CN110016691A - 一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法 - Google Patents
一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法 Download PDFInfo
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012528 membrane Substances 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 33
- 238000001354 calcination Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229940071125 manganese acetate Drugs 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 230000005693 optoelectronics Effects 0.000 abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract 2
- 239000010405 anode material Substances 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000004528 spin coating Methods 0.000 description 22
- 229960000935 dehydrated alcohol Drugs 0.000 description 15
- 229960004756 ethanol Drugs 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229940097156 peroxyl Drugs 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241001464837 Viridiplantae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
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Abstract
本发明涉及一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,属于光电催化技术领域。所述的复合光电极能够吸收可见光,在光电催化水分解过程中实现长期稳定运行,是一种极具应用潜力的光阳极材料。该光阳极薄膜的制备方法主要包括以下步骤:140℃水热反应6h,制备WO3薄膜电极;配置铁盐的胶体溶液,将该胶体溶液旋涂在WO3薄膜表面,高温煅烧,即得WO3/Fe2O3薄膜电极;然后水热制备Mn3O4纳米颗粒,超声分散于乙醇溶液中,进一步旋涂至WO3/Fe2O3薄膜电极表面,N2气氛下高温煅烧,即得三元复合光电极材料。该复合光电极制备所需原料地球储量丰富,成本低廉,在能源领域具有较好的应用前景。
Description
技术领域
本发明涉及一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,属于光电催化技术领域,更加具体的是本发明提供了一种具有高光电催化活性、高稳定性和高选择性的WO3/Fe2O3/Mn3O4三元复合光电极的制备方法。
背景技术
光电催化水分解技术是利用太阳能制备燃料的绿色环保途径,它利用半导体光电极材料吸收太阳能,在少量偏压的协助下,就能有效抑制光生载流子的复合,实现高效的水分解制氢。由于氧化和还原两个反应在空间上分离,氢气和氧气分别在阴阳两极析出,避免了H2和O2的直接接触,有效避免了爆炸风险。光电催化技术是目前极为有效的氢能制备方法,对解决未来能源危机提供了一条重要的解决途径,相应的高活性、高选择性半导体光电极材料成为近年来能源与材料领域的研究热点。
WO3的带隙为2.6eV,理论上可以吸收12%的太阳光,成为近年来的明星半导体材料。但是,WO3的稳定性较差,严重限制了其光电催化应用。在pH值大于4的溶液中,WO3会与溶液中的OH-离子反应而发生化学溶解;光照时,WO3的光生空穴氧化水,表面会产生过氧物种,生成的过氧物种会与水氧化反应竞争,降低H2的产量。且过氧物种的累积,导致WO3稳定性下降。因此,提高WO3在碱性溶液中的稳定性,抑制光照下过氧物种的产生,对WO3的商业化应用具有重要的意义。Fe2O3是另一种可见光半导体材料,自然界中储量丰富,能够在碱性溶液中稳定存在,且光照下难以光腐蚀,已成为最具应用前景的光电极材料。通过旋涂法将Fe2O3负载在WO3光电极表面,能够避免WO3与溶液的直接接触,还能避免过氧物种在WO3表面的累计,有望大幅提高WO3光电极的稳定性和产物选择性。Mn3O4是一种氧析出助催化剂,广泛存在于绿色植物光合作用过程中,进一步采用Mn3O4修饰WO3/Fe2O3,可以促进WO3/Fe2O3界面空穴转移速率,进而提高水分解效率。该制备方法均采用自然界储量丰富的元素作为原料,成本低廉,制备过程简单,有望实现WO3光电极的商业化应用。
发明内容
本发明的目的在于提供一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,本发明的目的通过以下操作步骤实现:
1)WO3薄膜电极的制备:将0.12g钨酸钠溶解于15ml水溶液中,滴加1.25ml浓盐酸;然后,将0.11g草酸铵溶解于15ml水溶液中,缓慢加入到上述钨酸钠溶液中,搅拌30min;放入FTO导电玻璃,140℃下水热反应6h,自然冷却后水洗,自然干燥,500℃下煅烧2h;
2)WO3/Fe2O3薄膜电极的制备:取一定量的无机铁盐,溶解于乙醇溶液中,控制铁盐的浓度为5-100mmol/L;将WO3薄膜电极固定于旋涂仪上,低速旋转,用移液器移取100μL铁盐溶液,逐滴滴加到WO3薄膜电极表面;空气中干燥,后转入350℃马弗炉中煅烧5min,重复该步骤1-7次;
3)WO3/Fe2O3/Mn3O4薄膜电极的制备:将乙酸锰溶解于乙醇溶液中,浓度为10-200mmol/L,120-200℃条件下水热2-24h,得到Mn3O4的纳米颗粒,离心分离,60℃干燥过夜,研磨,得Mn3O4纳米颗粒;称取1.6-32mg Mn3O4加入到40ml乙醇溶液中,超声分散,移取100μL该溶液旋涂于WO3/Fe2O3薄膜电极上,室温下干燥,在N2保护气氛下煅烧,煅烧温度为200-350℃,煅烧时间为0.5-5h。
本发明引入Fe2O3来修饰WO3,能够避免WO3在碱性溶液中的化学溶解,同时可避免水分解过程中过氧物种的累积,进而大幅提高WO3光电极的稳定性和氢气析出的选择性。进一步将Mn3O4旋涂于WO3/Fe2O3表面,促进了WO3/Fe2O3电极界面的空穴转移,有效提高了光电催化水分解效率。该技术方案操作简单,成本低廉,适用于大规模制备WO3/Fe2O3/Mn3O4薄膜电极;特别地,该电极可实现长时间光电催化产氢,能够破解WO3商业应用的困局,在未来能源领域具有广阔的应用前景。
附图说明
图1为实施例一中制备的WO3/Fe2O3/Mn3O4薄膜的X射线衍射图谱。
图2为实施例二中制备的WO3、WO3/Fe2O3和WO3/Fe2O3/Mn3O4薄膜的紫外可见漫反射图谱;
图3为实施例三中制备的WO3和WO3/Fe2O3/Mn3O4薄膜的扫描电镜图;
图4为实施例四中制备的WO3/Fe2O3和WO3/Fe2O3/Mn3O4薄膜的线性扫描伏安曲线图;
图5为实施例五中制备的WO3、WO3/Fe2O3和WO3/Fe2O3/Mn3O4薄膜电极在0.5V
(vs.Ag/AgCl)电位下的电流-时间曲线图;
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WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,具体步骤如下:
将0.12g钨酸钠溶解于15ml水溶液中,滴加1.25ml浓盐酸;然后,将0.11g草酸铵溶解于15ml水溶液中,缓慢加入到上述钨酸钠溶液中,搅拌30min;转移至50ml水热反应釜中,放入FTO导电玻璃,140℃下水热6h,冷却,水洗,空气中干燥,500℃下煅烧2h,即得WO3薄膜电极;称取0.81g的FeCl3,加入50mL的乙醇,搅拌30min,得到FeCl3胶体溶液,再往WO3薄膜上旋涂100μL上述胶体,旋涂后取下导电玻璃在室温下干燥,接着放入马弗炉中350℃煅烧5min,取出再旋涂,重复上述操作1次;称取0.88g乙酸锰,溶解到40ml无水乙醇中,转移到100ml反应釜中,180℃水热反应11h,自然冷却,离心分离,用无水乙醇反复洗涤,60℃下干燥,即得Mn3O4纳米颗粒;称取5mg的上述Mn3O4纳米颗粒,加入10ml的无水乙醇,超声分散;在WO3/Fe2O3薄膜电极表面旋涂100μL上述Mn3O4分散液,室温下干燥,氮气气氛下300℃煅烧2h,即得WO3/Fe2O3/Mn3O4复合光阳极。
图1给出了WO3和WO3/Fe2O3/Mn3O4复合光阳极薄膜的X射线衍射图谱,经Jade软件检索可发现WO3、Fe2O3以及SnO2的衍射峰,其中,SnO2为四方晶系,来自于FTO导电玻璃;而WO3和Fe2O3很好的匹配为单斜晶系。此外,未出现Mn3O4的晶相,很可能因为Mn3O4含量太低或者结晶度不好。
实施例二
一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,具体步骤如下:
将0.12g钨酸钠溶解于15ml水溶液中,滴加1.25ml浓盐酸;然后,将0.11g草酸铵溶解于15ml水溶液中,缓慢加入到上述钨酸钠溶液中,搅拌30min;转移至50ml水热反应釜中,放入FTO导电玻璃,140℃下水热6h,冷却,水洗,空气中干燥,500℃下煅烧2h,即得WO3薄膜电极;称取1g的硝酸铁,加入50mL的乙醇,搅拌30min,得到硝酸铁胶体溶液,再往WO3薄膜上旋涂100μL上述胶体,旋涂后取下导电玻璃在室温下干燥,接着放入马弗炉中350℃煅烧5min,取出再旋涂,重复上述操作1次;称取0.7g乙酸锰,溶解到40ml无水乙醇中,转移到100ml反应釜中,160℃水热反应12h,自然冷却,离心分离,用无水乙醇反复洗涤,60℃下干燥,即得Mn3O4纳米颗粒;称取5mg的上述Mn3O4纳米颗粒,加入10ml的无水乙醇,超声分散;在WO3/Fe2O3薄膜电极表面旋涂100μL上述Mn3O4分散液,室温下干燥,氮气气氛下300℃煅烧2h,即得WO3/Fe2O3/Mn3O4复合光阳极。
图2给出了WO3、WO3/Fe2O3和WO3/Fe2O3/Mn3O4薄膜的紫外可见漫反射图,由图可知,450nm处出现了WO3的带边吸收,表明WO3是一种可见光半导体。当Fe2O3旋涂至WO3表面后,WO3带边吸收明显红移,600nm波长以下产生明显的光吸收,说明Fe2O3的带隙较WO3更小,而Mn3O4负载之后,480-700nm处的光吸收增加,这是因为Mn3O4为黑色,可以有效拓展WO3/Fe2O3的光吸收范围,但是由于Mn3O4的负载量较低,因此吸收度增加较小。
实施例三
一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,具体步骤如下:
将0.12g钨酸钠溶解于15ml水溶液中,滴加1.25ml浓盐酸;然后,将0.11g草酸铵溶解于15ml水溶液中,缓慢加入到上述钨酸钠溶液中,搅拌30min;转移至50ml水热反应釜中,放入FTO导电玻璃,140℃下水热6h,冷却,水洗,空气中干燥,500℃下煅烧2h,即得WO3薄膜电极;称取0.6g的硫酸铁,加入50mL的乙醇,搅拌30min,得到硫酸铁胶体溶液,再往WO3薄膜上旋涂100μL上述胶体,旋涂后取下导电玻璃在室温下干燥,接着放入马弗炉中350℃煅烧5min,取出再旋涂,重复上述操作2次;称取0.6g乙酸锰,溶解到40ml无水乙醇中,转移到100ml反应釜中,150℃水热反应15h,自然冷却,离心分离,用无水乙醇反复洗涤,60℃下干燥,即得Mn3O4纳米颗粒;称取10mg的上述Mn3O4纳米颗粒,加入10ml的无水乙醇,超声分散;在WO3/Fe2O3薄膜电极表面旋涂100μL上述Mn3O4分散液,室温下干燥,氮气气氛下250℃煅烧3h,即得WO3/Fe2O3/Mn3O4复合光阳极。
图3给出了WO3和WO3/Fe2O3/Mn3O4复合光阳极薄膜的扫描电镜图,由图可知,140℃水热生长6h的WO3形貌很均匀,呈现板状结构,且这些板状结构垂直分布在FTO导电玻璃之上,增加了半导体与溶液的接触面积,有利于水分解产物的扩散。而Fe2O3胶体旋涂至WO3表面之后,使WO3表面厚度增加,且表面粗糙度减少,表明Fe2O3可以有效覆盖在WO3表面,从而减少WO3与溶液的接触,从而有效避免WO3的化学溶解。
实施例四
一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,具体步骤如下:
将0.12g钨酸钠溶解于15ml水溶液中,滴加1.25ml浓盐酸;然后,将0.11g草酸铵溶解于15ml水溶液中,缓慢加入到上述钨酸钠溶液中,搅拌30min;转移至50ml水热反应釜中,放入FTO导电玻璃,140℃下水热6h,冷却,水洗,空气中干燥,500℃下煅烧2h,即得WO3薄膜电极;称取0.81g的FeCl3,加入50mL的乙醇,搅拌30min,得到FeCl3胶体溶液,再往WO3薄膜上旋涂100μL上述胶体,旋涂后取下导电玻璃在室温下干燥,接着放入马弗炉中350℃煅烧5min,取出再旋涂,重复上述操作2次;称取0.5g乙酸锰,溶解到40ml无水乙醇中,转移到100ml反应釜中,170℃水热反应15h,自然冷却,离心分离,用无水乙醇反复洗涤,60℃下干燥,即得Mn3O4纳米颗粒;称取10mg的上述Mn3O4纳米颗粒,加入10ml的无水乙醇,超声分散;在WO3/Fe2O3薄膜电极表面旋涂100μL上述Mn3O4分散液,室温下干燥,氮气气氛下300℃煅烧3h,即得WO3/Fe2O3/Mn3O4复合光阳极。
图4为pH为7磷酸钾缓冲液(0.1mol/L)中测试的WO3/Fe2O3和WO3/Fe2O3/Mn3O4薄膜的线性扫描伏安曲线图,由图可知,暗态下,两个电极的电流均很小。光照时,0V左右开始出现光电流,且两个电极的光电流均随着电压的增加而增大,但是Mn3O4存在时,WO3/Fe2O3的光电流明显增加,表明Mn3O4能够促进WO3/Fe2O3光电催化水分解,进一步表明Mn3O4是一种很有应用前景的氧析出催化剂。
实施例五
一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,具体步骤如下:
将0.12g钨酸钠溶解于15ml水溶液中,滴加1.25ml浓盐酸;然后,将0.11g草酸铵溶解于15ml水溶液中,缓慢加入到上述钨酸钠溶液中,搅拌30min;转移至50ml水热反应釜中,放入FTO导电玻璃,140℃下水热6h,冷却,水洗,空气中干燥,500℃下煅烧2h,即得WO3薄膜电极;称取0.6g的FeCl3,加入50mL的乙醇,搅拌30min,得到FeCl3胶体溶液,再往WO3薄膜上旋涂100μL上述胶体,旋涂后取下导电玻璃在室温下干燥,接着放入马弗炉中350℃煅烧5min,取出再旋涂,重复上述操作3次;称取0.5g乙酸锰,溶解到40ml无水乙醇中,转移到100ml反应釜中,180℃水热反应15h,自然冷却,离心分离,用无水乙醇反复洗涤,60℃下干燥,即得Mn3O4纳米颗粒;称取8mg的上述Mn3O4纳米颗粒,加入10ml的无水乙醇,超声分散;在WO3/Fe2O3薄膜电极表面旋涂100μL上述Mn3O4分散液,室温下干燥,氮气气氛下250℃煅烧4h,即得WO3/Fe2O3/Mn3O4复合光阳极。
图5给出了WO3、WO3/Fe2O3和WO3/Fe2O3/Mn3O4薄膜电极在0.5V(vs.Ag/AgCl)电位下的电流-时间曲线图,由图可知,WO3电极的稳定性很差,光电流随着时间的增加快速衰减,但是负载Fe2O3后,WO3电极的稳定性明显改善,光电流能够维持长时间的稳定,而Mn3O4负载后光电流进一步增加,该复合光电极的稳定性依然很好,有望实现商业应用。
Claims (7)
1.一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,其特征在于包括以下步骤:
1)将0.12g钨酸钠溶解于15ml水溶液中,滴加1.25ml浓盐酸;然后,将0.11g草酸铵溶解于15ml水溶液中,缓慢加入到上述钨酸钠溶液中,搅拌30min;转移至50ml水热反应釜中,放入FTO导电玻璃,140℃下水热6h,自然冷却,取出FTO玻璃,水洗,空气中干燥,500℃下煅烧2h,即得WO3薄膜电极;
2)配置无机铁盐的乙醇溶液,移取100μL该溶液旋涂于WO3薄膜电极上,室温下干燥,放入350℃马弗炉中煅烧5min,重复该步骤1-7次,即得WO3/Fe2O3薄膜电极;
3)配置乙酸锰的乙醇溶液,不同温度下水热反应,自然冷却,离心,醇洗,40-100℃下干燥,得到Mn3O4的纳米颗粒;
4)将上述Mn3O4纳米颗粒分散于乙醇溶液中,超声,移取100μL该溶液旋涂于WO3/Fe2O3薄膜电极上,室温下干燥,N2气氛下煅烧,即得WO3/Fe2O3/Mn3O4复合光阳极薄膜。
2.根据权利要求1所述的一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,其特征在于所述步骤2使用的无机铁盐是氯化铁、硝酸铁、硫酸铁中的一种或几种。
3.根据权利要求1所述的一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,其特征在于步骤2所述铁盐浓度为5-100mmol/L。
4.根据权利要求1所述的一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,其特征在于,步骤3所述的乙酸锰溶液浓度为10-200mmol/L。
5.根据权利要求1所述的一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,其特征在于,步骤3所述水热温度为120-200℃,水热时间为2-24h。
6.根据权利要求1所述的一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,其特征在于步骤4所述Mn3O4纳米颗粒质量分数为5-50wt%。
7.根据权利要求1所述的一种WO3/Fe2O3/Mn3O4复合光阳极薄膜的制备方法,其特征在于,步骤4所述N2煅烧温度为200-350℃,升温速率为1-10℃/min,煅烧时间为0.5-5h。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110273165A (zh) * | 2019-07-24 | 2019-09-24 | 台州学院 | 一种低温等离子体技术制备氧缺陷型钨酸铋光电极的方法 |
CN110565111A (zh) * | 2019-07-24 | 2019-12-13 | 台州学院 | 一种六角柱型WO3/Bi2WO6复合光电极薄膜的制备方法 |
JP2021070850A (ja) * | 2019-10-31 | 2021-05-06 | 国立研究開発法人産業技術総合研究所 | 光電極、電気分解装置および酸素の製造方法 |
CN113145136A (zh) * | 2021-03-31 | 2021-07-23 | 天津城建大学 | 一种用于光电催化降解污染物的WO3/CdS/MoS2复合薄膜的制备方法 |
CN116251583A (zh) * | 2023-02-01 | 2023-06-13 | 四川农业大学 | 一种WO3/Mn3O4纳米酶的制备方法及其应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070020400A1 (en) * | 2005-07-22 | 2007-01-25 | State of Oregon acting by and through the State Board of Higher Education on behalf of Oregon | Method and apparatus for chemical deposition |
US20130168228A1 (en) * | 2011-04-12 | 2013-07-04 | Geoffrey A. Ozin | Photoactive Material Comprising Nanoparticles of at Least Two Photoactive Constituents |
EP2743946A2 (en) * | 2012-12-13 | 2014-06-18 | Instytut Technologii Materialów Elektronicznych | Use of Material, Especially an Eutectic One, as an Active Layer in an Electrode and an Electrode Comprising an Active Layer of Material, Especially an Eutectic One |
CN105384358A (zh) * | 2015-10-29 | 2016-03-09 | 上海交通大学 | 一种wo3纳米片阵列薄膜制备方法及其应用研究 |
-
2019
- 2019-04-02 CN CN201910263323.2A patent/CN110016691B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070020400A1 (en) * | 2005-07-22 | 2007-01-25 | State of Oregon acting by and through the State Board of Higher Education on behalf of Oregon | Method and apparatus for chemical deposition |
US20130168228A1 (en) * | 2011-04-12 | 2013-07-04 | Geoffrey A. Ozin | Photoactive Material Comprising Nanoparticles of at Least Two Photoactive Constituents |
EP2743946A2 (en) * | 2012-12-13 | 2014-06-18 | Instytut Technologii Materialów Elektronicznych | Use of Material, Especially an Eutectic One, as an Active Layer in an Electrode and an Electrode Comprising an Active Layer of Material, Especially an Eutectic One |
CN105384358A (zh) * | 2015-10-29 | 2016-03-09 | 上海交通大学 | 一种wo3纳米片阵列薄膜制备方法及其应用研究 |
Non-Patent Citations (5)
Title |
---|
GUIMIN AN等: ""low temperature synthesis of Mn3O4 nanoparticles loaded on multi-walled carbon nanotubes and their application in electrochemical capacitors"", 《NANOTECHNOLOGY》 * |
JIAO YANG等: ""hydrothermal synthesis and photoelectrochemical properties of vertically aligned tungsten trioxide(hydrate) plate-like arrays fabricated directly on FTO substrates"", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
WENJUN LUO等: ""Enhanced photocurrent-volage characteristics of WO3/Fe2O3 nano-electrodes"", 《JOURNAL OF PHYSICS D:APPLIED PHYSICS》 * |
YING LIU等: ""An operando investigation of Mn3O4+δ co-catalyst on Fe2O3 photoanode: Mn-Valancy determined enhancement at varied potentials "", 《ACS APPLIED ENERGY MATERIALS》 * |
YUAN LI等: ""WO3@α-Fe2O3 heterojunction arrays with improved photoelectrochemical behavior for neutral pH water splitting"", 《CHEM CATCHEM》 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110273165A (zh) * | 2019-07-24 | 2019-09-24 | 台州学院 | 一种低温等离子体技术制备氧缺陷型钨酸铋光电极的方法 |
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JP2021070850A (ja) * | 2019-10-31 | 2021-05-06 | 国立研究開発法人産業技術総合研究所 | 光電極、電気分解装置および酸素の製造方法 |
JP7376913B2 (ja) | 2019-10-31 | 2023-11-09 | 国立研究開発法人産業技術総合研究所 | 電気分解装置 |
CN113145136A (zh) * | 2021-03-31 | 2021-07-23 | 天津城建大学 | 一种用于光电催化降解污染物的WO3/CdS/MoS2复合薄膜的制备方法 |
CN116251583A (zh) * | 2023-02-01 | 2023-06-13 | 四川农业大学 | 一种WO3/Mn3O4纳米酶的制备方法及其应用 |
CN116251583B (zh) * | 2023-02-01 | 2024-02-13 | 四川农业大学 | 一种WO3/Mn3O4纳米酶的制备方法及其应用 |
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