.5~4 mg/cm2。
6.根据权利要求4所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述WO3、Cu2O和NiOOH摩尔比为1:(0.5~1):(0.01~0.05)。
7.根据权利要求4所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述生长有NiOOH和Cu2O的泡沫铜的制备方法包括:
(1)将镍源溶于水中,得到溶液A;
(2)将泡沫铜浸渍于含有溶液A的高压反应釜中,然后在160~200 ℃下反应6~12 h,再经洗涤和干燥,得到生长有NiOOH和Cu2O的泡沫铜。
8. 根据权利要求7所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述镍源选自乙酸镍 Ni(CH3COO)2、二水合草酸镍 NiC2O4·2H2O、六水合氯化镍 NiCl2·6H2O和六水合硝酸镍 NiN2O6·6H2O中的至少一种;所述镍源的浓度为0.01~5 mol/L;所述含有溶液A的高压反应釜的体积填充比为20~80%。
9. 根据权利要求1或4所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述钨源选自钨酸铵 (NH4)6W7O24·6H2O、仲钨酸铵 (NH4)10[H2W12O42]、偏钨酸铵 (NH4)6H2W12O40和异丙醇钨 W(OCH(CH3)2)6、六氯化钨WCl6中的至少一种;所述溶液B中钨源的浓度为0.01~5mol/L。
10.根据权利要求1或4所述的Cu2O/WO3/CF自支撑电催化材料,其特征在于,所述含有溶液B的高压反应釜的体积填充比为20~60%。
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