CN111534835B - 一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法 - Google Patents
一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法 Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 66
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 66
- OQFRENMCLHGPRB-UHFFFAOYSA-N copper;dioxido(dioxo)tungsten Chemical compound [Cu+2].[O-][W]([O-])(=O)=O OQFRENMCLHGPRB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002950 deficient Effects 0.000 title claims description 31
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002121 nanofiber Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 38
- 239000002134 carbon nanofiber Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
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- 239000000843 powder Substances 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
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- 238000009987 spinning Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 4
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 42
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- 230000031700 light absorption Effects 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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Abstract
本发明涉及一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,属于光电催化技术领域。本项目以高比表面积的一维CuWO4中空纳米纤维光阳极作为载体,采用表面缺陷工程策略,通过CuWO4表面的氧空位来锚定Co单原子电催化剂。该单原子负载过程可避免高温煅烧步骤,为Ni单原子在钨酸铜光电极表面的均匀分散提供了一种新方法,所制备的Ni单原子/氧缺陷钨酸铜光阳极可实现高活性、高稳定性水分解,在氢能制备领域具有广泛的应用前景。
Description
技术领域
本发明属于光电催化技术领域,具体涉及一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,该方法采用缺陷工程策略将Ni单原子牢牢锚定在钨酸铜光电极表面,无需高温煅烧步骤,制备的Ni单原子/氧缺陷钨酸铜光阳极可利用太阳能实现低电位下水分解。
背景技术
环境污染和能源短缺是人类可持续发展面临的主要挑战,氢气具有能量密度大和零碳排放的优点,是一种理想的清洁能源,因此氢能的制备和储存成为能源领域研究的热点。光电催化分解水产氢,已被证实是将太阳能转化为氢能的一种有效手段。相比于传统的电解水产氢,光电催化分解水产氢器件具有组装简单、成本低廉、能耗较低和易于大规模生产等优点,具有很大的应用潜力,受到研究者们的极大关注。在光电催化分解水过程中,光阴极还原质子产氢(HER)是2电子转移过程,而光阳极氧化水产氧(OER)是4电子转移过程,这使得后者反应过程较为复杂,过电位较大,成为动力学上水分解的决速步骤。
单原子处于离散状态时具备更多的悬挂空轨道而表现出更强的吸附与活化性能。且理论上可达到100%的原子利用率,最大限度地减少金属的负载量而节约成本。此外,单原子尺寸均一,可在原子尺度调控活性位点的配位环境和几何构型,便于催化性能的优化。因此,将单原子负载在半导体光电极表面,有望解决水氧化动力学缓慢的问题。但是,在单原子催化剂制备过程中,一般利用空间限域、配位点锚定、分子热运动的抑制等方法实现金属前驱体在载体上的原子级分散和隔离,随后在惰性气氛下热裂解(700-900℃),以获得分散的单原子电催化剂。然而,这种传统的热裂解步骤并不适合构筑单原子修饰光阳极,这是因为热裂解会改变半导体自身的物理化学性质,比如晶型、形貌、颗粒尺寸、导电性等,甚至有可能造成半导体的分解和金属单原子的团聚。因此,如何实现单原子电催化剂在半导体光阳极表面的原子级分散和稳定负载仍然存在较大挑战。本发明通过等离子技术在钨酸铜表面引入氧缺陷,以此为“陷阱”来捕获Ni金属前驱体,再利用Ni金属单原子与氧缺陷位点的电荷转移效应来稳定形成的单原子,制备的Ni单原子/氧缺陷钨酸铜光阳极具有优异的光电催化水分解活性。本发明为今后合理设计制备新型、高效、稳定的单原子/半导体光电极提供有益的思路,也为单原子助催化剂在光电催化领域的深入应用提供理论参考和示例,是一项兼具科学意义和社会经济意义的重要发明。
发明内容
本发明针对现有技术的不足,提供一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法。其目的在于采用等离子体技术在CuWO4纳米纤维表面引入氧缺陷,实现单原子电催化剂在CuWO4光阳极表面的原子级分散,为构筑廉价、高效和稳定的单原子修饰的半导体材料提供新工艺。本发明的目的通过以下技术方案实现:
1)将聚乙烯醇旋涂至FTO玻璃表面,增强FTO表面的粘性。固定FTO玻璃于静纺装置的滚筒上。将聚丙烯腈粉体加入二甲基甲酰胺溶液中,搅拌过夜,后转至静电纺丝机,通高压电拉丝成纳米纤维,收集FTO表面的纳米纤维,先250℃低温预处理,后900℃高温碳化处理,获得碳纳米纤维电极(CNFs);
2)配制铜盐和钨酸盐的前驱体水溶液,转入反应釜中,将CNFs电极加入到该前驱体溶液中,密封,置于恒温干燥箱中保温一定时间,水热完毕,水洗多次,获得CuWO4/CNFs复合纤维。空气条件下高温煅烧,去除CNFs硬质模板,获得中空结构的CuWO4纳米纤维电极;
3)利用空气等离子体对CuWO4电极进行射频放电改性处理,设置等离子体清洗机的处理时间、功率和空气流量等参数,获得表面氧缺陷的CuWO4薄膜;
4)将所制备的氧缺陷CuWO4薄膜浸泡至金属Ni的前驱体溶液中,暗吸附,之后取出,水洗。配制一定浓度的NaBH4水溶液,鼓氮气,排尽溶液中的氧气,将吸附有Ni前驱体的CuWO4薄膜放置于NaBH4水溶液中一段时间,Ni离子被还原为单质Ni,实现单原子Ni在CuWO4薄膜表面的负载。
优选地,步骤2所述铜盐为硝酸铜或醋酸铜中的一种,钨酸盐为钨酸铵或六氯化钨中的一种。
优选地,步骤3所述等空气离子体处理参数为:时间10-500s,功率50-200W,空气流量为5-200ml/min。
优选地,步骤4所述Ni的前驱体为NiCl2、Ni(NO3)2或者Ni(CH3COO)2中的一种。
优选地,步骤4所述Ni的前驱体浓度为0.01-10mmol/L
优选地,步骤4所述NaBH4水溶液浓度为0.1-1mol/L。
本发明的有益效果:本发明通过静电纺丝工艺制备一维中空CuWO4纳米纤维薄膜,能够有效增加CuWO4的比表面积,缩短电荷传输距离,增强光在材料中的散射现象,提高光吸收效率;此外,使用等离子体处理技术来获得氧缺陷型钨酸铜,具有成本低、操作安全和处理效率高等优点,从而为单原子Ni电催化剂在氧缺陷CuWO4纳米纤维光阳极表面的原子级分散和稳定负载提供技术支持。另外,制备的Ni单原子/氧缺陷钨酸铜光阳极相较单一的钨酸铜电极的光电流密度显著增加,起始电位负移,为低能耗、高效率转化水分子提供了一条新途径。
附图说明
图1为实施例一中制备的一维中空CuWO4纳米纤维的扫描电镜图;
图2为实施例二中制备的CuWO4和氧缺陷CuWO4的接触角测试结果;
图3为实施例三中制备的Ni单原子/表面氧缺陷CuWO4和表面氧缺陷CuWO4的线性扫描伏安曲线图;
图4为实施例四中制备的Ni单原子/表面氧缺陷CuWO4和表面氧缺陷CuWO4光生载流子在飞秒-纳秒时间范围内的瞬态吸收谱图。
具体实施方式
为了更好的理解本发明,下面结合实施例和附图进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例一
一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,具体步骤如下:用移液枪移取100μL聚乙烯醇,旋涂至FTO玻璃表面,增强FTO表面的粘性。固定FTO玻璃于静纺装置的滚筒上。称取0.6g聚丙烯腈粉体加入到10ml二甲基甲酰胺溶液中,搅拌过夜,后转至静电纺丝机,通18kV高压电,纺丝液拉丝成纳米纤维,收集FTO表面的纳米纤维,先250℃低温预处理,后900℃高温碳化处理,获得碳纳米纤维电极(CNFs);配制乙酸铜和钨酸铵的前驱体水溶液,转入反应釜中,将CNFs电极加入到该前驱体溶液中,密封,置于150℃恒温干燥箱中保温5h,水热完毕,水洗多次,获得CuWO4/CNFs复合纤维。550℃空气条件下高温煅烧,去除CNFs硬质模板,获得中空结构的CuWO4纳米纤维电极;利用空气等离子体对CuWO4电极进行射频放电改性处理,设置等离子体清洗机的处理时间为60s、功率80W、空气流量20ml/mim,获得表面氧缺陷的CuWO4薄膜;将所制备的氧缺陷CuWO4薄膜浸泡至硝酸镍的前驱体溶液中,暗吸附,之后取出,水洗。配制0.5mol/L的NaBH4水溶液,鼓氮气,排尽溶液中的氧气,将吸附有硝酸镍的CuWO4薄膜放置于NaBH4水溶液中10min,Ni离子被还原为单质Ni,即得Ni单原子/氧缺陷钨酸铜光电极。
图1为本实施例制备的一维中空CuWO4纳米纤维的扫描电镜图,由图可知,形成的一维CuWO4纳米纤维是中空结构,纤维之间相互堆叠,形成三维网毡。该中空结构表面含有大量纳米薄片,有效增加了CuWO4的比表面积,还能增加光反射,提高光吸收效率。
实施例二
一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,具体步骤如下:用移液枪移取100μL聚乙烯醇,旋涂至FTO玻璃表面,增强FTO表面的粘性。固定FTO玻璃于静纺装置的滚筒上。称取1.0g聚丙烯腈粉体加入到10ml二甲基甲酰胺溶液中,搅拌过夜,后转至静电纺丝机,通15kV高压电,纺丝液拉丝成纳米纤维,收集FTO表面的纳米纤维,先250℃低温预处理,后900℃高温碳化处理,获得碳纳米纤维电极(CNFs);配制硝酸铜和钨酸铵的前驱体水溶液,转入反应釜中,将CNFs电极加入到该前驱体溶液中,密封,置于150℃恒温干燥箱中保温6h,水热完毕,水洗多次,获得CuWO4/CNFs复合纤维。550℃空气条件下高温煅烧,去除CNFs硬质模板,获得中空结构的CuWO4纳米纤维电极;利用空气等离子体对CuWO4电极进行射频放电改性处理,设置等离子体清洗机的处理时间为60s、功率80W、空气流量20ml/min,获得表面氧缺陷的CuWO4薄膜;将所制备的氧缺陷CuWO4薄膜浸泡至硝酸镍的前驱体溶液中,暗吸附,之后取出,水洗。配制0.5mol/L的NaBH4水溶液,鼓氮气,排尽溶液中的氧气,将吸附有硝酸镍的CuWO4薄膜放置于NaBH4水溶液中10min,Ni离子被还原为单质Ni,即得Ni单原子/氧缺陷钨酸铜光电极。
图2为本实施例制备的CuWO4和氧缺陷CuWO4的接触角测试结果,实施例三
一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,具体步骤如下:用移液枪移取100μL聚乙烯醇,旋涂至FTO玻璃表面,增强FTO表面的粘性。固定FTO玻璃于静纺装置的滚筒上。称取0.7g聚丙烯腈粉体加入到10ml二甲基甲酰胺溶液中,搅拌过夜,后转至静电纺丝机,通18kV高压电,纺丝液拉丝成纳米纤维,收集FTO表面的纳米纤维,先250℃低温预处理,后950℃高温碳化处理,获得碳纳米纤维电极(CNFs);配制乙酸铜和钨酸铵的前驱体水溶液,转入反应釜中,将CNFs电极加入到该前驱体溶液中,密封,置于160℃恒温干燥箱中保温3h,水热完毕,水洗多次,获得CuWO4/CNFs复合纤维。550℃空气条件下高温煅烧,去除CNFs硬质模板,获得中空结构的CuWO4纳米纤维电极;利用空气等离子体对CuWO4电极进行射频放电改性处理,设置等离子体清洗机的处理时间为300s、功率100W、空气流量50ml/mim,获得表面氧缺陷的CuWO4薄膜;将所制备的氧缺陷CuWO4薄膜浸泡至硝酸镍的前驱体溶液中,暗吸附,之后取出,水洗。配制0.1mol/L的NaBH4水溶液,鼓氮气,排尽溶液中的氧气,将吸附有硝酸镍的CuWO4薄膜放置于NaBH4水溶液中5min,Ni离子被还原为单质Ni,即得Ni单原子/氧缺陷钨酸铜光电极。
将上述Ni单原子/表面氧缺陷CuWO4和表面氧缺陷CuWO4放入光电化学反应器内,与铂片对电极和饱和甘汞参比电极组装成三电极体系,选用0.1M磷酸钾作为电解质溶液(pH=7),采用上海辰华CHI660E电化学工作站测试复合电极在模拟太阳光照和暗态下的电流密度。光电流测试前,往电解质溶液中鼓N2半个小时,以除去溶液中的氧气,避免氧气干扰。图3为本实施例制备的Ni单原子/表面氧缺陷CuWO4和表面氧缺陷CuWO4的线性扫描伏安法图,扫描速度设置为20mV/s。由图可知,随着电极电位逐渐增加,光电流密度逐渐增加,说明在在光电协同催化作用下,电极的载流子分离效率提高。表面氧缺陷CuWO4的起始电位大约为0.61V(vs.RHE),负载单原子Ni之后,起始电位负移至0.52V(vs.RHE)左右,且光电流显著提高,说明单原子Ni不仅能提高钨酸铜光电极的电流密度,还能降低反应的过电位,对钨酸铜光电极的实际应用具有重要的推动作用。
实施例四
一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,具体步骤如下:用移液枪移取100μL聚乙烯醇,旋涂至FTO玻璃表面,增强FTO表面的粘性。固定FTO玻璃于静纺装置的滚筒上。称取0.6g聚丙烯腈粉体加入到10ml二甲基甲酰胺溶液中,搅拌过夜,后转至静电纺丝机,通16kV高压电,纺丝液拉丝成纳米纤维,收集FTO表面的纳米纤维,先250℃低温预处理,后900℃高温碳化处理,获得碳纳米纤维电极(CNFs);配制乙酸铜和钨酸铵的前驱体水溶液,转入反应釜中,将CNFs电极加入到该前驱体溶液中,密封,置于170℃恒温干燥箱中保温5h,水热完毕,水洗多次,获得CuWO4/CNFs复合纤维。550℃空气条件下高温煅烧,去除CNFs硬质模板,获得中空结构的CuWO4纳米纤维电极;利用空气等离子体对CuWO4电极进行射频放电改性处理,设置等离子体清洗机的处理时间为180s、功率50W、空气流量200ml/mim,获得表面氧缺陷的CuWO4薄膜;将所制备的氧缺陷CuWO4薄膜浸泡至硝酸镍的前驱体溶液中,暗吸附,之后取出,水洗。配制0.3mol/L的NaBH4水溶液,鼓氮气,排尽溶液中的氧气,将吸附有硝酸镍的CuWO4薄膜放置于NaBH4水溶液中10min,Ni离子被还原为单质Ni,即得Ni单原子/氧缺陷钨酸铜光电极。
图4为本实施例制备的Ni单原子/表面氧缺陷CuWO4和表面氧缺陷CuWO4光生载流子在飞秒-纳秒时间范围内的瞬态吸收谱图。由图可知,在fs-ns的时间范围内,Ni单原子修饰后,氧缺陷CuWO4的载流子寿命明显增加。考虑到长寿命载流子是实现有效水氧化的前提条件,本发明开发的单原子催化剂/氧缺陷CuWO4光阳极将有效提高光电催化过程中析氧反应的活性,与图3观察到的宏观光电流效果一致。
Claims (6)
1.一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,其特征在于由以下步骤组成:
1)将聚乙烯醇旋涂至FTO玻璃表面,增强FTO表面的粘性,固定FTO玻璃于静纺装置的滚筒上,将聚丙烯腈粉体加入二甲基甲酰胺溶液中,搅拌过夜,后转至静电纺丝机,通高压电拉丝成纳米纤维,收集FTO表面的纳米纤维,先250℃低温预处理,后900℃高温碳化处理,获得碳纳米纤维电极CNFs;所述高压电为15kV、16kV或18kV;
2)配制铜盐和钨酸盐的前驱体水溶液,转入反应釜中,将CNFs电极加入到该前驱体溶液中,密封,置于恒温干燥箱中保温一定时间,水热完毕,水洗多次,获得CuWO4/CNFs复合纤维,空气条件下高温煅烧,去除CNFs硬质模板,获得中空结构的CuWO4纳米纤维电极;
3)利用空气等离子体对CuWO4电极进行射频放电改性处理,设置等离子体清洗机的处理时间、功率和空气流量参数,获得表面氧缺陷的CuWO4薄膜;
4)将所制备的氧缺陷CuWO4薄膜浸泡至金属Ni的前驱体溶液中,暗吸附,之后取出,水洗,配制一定浓度的NaBH4水溶液,鼓氮气,排尽溶液中的氧气,将吸附有Ni前驱体的CuWO4薄膜放置于NaBH4水溶液中一段时间,Ni离子被还原为单质Ni,实现单原子Ni在CuWO4薄膜表面的负载。
2.根据权利要求1所述的一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,其特征在于,步骤2所述铜盐为硝酸铜或醋酸铜中的一种,钨酸盐为钨酸铵。
3.根据权利要求1所述的一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,其特征在于,步骤3所述空气等离子体处理参数为:时间10-500s,功率50-200W,空气流量为5-200ml/min。
4.根据权利要求1所述的一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,其特征在于,步骤4所述Ni的前驱体为NiCl2、Ni(NO3)2或者Ni(CH3COO)2中的一种。
5.根据权利要求1所述的一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,其特征在于,步骤4所述Ni的前驱体浓度为0.01-10mmol/L。
6.根据权利要求1所述的一种Ni单原子/氧缺陷钨酸铜光阳极的制备方法,其特征在于,步骤4所述NaBH4水溶液浓度为0.1-1mol/L。
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CN110947376B (zh) * | 2019-12-19 | 2021-04-06 | 华中科技大学 | 单原子贵金属锚定缺陷型WO3/TiO2纳米管、其制备和应用 |
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