CN110433818B - 一种钼酸镍碳复合纳米球、制备方法及其作为电解水析氢催化剂的应用 - Google Patents
一种钼酸镍碳复合纳米球、制备方法及其作为电解水析氢催化剂的应用 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002077 nanosphere Substances 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- -1 molybdate ions Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- ZMBGEOHZPOUFHR-UHFFFAOYSA-N methanol;nickel Chemical compound [Ni].OC ZMBGEOHZPOUFHR-UHFFFAOYSA-N 0.000 claims description 8
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 8
- 235000015393 sodium molybdate Nutrition 0.000 claims description 8
- 239000011684 sodium molybdate Substances 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 3
- KHSTZMGCKHBFJX-UHFFFAOYSA-N 3-(dibutylamino)phenol Chemical compound CCCCN(CCCC)C1=CC=CC(O)=C1 KHSTZMGCKHBFJX-UHFFFAOYSA-N 0.000 claims description 2
- TVKZDKSHNITMRZ-UHFFFAOYSA-N 3-(ethylamino)phenol Chemical compound CCNC1=CC=CC(O)=C1 TVKZDKSHNITMRZ-UHFFFAOYSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- DSEQJUPGRWESKP-UHFFFAOYSA-N n-(2-hydroxy-5-methylphenyl)acetamide Chemical compound CC(=O)NC1=CC(C)=CC=C1O DSEQJUPGRWESKP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- GAIQJSWQJOZOMI-UHFFFAOYSA-L nickel(2+);dibenzoate Chemical compound [Ni+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAIQJSWQJOZOMI-UHFFFAOYSA-L 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-M 2-carboxy-5-hydroxyphenolate Chemical compound OC1=CC=C(C([O-])=O)C(O)=C1 UIAFKZKHHVMJGS-UHFFFAOYSA-M 0.000 claims 1
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
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- 238000005265 energy consumption Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000003828 vacuum filtration Methods 0.000 description 5
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940114055 beta-resorcylic acid Drugs 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 239000012716 precipitator Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Abstract
本发明公开了一种钼酸镍碳复合纳米球、制备方法及其作为电解水析氢催化剂的应用,属于纳米复合纳米球合成领域。本发明的钼酸镍碳复合纳米球的制备方法,前期在100℃之下反应下利用共沉淀法快速制备出钼酸镍前驱体,中期利用氨基苯酚衍生物在室温下裁剪钼酸镍前驱体的结构,后期通过简单的煅烧处理最终制备了钼酸镍碳复合纳米球,整体制备工艺安全环保,能耗低、操作简单,可重复性较强;不同于现有技术自下而上的制备方法,本发明利用氨基苯酚衍生物所含活性官能团对钼酸镍的配位、刻蚀作用,自上而下的对其进行结构裁剪,克服了现有技术反应条件苛刻、工艺参数复杂、能耗偏高的问题。
Description
技术领域
本发明属于纳米复合纳米球合成领域,尤其是一种钼酸镍碳复合纳米球、制备方法及其作为电解水析氢催化剂的应用。
背景技术
持续的能源危机和环境污染使得开发清洁与可持续能源越来越重要。氢气作为一种绿色能源在未来有望取代传统的化石燃料。电催化水分解是一种有效的析氢方法。但是商业化的铂碳电极由于贵金属的使用限制了电解水析氢的大规模应用。含镍化合物价格低廉,催化活性较好,正逐渐成为电解水析氢催化剂电极的研究热点。中国发明专利201280053710.X公开了一系列含镍二元或三元金属氧化物,具有较好的电催化活性。中国发明专利201810320864.X,以泡沫镍为导电基体并提供反应所需要的镍源,以尿素为沉淀剂,以氟化氢为刻蚀剂,在泡沫镍骨架结构表面制备镍基电催化材料,其中氟化氢腐蚀性较强,对人体及环境均具有一定的危害。中国发明专利201611213851.X,公开了一种采用电沉积法制备PS/Ni复合材料,并通过酸刻蚀及表面涂覆制备了Ni-Mo-Co泡沫析氢电极,具有较好的电催化活性,但是电沉积法对设备要求比较苛刻,不利于产品的工业化大规模制备。中国发明专利201810447414.7,采用水热法制备了钼酸镍/石墨烯复合材料,并通过控制反应物的质量比,水热温度、水热时间等提高钼酸镍/石墨烯的催化活性。但是催化剂的制备条件比较严格,且析氢活性仍需进一步提高。
发明内容
本发明的目的在于克服上述现有技术的缺点,提供一种钼酸镍碳复合纳米球、制备方法及其作为电解水析氢催化剂的应用。
为达到上述目的,本发明采用以下技术方案予以实现:
一种钼酸镍碳复合纳米球的制备方法,包括以下步骤:
1)配制镍盐甲醇溶液和钼酸盐水溶液;所述镍盐甲醇溶液中镍离子的浓度为0.1~0.4mol/L,钼酸盐水溶液中钼酸根离子的浓度为0.05~0.1mol/L;
2)将体积比为1:(1~3)的镍盐甲醇溶液和钼酸盐水溶液混合,得到反应液,将反应液置于50~70℃搅拌10~24h进行反应,反应结束后再次置于80~100℃搅拌1~3h进行反应,反应结束后进行抽滤、洗涤、干燥,得到产物A;
3)将产物A分散在氨基苯酚衍生物水溶液中,得到混合液;将混合液在室温下搅拌7~12h进行反应,反应结束后经过滤、清洗、干燥后得到产物B;
其中,氨基苯酚衍生物水溶液的浓度为0.01~0.04mol/L,每100mL氨基苯酚衍生物水溶液中加入30mg产物A;
4)将产物B在惰性气体气氛下、500~700℃煅烧2h,得到钼酸镍碳复合纳米球。
进一步的,步骤1)中镍盐为苯甲酸镍或2,4-二羟基苯甲酸镍。
进一步的,所述步骤1)中钼酸盐为钼酸钠或钼酸铵。
进一步的,所述步骤3)中氨基苯酚衍生物为2-羟基-5-甲基乙酰苯胺、3-(二丁氨基)苯酚、4-(2-氨基乙基)-1,2-苯二酚或3-乙基氨基苯酚。
上述制备方法制备得到的钼酸镍碳复合纳米球,纳米球的粒径为150~170nm。
上述钼酸镍碳复合纳米球作为电解水析氢催化剂的应用。
与现有技术相比,本发明具有以下有益效果:
本发明的钼酸镍碳复合纳米球的制备方法,前期在100℃之下反应,利用共沉淀法快速制备出钼酸镍前驱体,中期利用氨基苯酚衍生物在室温下裁剪钼酸镍前驱体的结构,后期通过简单的煅烧处理最终制备了钼酸镍碳复合纳米球,整体制备工艺安全环保,能耗低、操作简单,可重复性较强;不同于现有技术自下而上的制备方法,本发明利用氨基苯酚衍生物所含活性官能团对钼酸镍的配位、刻蚀作用,自上而下的对其进行结构裁剪,克服了现有技术反应条件苛刻、工艺参数复杂、能耗偏高的问题。
本发明的钼酸镍碳复合纳米球,形貌规整、粒径较小、纯度与结晶度较高。
本发明的钼酸镍碳复合纳米球作为电解水析氢催化剂,纳米球结构能够提供较多的催化活性位点,表面包覆碳材料可以提高催化剂的导电性,二者结合使其具有较好的电解水析氢催化活性。
附图说明
图1为钼酸镍碳复合纳米球的扫描电镜图;
图2为钼酸镍碳复合纳米球的XRD图;
图3为钼酸镍碳复合纳米球的电化学性能图;
其中:上述测试样品均取自实施例1。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分的实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都应当属于本发明保护的范围。
需要说明的是,本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象,而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换,以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外,术语“包括”和“具有”以及他们的任何变形,意图在于覆盖不排他的包含,例如,包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元,而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
下面结合附图对本发明做进一步详细描述:
实施例1
1)配制浓度为0.4mol/L的苯甲酸镍甲醇溶液,配制0.1mol/L的钼酸钠水溶液;
2)将体积比为1:3钼酸钠水溶液缓慢滴加到苯甲酸镍甲醇溶液中,在60℃搅拌24h,接着在90℃继续搅拌反应3h,反应结束后经真空抽滤、洗涤、干燥,得到产物A;
3)将60mg产物A超声分散在200mL浓度为0.04mol/L的2-羟基-5-甲基乙酰苯胺水溶液,常温常压下搅拌12h,过滤,清洗,干燥后得到产物B;
4)将产物B在氩气气氛下700℃煅烧2h,得到钼酸镍碳复合纳米球。
参见图1,图1为本发明制备的钼酸镍碳复合纳米球的扫描电子显微镜图;从图中可见所制备的产品呈球状形貌,直径为150~170nm。
参见图2,图2为钼酸镍碳复合纳米球的XRD图;产品测试的2θ范围为20°~80°。产品的XRD衍射峰比较尖锐,与标准卡片JCPDS:45-0142基本对应,并未出现其它的杂峰,说明制备的产品纯度与结晶度较高。
参见图3,图3为钼酸镍碳复合纳米球电极的极化曲线;从图中可以看出该样品在电流密度为10mA/cm2时,电极析氢反应的过电位为401mV,说明粒径小、形貌规整的纳米球结构和表面包覆的碳材料使钼酸镍碳复合纳米球具有较好的电催化性能;测试条件为,以制备的钼酸镍碳复合纳米球作为催化剂活性物质,全氟磺酸-聚四氟乙烯共聚物(Nafion)为粘结剂,在玻碳电极上组装为工作电极,0.5mol/L的硫酸溶液为电解液。
实施例2
1)配制浓度为0.1mol/L的2,4-二羟基苯甲酸镍甲醇溶液,配制0.05mol/L的钼酸铵水溶液;
2)将体积比为1:1的钼酸铵水溶液缓慢滴加到2,4-二羟基苯甲酸镍甲醇溶液中,60℃搅拌10h,接着90℃继续搅拌反应1h,反应结束后经真空抽滤、洗涤、干燥,得到产物A;
3)将30mg的产物A超声分散于100mL的浓度为0.01mol/L的3-(二丁氨基)苯酚水溶液,常温常压下搅拌7h,过滤,清洗,干燥后得到产物B;
4)将产物B在氩气气氛下500℃煅烧2h,得到钼酸镍碳复合纳米球。
实施例3
1)配制浓度为0.2mol/L的苯甲酸镍甲醇溶液,配制0.07mol/L的钼酸钠水溶液;
2)将体积比为1:2的钼酸钠水溶液缓慢滴加到苯甲酸镍甲醇溶液,50℃搅拌20h,接着80℃继续搅拌反应2h,反应结束后经真空抽滤、洗涤、干燥,得到产物A;
3)将45mg产物A超声分散于150mL的浓度为0.02mol/L的4-(2-氨基乙基)-1,2-苯二酚水溶液,常温常压下搅拌10h,过滤,清洗,干燥后得到产物B;
4)将产物B在氩气气氛下600℃煅烧2h,得到钼酸镍碳复合纳米球。
实施例4
1)配制浓度为0.3mol/L的2,4-二羟基苯甲酸镍甲醇溶液,配制0.08mol/L的钼酸铵水溶液;
2)将体积比为1:3的钼酸铵水溶液缓慢滴加到2,4-二羟基苯甲酸镍甲醇溶液中,在70℃搅拌17h,接着90℃继续搅拌反应3h,反应结束后经真空抽滤、洗涤、干燥,得到产物A;
3)将30mg产物A超声分散于100mL的浓度为0.03mol/L的3-乙基氨基苯酚水溶液,常温常压下搅拌11h,过滤,清洗,干燥后得到产物B;
4)将产物B在氮气气氛下600℃煅烧2h,得到钼酸镍碳复合纳米球。
实施例5
1)配制浓度为0.4mol/L的苯甲酸镍甲醇溶液,配制0.07mol/L的钼酸钠水溶液;
2)将体积比为1:3的钼酸钠水溶液缓慢滴加到苯甲酸镍甲醇溶液,在60℃搅拌20h,接着在100℃继续搅拌反应3h,反应结束后经真空抽滤、洗涤、干燥,得到产物A;
3)将60mg产物A超声分散于200mL的浓度为0.04mol/L的4-(2-氨基乙基)-1,2-苯二酚水溶液,常温常压下搅拌12h,过滤,清洗,干燥后得到产物B;
4)将产物B在氩气气氛下650℃煅烧2h,得到钼酸镍碳复合纳米球。
以上内容仅为说明本发明的技术思想,不能以此限定本发明的保护范围,凡是按照本发明提出的技术思想,在技术方案基础上所做的任何改动,均落入本发明权利要求书的保护范围之内。
Claims (4)
1.一种钼酸镍碳复合纳米球的制备方法,其特征在于,包括以下步骤:
1)配制镍盐甲醇溶液和钼酸盐水溶液;所述镍盐甲醇溶液中镍离子的浓度为0.1~0.4mol/L,钼酸盐水溶液中钼酸根离子的浓度为0.05~0.1mol/L;
2)将体积比为1:(1~3)的镍盐甲醇溶液和钼酸盐水溶液混合,得到反应液,将反应液置于50~70℃搅拌10~24h进行反应,反应结束后再次置于80~100℃搅拌1~3h进行反应,反应结束后进行抽滤、洗涤、干燥,得到产物A;
3)将产物A分散在氨基苯酚衍生物水溶液中,得到混合液;将混合液在室温下搅拌7~12h进行反应,反应结束后经过滤、清洗、干燥后得到产物B;
其中,氨基苯酚衍生物水溶液的浓度为0.01~0.04mol/L,每100mL氨基苯酚衍生物水溶液中加入30mg产物A;
4)将产物B在惰性气体气氛下、500~700℃煅烧2h,得到钼酸镍碳复合纳米球;
步骤1)中镍盐为苯甲酸镍或2,4-二羟基苯甲酸镍;
所述步骤3)中氨基苯酚衍生物为2-羟基-5-甲基乙酰苯胺、3-(二丁氨基)苯酚、4-(2-氨基乙基)-1,2-苯二酚或3-乙基氨基苯酚。
2.根据权利要求1所述的钼酸镍碳复合纳米球的制备方法,其特征在于,所述步骤1)中钼酸盐为钼酸钠或钼酸铵。
3.一种根据权利要求1或2所述的制备方法制备得到的钼酸镍碳复合纳米球,其特征在于,纳米球的粒径为150~170nm。
4.一种根据权利要求3所述的钼酸镍碳复合纳米球作为电解水析氢催化剂的应用。
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