CN114807961B - 一种微量铜掺杂的氧化石墨烯复合NiMo基催化剂及制备方法 - Google Patents
一种微量铜掺杂的氧化石墨烯复合NiMo基催化剂及制备方法 Download PDFInfo
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- 229910003294 NiMo Inorganic materials 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 title claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006260 foam Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006262 metallic foam Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000005234 chemical deposition Methods 0.000 abstract description 2
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Abstract
本发明提出了一种微量铜掺杂的氧化石墨烯复合NiMo基催化剂及制备方法,属于电催化水分解领域。首先通过化学沉积法,将氧化石墨烯(GO)包覆于镍钼泡沫片(NMF)上得到GO/NMF,从而在材料表面构筑晶格缺陷,为后续Cu的吸附提供位点。随后用微量Cu元素修饰GO/NMF,制得Cu@GO/NMF。氧化石墨烯包覆与微量Cu元素修饰能够实现对NiMo金属泡沫的表面化学改性,所得Cu@GO/NMF具有良好的HER活性。
Description
技术领域
本发明涉及催化剂材料制备技术领域,具体为一种可应用于电解水制氢的氧化石墨烯复合NiMo基催化剂的制备方法。
背景技术
风电、光伏发电等新能源易受气候因素的影响,能量供应不稳定;偶联新能源发电与电解水制氢技术能够将不稳定的电能转化为稳定易储存的化学能,有效解决其间歇性问题。电解水反应包括发生在阴极的析氢反应(HER)与阳极的析氧反应(OER),其能量转化效率主要取决于电极材料的催化性能。对于阴极的析氢反应而言,以铂为代表的贵金属是性能最好的催化剂,但高昂的成本阻碍了其大规模应用,开发储量丰富、价格低廉非贵金属催化剂具有重要研究意义。在这样的背景下,NiMo合金材料因具有良好的HER活性而被广泛关注。大量研究表明Ni、Mo元素之间的电子协同效应能有效提升其HER活性,同时Mo元素带来的形貌调控作用也使NiMo材料较单金属Ni材料具备更丰富的电化学比表面积。
发明内容
NiMo基合金已作为一种优异的HER催化剂被大量报道,本发明致力于进一步提升现有NiMo基材料的HER性能,制备了一种微量铜掺杂的氧化石墨烯复合NiMo基催化剂。本发明采用化学沉积的方法,首先将氧化石墨烯(GO)包覆于镍钼泡沫片(NMF)上得到GO/NMF,从而在材料表面构筑晶格缺陷,为后续Cu的吸附提供位点。随后用微量Cu元素修饰GO/NMF,制得Cu@GO/NMF。氧化石墨烯包覆与微量Cu元素修饰能够实现对NiMo金属泡沫的表面化学改性,所得Cu@GO/NMF具有良好的HER活性。本发明的技术方案如下:
(1)GO/NMF的制备:
剪取1×1cm2的NiMo金属泡沫置于50mL的小烧杯中,依次加入10mL乙醇溶液和10mg的氧化石墨烯,超声20min后静止30min,取出制备好的GO/NMF,清水漂洗3次备用;
(2)Cu@GO/NMF的制备:
依次称取0.123g五水硫酸铜、2.941g柠檬酸钠和2.641g L-抗坏血酸于50mL的小烧杯中,加入50mL纯水溶解,将(1)中的GO/NMF放入溶液中,静置沉积1h得到Cu@GO/NMF。
附图说明
图1为相关的XRD图谱;
图2为GO/NMF沉积1h所得Cu@GO/NMF的极化曲线图;
图3为相关的红外拉曼图谱;
图4为NiMo泡沫的XPS图谱;
图5为Cu@GO/NMF的XPS图谱;
图6为不同倍数下NiMo泡沫的SEM图谱;
图7为不同倍数下Cu@GO/NMF的SEM图谱。
具体实施方式
本发明提供了一种微量铜掺杂的氧化石墨烯复合NiMo基催化剂及制备方法,具体实施方式如下。
剪取1×1cm2的NiMo金属泡沫置于50mL的小烧杯中,依次加入10mL乙醇溶液和10mg的氧化石墨烯,超声20min后静止30min,取出制备好的GO/NMF,清水漂洗3次备用;
依次称取0.123g五水硫酸铜、2.941g柠檬酸钠和2.641g L-抗坏血酸于50mL的小烧杯中,然后加入50mL纯水溶解,将(1)中的GO/NMF放入溶液中,静置沉积1h得到Cu@GO/NMF。
Claims (2)
1.一种微量铜掺杂的氧化石墨烯复合NiMo基催化剂的制备方法,其特征在于,包括以下步骤:
(1)GO/NMF的制备:
剪取1×1cm2的镍钼泡沫片置于50mL的小烧杯中,依次加入10mL乙醇溶液和10mg的氧化石墨烯,超声20min后静止30min,取出制备好的GO/NMF,清水漂洗3次;
(2)Cu@GO/NMF的制备
依次称取0.123g五水硫酸铜、2.941g柠檬酸钠和2.641gL-抗坏血酸于50mL的小烧杯中,然后加入50mL纯水溶解,将(1)中的GO/NMF放入溶液中,静置沉积1h得到Cu@GO/NMF。
2.按照权利要求1所述的方法制备得到的微量铜掺杂的氧化石墨烯复合NiMo基催化剂。
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