CN113832489A - 泡沫镍负载镍铜锰金属纳米电催化剂及其制备方法 - Google Patents
泡沫镍负载镍铜锰金属纳米电催化剂及其制备方法 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 71
- 239000006260 foam Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 title claims abstract description 19
- UTICYDQJEHVLJZ-UHFFFAOYSA-N copper manganese nickel Chemical compound [Mn].[Ni].[Cu] UTICYDQJEHVLJZ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004070 electrodeposition Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 9
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical class [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 55
- 239000011572 manganese Substances 0.000 abstract description 19
- 239000000243 solution Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000008364 bulk solution Substances 0.000 abstract 1
- 229910003322 NiCu Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 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 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- 241000282414 Homo sapiens Species 0.000 description 1
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- 229940044197 ammonium sulfate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229960000355 copper sulfate Drugs 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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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
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
本发明实施例公开了一种泡沫镍负载镍铜锰金属纳米电催化剂及其制备方法,该制备方法包括如下步骤:⑴对泡沫镍进行预处理,以去除其表面的镍氧化物;⑵将水溶性的锰盐、铜盐和镍盐按预定比例溶于去离子水中,得到前驱体溶液,并调节前驱体溶液的pH为酸性;⑶以预处理过的泡沫镍作为工作电极,在前驱体溶液中进行电沉积而在泡沫镍上负载镍铜锰金属纳米粒子;其中,沉积电位为‑0.5~‑1.2V。本发明通过掺杂催化惰性的金属Cu优化Ni活性位对*H的吸附能,同时加入电极电位远低于Ni和Cu的Mn元素,促进Ni/Ni(OH)2结构形成,具有制备工艺简单、成本低、效率高的优点,且所制备的催化剂对碱性HER反应具有极佳的电催化性能。
Description
技术领域
本发明属于电催化技术领域;更具体地,是涉及一种用于氢析出反应的非贵金属纳米电催化剂及其制备方法。
背景技术
近年来,氢能源由于高能量密度和高清洁度受到广泛关注。现有的制氢技术中,电解水制氢可谓最具发展潜力,因为水解产物只有氧气和氢气,不仅对环境零污染,还可以作为燃料电池的原料,所以电解水既能从根本上减少环境污染问题,还能解决人类所面临的能源危机。
但是,电解水阴极侧的氢析出反应(hydrogen evolution reaction,HER)需要提供远高于理论的电势来克服反应动力学限制(特别是碱性条件下),由此造成了电能的浪费和较低的能源转换效率。目前,相对高效的析氢催化剂为铂基贵金属催化剂,但由于其稀缺性及高昂的成本,导致无法实现大规模生产。同时,铂基催化剂在碱性环境中的活性也远低于酸性环境。所以,寻找在地壳中储量丰富,且在碱性环境下仍具有高活性和耐久性的析氢反应电催化剂,在水电解的可扩展应用中具有至关重要的意义。
电解水析氢分为两个步骤,首先电解液中的H2O分子解离形成反应中间体吸附氢(*H)吸附在催化剂表面,接着吸附氢从催化剂表面脱附形成氢气(H2)。因此,提升碱性HER活性关键在于同时加速水分子的解离和*H的吸/脱附。基于非贵金属和非金属材料的碱性HER电催化剂已经有大量的研究报道,在这些材料中,由于Ni对H的吸附能约为-0.3eV,可以作为*H吸/脱附位点,而氢氧化镍具有优异的水解离能力,使得由Ni和Ni(OH)2构成的多组分界面结构表现出良好的碱性HER活性和稳定性。但现有技术中制备Ni/Ni(OH)2结构存在工艺复杂、成本高和效率低的问题,同时由于Ni对*H的吸附能较强,导致Ni/Ni(OH)2活性需进一步改善。
发明内容
针对现有技术的以上缺陷或改进需求,本发明的主要目的在于提供一种泡沫镍负载镍铜锰金属纳米电催化剂及其制备方法,不仅具有工艺简单、成本低和效率高的优点,而且在碱性条件下对HER反应具有极佳的电催化性能。
为实现上述目的,本发明的第一方面提供了一种泡沫镍负载镍铜锰金属纳米电催化剂的制备方法,包括如下步骤:
⑴对泡沫镍进行预处理,以去除其表面的镍氧化物;
⑵将水溶性的锰盐、铜盐和镍盐按预定比例溶于去离子水中,得到前驱体溶液,并调节前驱体溶液的pH为酸性;
⑶以预处理过的泡沫镍作为工作电极,在前驱体溶液中进行电沉积而在泡沫镍上负载镍铜锰金属纳米粒子;其中,电沉积的沉积电位为-0.5~-1.2V。
根据本发明的一种具体实施方式,步骤⑴所述的预处理包括依次对泡沫镍进行酸洗、水洗和真空干燥。其中,酸洗可以采用盐酸,例如浓度为6mol/L的盐酸。
根据本发明的一种具体实施方式,所述水溶性的锰盐、铜盐和镍盐分别为硫酸锰、硫酸铜和硫酸镍。
根据本发明的一种具体实施方式,前驱体溶液中锰、铜和镍的摩尔比为0.9~1.8:1.5~0.6:4。
根据本发明的一种具体实施方式,前驱体溶液中锰、铜和镍的总摩尔浓度为3~8mol/L。
根据本发明的一种具体实施方式,步骤⑵采用硫酸铵作为pH调节剂。
根据本发明的一种具体实施方式,步骤⑵调节前驱体溶液的pH为4~5。
根据本发明的一种具体实施方式,步骤⑶的电沉积时间为300~1500s。
本发明的制备方法中,通过掺杂催化惰性的金属Cu优化Ni活性位对*H的吸附能,同时加入电极电位远低于Ni和Cu的Mn元素,使Mn以氢氧化物形式存在,促使一步合成Ni/Ni(OH)2结构,由此解决了现有技术存在的制备工艺复杂、成本高和效率低的技术问题,且所制备的催化剂即使在碱性条件下也具有极佳的析氢催化性能。
为了实现上述主要目的,本发明的第二方面提供了一种用于碱性HER反应的泡沫镍负载镍铜锰金属纳米电催化剂,其根据上述的任意一种制备方法得到。
本发明提供的泡沫镍负载镍铜锰金属纳米电催化剂用一步电沉积技术制备而成,具有制作工艺简单、成本低和效率高的优点,且即使在碱性条件下也具有极佳的电催化活性和稳定性。
为了更清楚地说明本发明的目的、技术方案和优点,下面结合附图和具体实施方式对本发明作进一步的详细说明。
附图说明
图1a、1b和1c分别为Ni、Cu和Mn三种金属的Pourbaix图;
图2为实施例1制得的NiCuMn催化剂的电沉积图;
图3a和3b分别为本发明预处理好的多孔泡沫镍及实施例1所制备NiCuMn催化剂的实物图;
图4为实施例1制得的NiCuMn催化剂的FESEM图及EDS能谱图;
图5是本发明实施例1制得的NiCuMn催化剂、对比例1制得的Ni催化剂、对比例2制得的NiCu催化剂及对比例3制得的NiMn催化剂的XRD图;
图6是本发明实施例1制得的NiCuMn催化剂的HAADF-STEM图;
图7a和7b分别为参考样Ni箔和Ni(OH)2,以及本发明发明实施例1制得的NiCuMn催化剂、对比例2制得的NiCu催化剂和对比例3制得的NiMn催化剂,在Ni K边的XANES谱和Ni K边的EXAFS数据对应的K3加权傅立叶变换曲线;
图8是实施例1制得的NiCuMn催化剂、对比例1制得的Ni催化剂、对比例2制得的NiCu催化剂的价带谱图;
图9为实施例1至5所制得镍铜锰催化剂的线性扫描伏安曲线图;
图10是实施例1制得的NiCuMn催化剂、对比例1制得的Ni催化剂、对比例2制得的NiCu催化剂、对比例3制得的NiMn催化剂及预处理好的多孔泡沫镍(NF)的线性扫描伏安曲线图;
图11是实施例1制得的NiCuMn催化剂的稳定性测试图。
具体实施方式
本发明实施例公开了一种泡沫镍负载镍铜锰金属纳米电催化剂的制备方法,包括如下步骤:
⑴对泡沫镍进行预处理,以去除其表面的镍氧化物;具体的,可以先裁剪得到尺寸为1cm*1cm的泡沫镍,再将裁剪好的泡沫镍放入盐酸中超声清洗,去除其表面的NiOx层,然后用去离子水多次清洗去除其表面残余的酸,最后再真空干燥备用。
⑵将水溶性的锰盐、铜盐和镍盐按预定比例溶于去离子水中,得到前驱体溶液,并调节前驱体溶液的pH为酸性。其中,水溶性的锰盐、铜盐和镍盐可以为硫酸锰、硫酸铜和硫酸镍,并采用硫酸铵作为pH调节剂,调节前驱体溶液为弱酸性,优选为4~5。其中,前驱体溶液中锰、铜和镍的摩尔比优选为0.9~1.8:1.5~0.6:4,锰、铜和镍的总摩尔浓度优选为3~8mol/L。
⑶以预处理过的泡沫镍作为工作电极,在前驱体溶液中进行恒电位沉积而在泡沫镍上负载镍铜锰金属纳米粒子。具体的,可以在如下的三电极体系下进行电沉积:以泡沫镍为工作电极,饱和Ag/AgCl为参比电极,石墨棒为对电极。其中,沉积电位可以为-0.5~-1.2V,电沉积时间可以为300~1500s。
图1a、1b和1c为分别为Ni、Cu和Mn三种金属的Pourbaix图,可以看出在酸性条件下提供低于-0.5V的低电压即可将镍离子和铜离子还原,而需提供低于-1.2V的高电压才可还原出金属锰。因此,有理由认为在含有Ni、Cu和Mn金属盐的混合溶液中,在pH为4~5、-0.5~-1.2V的沉积电位下可生成Ni和Cu单质,而Mn为离子态形式存在。本发明中,所描述的电位都是相对于标准氢电极电位。
本发明实施例采用简单的一步电沉积方法,控制沉积电位为-0.5~-1.2V,并通过调节电解液pH为酸性,使电极电势较高的Ni2+和Cu2+还原位Ni和Cu单质,形成NiCu合金,优化Ni对*H的吸/脱附;而电极电势较低的Mn2+以氢氧化物形式存在,促进Ni/Ni(OH)2结构形成,由此提升催化剂的催化性能。
以下,根据具体实施例和对比例更详细地描述本发明。
实施例1
实施例1中泡沫镍负载镍铜锰金属纳米电催化剂的制备包括如下步骤:
⑴将泡沫镍裁剪成1cm*1cm的尺寸,放入浓度为6mol/L的盐酸中超声10min,用去离子水进行数次清洗,在60℃下真空干燥2小时备用。其中,使用盐酸是为了去除表面的氧化物(NiOx),去离子水反复清洗是为了去除泡沫镍上残留的盐酸。
⑵将1.2mmol的五水合硫酸铜(CuSO4﹒5H2O),1.2mmol的一水合硫酸锰(MnSO4﹒H2O),4mmol的六水合硫酸镍(NiSO4﹒6H2O)和2.6mmol硫酸铵((NH4)2SO4),分散于100ml去离子水中,超声20分钟即可得到混合均匀、pH为4~5的电化学沉积电解液。其中,硫酸铵的主要作用是调节溶液pH,五水合硫酸铜提供铜源,一水合硫酸锰提供锰源,六水合硫酸镍提供镍源。
⑶采用三电极体系,以步骤⑴中预处理好的泡沫镍作为工作电极,石墨棒作为对电极,饱和Ag/AgCl作为参比电极,置入步骤⑵的电解液中,在-200mA cm-2的电流密度下保持800秒,即得到NiCuMn催化剂。
如图2所示,实施例1中电沉积电位大约为-0.5~-1V,该沉积条件并未达到Mn2+的还原电位,Mn以离子态形式存在,而Ni2+和Cu2+已被还原。
实施例2-5
实施例2-5的制备流程与实施例1中NiCuMn催化剂一致,区别仅在于改变Cu和Mn的配比。具体的,实施例2-5将Cu与Mn的摩尔量分别调整为1.5mmol与0.9mmol、0.9mmol与1.5mmol、0.6mmol与1.8mmol、0.3mmol与2.1mmol,在此不做赘述。
对比例1-3
对比例1至3分别为:泡沫镍负载镍金属纳米催化剂(Ni)、泡沫镍负载镍铜金属纳米催化剂(NiCu)、泡沫镍负载镍锰金属纳米催化剂(NiMn)。
对比例1-3的具体制备步骤均与实施例1中NiCuMn催化剂的制备工艺相同,区别仅在于制备Ni催化剂时,沉积液中未加入铜源(CuSO4﹒5H2O)和锰源(MnSO4﹒H2O),相应的NiCu催化剂制备时未加入锰源(MnSO4﹒H2O),而NiMn催化剂则未加入铜源(CuSO4﹒5H2O),在此不再赘述。
催化剂结构与形貌分析
图3a和3b分别为预处理好的多孔泡沫镍及实施例1所制备NiCuMn催化剂的实物图,对比两张图可看出在多孔泡沫镍上沉积有一层十分明显的黑色物质。图4为实施例1所制备NiCuMn催化剂的FESEM图,可以看出多孔泡沫镍上负载了均匀的球状颗粒,颗粒大小约为200纳米,其多孔形态不仅提供了丰富的活性位点,而且还有利于电荷传输和气泡的排空。
图5为Ni、NiCu、NiMn、NiCuMn催化剂的XRD图,从图中可观察到NiCu和NiCuMn催化剂在43.9°处均出现了NiCu合金的衍射峰,且相比于Ni催化剂中Ni的衍射峰也整体发生小角度偏移,说明Cu加入后与Ni形成了NiCu合金;而Mn的加入并未改变衍射峰的位置,但是能观察到衍射峰强度明显减弱,同时NiMn合金未显示XRD衍射峰,说明Mn促进非晶相形成。
进一步地,通过NiCuMn催化剂的HAADF-STEM图(图6)可以看出该样品中存在结晶相Ni和非晶相Ni(OH)2;Ni/Ni(OH)2结构进一步通过同步辐射吸收谱得到证实。
图7a和7b分别为参考样Ni箔和Ni(OH)2,以及本发明制备的NiCu、NiMn、NiCuMn催化剂,在Ni K边的XANES谱和Ni K边的EXAFS数据对应的K3加权傅立叶变换曲线,从图7a中可以看出NiCu的XANES光谱的前线位于8335eV,接近于参考镍箔(位于约8336eV),NiMn几乎与位于8341eV的Ni(OH)2重合,NiCuMn位于8337eV处介于二者之间,这证明了NiCu的主要镍相是金属镍,NiMn中镍主要以氢氧化物形式存在,而NiCuMn中则既有二价镍(氢氧化镍)也有金属镍;从7b图可以看出NiCuMn的Ni-Ni峰显示出比Ni箔略小的R空间,表明一个Ni原子被一个Cu原子所取代,从而导致晶格畸变。
图8为Ni、NiCu、NiCuMn催化剂的价带谱图,可以看出NiCu形成合金后,d带中心相比于其他催化剂有明显下移,而已证实d带中心的位置与催化剂对*H中间体的吸附有关,下移说明其对*H中间体吸附有所削弱,即NiCu形成合金后优化了Ni对*H的吸/脱附。
碱性HER反应电催化性能测试
在浓度为1mol/L的KOH溶液、扫描速率为2mV/s的条件下,以所制备催化剂为工作电极,石墨棒为对电极,饱和Ag/AgCl为参比电极,测试实施1至5所制备催化剂的电催化性能。如图9所示,可以看出当Cu的占比逐渐增多时,催化剂的性能逐渐提高,相应的Mn占比增多时,性能变差。其中,当Ni、Cu和Mn的摩尔比为0.9~1.8:1.5~0.6:4时,催化剂均具有较佳的HER电催化活性;当Mn、Cu和Ni的摩尔比为1.2:1.2:4时(实施例1)催化剂的电催化性能最佳。
图10为Ni、NiCu、NiMn、NiCuMn催化剂及预处理好的多孔泡沫镍(NF)的线性扫描伏安曲线(LSV),可以看出在电流密度为10mA cm-2下,实施例1制备的NiCuMn催化剂具有非常低地过电位,仅为17mV,根据以往研究数据商业Pt/C的过电位一般在30mV左右,可见实施例1制备的催化剂性能优于商业Pt/C。
图11为NiCuMn催化剂的稳定性测试图,分别测试了10、50、100mA cm-2的电流密度下的稳定性,随着测试时间的延长,催化性能几乎保持稳定,可见实施例1制备的催化剂具有优异的稳定性。
综上所述,即使在碱性环境下,本发明的泡沫镍负载镍铜锰纳米电催化剂对于HER反应也具有优异的催化活性和稳定性。并且,该泡沫镍负载镍铜锰纳米电催化剂可以通过一步电沉积法制备,具有制备工艺简单、成本低、效率高的优点。
虽然以上通过具体实施例描绘了本发明,但应当理解的是,本领域普通技术人员在不脱离本发明的范围内,凡依照本发明所作的同等改变,应为本发明的保护范围所涵盖。
Claims (10)
1.泡沫镍负载镍铜锰金属纳米电催化剂的制备方法,包括如下步骤:
⑴对泡沫镍进行预处理,以去除其表面的镍氧化物;
⑵将水溶性的锰盐、铜盐和镍盐按预定比例溶于去离子水中,得到前驱体溶液,并调节所述前驱体溶液的pH为酸性;
⑶以预处理过的泡沫镍作为工作电极,在所述前驱体溶液中进行电沉积而在所述泡沫镍上负载镍铜锰金属纳米粒子;其中,所述电沉积的沉积电位为-0.5~-1.2V。
2.根据权利要求1所述的制备方法,其中,步骤⑴所述的预处理包括依次对泡沫镍进行酸洗、水洗和真空干燥。
3.根据权利要求1所述的制备方法,其中,所述水溶性的锰盐、铜盐和镍盐分别为硫酸锰、硫酸铜和硫酸镍。
4.根据权利要求1所述的制备方法,其中,所述前驱体溶液中锰、铜和镍的摩尔比为0.9~1.8:1.5~0.6:4。
5.根据权利要求1所述的制备方法,其中,所述前驱体溶液中锰、铜和镍的总摩尔浓度为3~8mol/L。
6.根据权利要求1所述的制备方法,其中,步骤⑵采用硫酸铵作为pH调节剂。
7.根据权利要求1所述的制备方法,其中,步骤⑵调节所述前驱体溶液的pH为4~5。
8.根据权利要求1所述的制备方法,其中,步骤⑶的电沉积时间为300~1500s。
9.根据权利要求1所述的制备方法,其中,步骤⑶在如下的三电极体系下进行电沉积:以泡沫镍为工作电极,饱和Ag/AgCl为参比电极,石墨棒为对电极。
10.一种用于碱性HER反应的泡沫镍负载镍铜锰金属纳米电催化剂,根据权利要求1至9任一项所述的制备方法得到。
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