CN108686645A - 一种TiO2/BiVO4异质结复合材料的制备方法和应用 - Google Patents
一种TiO2/BiVO4异质结复合材料的制备方法和应用 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 16
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229940005561 1,4-benzoquinone Drugs 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229940037003 alum Drugs 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 22
- 239000004065 semiconductor Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 238000006303 photolysis reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WRWQVSOJXAVREP-UHFFFAOYSA-J tetrachlorotitanium hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Cl-].[Cl-].[Ti+4] WRWQVSOJXAVREP-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
本发明涉及一种TiO2/BiVO4异质结复合材料的制备方法和应用。于含有硝酸铋、碘化钾和对苯醌的电沉积溶液中，采用三电极体系，在FTO上沉积BiOI膜，于BiOI膜上均匀滴加乙酰丙酮氧矾的DMSO溶液后，于450℃保温2h，冷却至室温后，放入无机碱溶液中浸泡30min；将得到的钒酸铋基底浸入二氧化钛水溶胶中，60℃保持30‑60min后，在500℃煅烧2h，得TiO2/BiVO4异质结。本发明制备方法简单，采用浸渍的方法，将纳米球状的二氧化钛负载在多孔的钒酸铋上，通过高温煅烧，形成二氧化钛钒酸铋异质结。不仅提高了半导体对光解水的催化活性，而且对于制备其他半导体异质结提供了一种思路。
Description
技术领域
本发明涉及光解水催化体系领域，具体为通过简单的方法制备TiO2/BiVO4异质结复合材料，实现高效光解水制氢。
背景技术
随着能源的日益枯竭，人们在不断地寻找可代替的再生能源。实现人工光合作用，利用太阳能光催化分解水制氢，使太阳能转化为便于人们利用的化学能，对当今社会的可持续发展有着重要的战略意义。光解水产氢，不仅是因为光能是取之不尽用之不完的，而且氢能还是一种绿色能源，其燃烧产物为水，对环境无污染。目前通过太阳光实现光解水产氢产氧已经逐渐热起来。
单独的半导体对水的催化活性低，在光激发电子后，其电子和空穴再结合速率快，所以实现高效的光解水产氢比较困难，但是半导体具有良好的吸光性能，因此人们在不断地修饰改造半导体，用于实现光解水产氢。在半导体表面修饰催化剂是一种提高催化效果的方法，可以修饰一些无机催化剂，用于加速半导体表面的电子传输效率，加快电子转移，提高水分解效率。
半导体材料在实现光解水体系中扮演者越来越重要的角色，使用半导体材料作为光催化体系中的基底，并通过修饰半导体，实现高效分解水已经成为研究热点。然而光催化体系的催化剂大部分是含有贵金属，不仅成本高，而且制备过程比较繁琐复杂。
发明内容
本发明的目的是提供一种方法简单，成本低，将两种半导体复合，形成异质结的一种TiO2/BiVO4异质结复合材料的制备方法。
本发明采用的技术方案是：一种TiO2/BiVO4异质结复合材料的制备方法，包括如下步骤：
1)制备钒酸铋基底：于含有硝酸铋、碘化钾和对苯醌的电沉积溶液中，采用三电极体系，在导电载体FTO上沉积一层BiOI膜，水洗，氮气吹干后，于BiOI膜上均匀滴加乙酰丙酮氧矾的DMSO溶液后，于450℃保持2h，冷却至室温后，放入无机碱溶液中浸泡30min，取出，用水冲洗，氮气吹干，得钒酸铋基底；
2)制备TiO2/BiVO4异质结复合材料：将钒酸铋基底浸入二氧化钛水溶胶中，60℃保持30-60min后，置于马弗炉中500℃煅烧2h。
上述的一种TiO2/BiVO4异质结复合材料的制备方法，所述的电沉积溶液的制备方法是：取适量去离子水，用硝酸调节其pH到1.7，加入硝酸铋和碘化钾，充分溶解后，加入对苯醌的乙醇溶液，充分搅拌，制成电沉积溶液。
上述的一种TiO2/BiVO4异质结复合材料的制备方法，采用三电极体系，沉积条件为：外加-0.1V vs Ag/AgCl的偏压沉积5分钟。
上述的一种TiO2/BiVO4异质结复合材料的制备方法，所述的无机碱为氢氧化钠或氢氧化钾。
上述的一种TiO2/BiVO4异质结复合材料的制备方法，所述的二氧化钛水溶胶的制备方法是：向四氯化钛的盐酸溶液中加入水，静止，待烟雾消失后，离心，去掉上清液，沉淀物加去离子水，超声分散，形成二氧化钛水溶胶。
上述的一种TiO2/BiVO4异质结复合材料的制备方法，所述的离心，转速为10000r/min，离心10分钟。
按照上述的方法制备的TiO2/BiVO4异质结复合材料可作为修饰电极在光催化分解水制氢中的应用。
本发明的有益效果是：
1、本发明，制备方法简单，采用浸渍的方法，将纳米球状的氧化钛负载在多孔的钒酸铋上，通过高温煅烧，形成氧化钛钒酸铋异质结。不仅提高了半导体对光解水的催化活性，而且对于制备其他半导体异质结提供了一种思路。
2、本发明，利用四氯化钛具有水解的特性，将四氯化钛水解为纳米球状的二氧化钛，同时通过电沉积的方法制备半导体钒酸铋，将钒酸铋浸渍在含有二氧化钛的水溶液中，将氧化钛负载在多孔钒酸铋上，通过高温煅烧，最后形成二氧化钛钒酸铋异质结。通过检测所制备的复合物具有良好光催化性能。
3、本发明，将两种半导体制成异质结，使得电子与空穴在半导体之间不断地转移，间接地加快了电荷与空穴的分离效率。进一步地提高了光激发的电子利用率，光能的利用率提高，间接地加速了光催化效率。
4、本发明，基于多孔性的钒酸铋，采用简单的浸渍法很容易将二氧化钛镶嵌在钒酸铋的孔隙中形成异质结，相比于其他的方法，本方法在于操作简单，催化效果显著。
附图说明
图1是多孔钒酸铋的扫描电镜图(SEM)。
图2是二氧化钛水溶胶的纳米粒子的动态光散射图(DLS)。
图3是二氧化钛钒酸铋异质结的扫描电镜图(SEM)。
图4是二氧化钛钒酸铋异质结的X射线光电子能谱图(XPS)全图。
图5是二氧化钛钒酸铋异质结的能谱图(EDS)。
图6是二氧化钛钒酸铋异质结在含有亚硫酸钠的线性扫描图(LSV)。
图7是二氧化钛钒酸铋异质结在磷酸缓冲液中的线性扫描图(LSV)。
具体实施方式
为了更好地理解本发明的技术方案，特以具体的实施例作进一步详细说明，但方案不限于此。
(一)制备方法
1、电沉积溶液的制备
量取150ml去离子水，用硝酸调节其pH到1.7。加入2.91g硝酸铋和9.96g碘化钾，充分溶解后，加入20ml溶有1.49g对苯醌的乙醇溶液，充分搅拌，形成电沉积溶液。
2、钒酸铋基底的制备
采用三电极体系，外加-0.1V vs Ag/AgCl的偏压沉积5分钟，于导电载体FTO上沉积一层BiOI膜，用水清洗BiOI膜，氮气吹干。最后在BiOI膜上均匀滴加50微升的含有1.06g乙酰丙酮氧矾的DMSO溶液，于450℃保持2h。待其冷却到室温后，将其放入0.1M的氢氧化钠溶液中，大约浸泡30min后取出，用水冲洗，氮气吹干，得到淡黄色的多孔的钒酸铋基底。用氢氧化钠水溶液浸泡的目的是溶掉基底表面的五氧化钒等杂质。
3、二氧化钛水溶胶的制备
吸取1ml浓度为99.9％的四氯化钛盐酸溶液，用水稀释到50ml，静止，待烟雾消失后，离心(转速为10000r/min)10分钟，去掉上清液，沉淀物加去离子水再稀释到50ml，超声分散5分钟，形成二氧化钛水溶胶。
4、TiO2/BiVO4异质结复合材料的制备
将钒酸铋基底浸入二氧化钛水溶胶中，60℃保持30-60min后，置于马弗炉中500℃煅烧2h。
(二)检测
1、图1为多孔钒酸铋的扫描电镜图(SEM)。由图1可见，得到的钒酸铋是多孔的、均匀的结构，其孔道可以为二氧化钛的负载提供适当的位置。
2、图2是二氧化钛水溶胶的纳米粒子的动态光散射图(DLS)。由图2可见，二氧化钛的粒径大约在200-500nm之间，进一步证明二氧化钛能进入到钒酸铋的孔道中。
3、图3是二氧化钛钒酸铋异质结的扫描电镜图(SEM)。由图3可见，球状的二氧化钛均匀地负载在多孔状的钒酸铋中。进一步证明本发明的可行性。
4、图4是二氧化钛钒酸铋异质结的X射线光电子能谱图(XPS)全图。由图4可以看到Ti，Bi,V,O,等元素，进一步证明二氧化钛和钒酸铋异质结的形成。
5、图5是二氧化钛钒酸铋异质结的能谱图(EDS)。由图5可见，二氧化钛均匀地分散在多孔状的钒酸铋上。
6、图6是二氧化钛钒酸铋异质结在含有亚硫酸钠的电化学测试图。由图6可见，从图中的Linear Sweep Voltammetry(LSV)curves可以看到复合材料在含有亚硫酸钠的电解液中的光电流比单独的钒酸铋有明显的提高，进一步证明异质结的形成。
7、图7是二氧化钛钒酸铋异质结在磷酸缓冲液中的电化学测试图。由图7可见，从图中的Linear Sweep Voltammetry(LSV)curves可以看出，在磷酸缓冲溶液中，单独的氧化钛与钒酸铋的光催化性能较低，而钒酸铋二氧化钛的异质结其催化性能明显的提高，说明异质结能提高光解水的催化性能。
Claims (7)
1.一种TiO2/BiVO4异质结复合材料的制备方法，其特征在于，包括如下步骤：
1)制备钒酸铋基底：于含有硝酸铋、碘化钾和对苯醌的电沉积溶液中，采用三电极体系，在导电载体FTO上沉积一层BiOI膜，水洗，氮气吹干后，于BiOI膜上均匀滴加乙酰丙酮氧矾的DMSO溶液后，于450℃保温2h，冷却至室温后，放入无机碱溶液中浸泡30min，取出，用水冲洗，氮气吹干，得钒酸铋基底；
2)制备TiO2/BiVO4异质结复合材料：将钒酸铋基底浸入二氧化钛水溶胶中，60℃保持30-60min后，置于马弗炉中500℃煅烧2h。
2.根据权利要求1所述的一种TiO2/BiVO4异质结复合材料的制备方法，其特征在于，所述的电沉积溶液的制备方法是：取适量去离子水，用硝酸调节其pH到1.7，加入硝酸铋和碘化钾，充分溶解后，加入对苯醌的乙醇溶液，充分搅拌，制成电沉积溶液。
3.根据权利要求1所述的一种TiO2/BiVO4异质结复合材料的制备方法，其特征在于，采用三电极体系，沉积条件为：外加-0.1V vs Ag/AgCl的偏压沉积5分钟。
4.根据权利要求1所述的一种TiO2/BiVO4异质结复合材料的制备方法，其特征在于，所述的无机碱为氢氧化钠或氢氧化钾。
5.根据权利要求1所述的一种TiO2/BiVO4异质结复合材料的制备方法，其特征在于，所述的二氧化钛水溶胶的制备方法是：向四氯化钛的盐酸溶液中加入水，静止，待烟雾消失后，离心，去掉上清液，沉淀物加去离子水，超声分散，形成二氧化钛水溶胶。
6.根据权利要求5所述的一种TiO2/BiVO4异质结复合材料的制备方法，其特征在于，所述的离心，转速为10000r/min，离心10分钟。
7.按照权利要求1-6任一项所述的方法制备的TiO2/BiVO4异质结复合材料作为修饰电极在光催化分解水制氢中的应用。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112391651A (zh) * | 2020-09-18 | 2021-02-23 | 厦门大学 | 含氧空穴的BiOBr/TiO2纳米管阵列复合电极及其制备方法和其光电催化固氮应用 |
| CN112538638A (zh) * | 2020-11-19 | 2021-03-23 | 中国科学院海洋研究所 | 一种高效的Bi2MoO6包覆BiVO4异质结光电极体系的制备方法 |
| CN113373470A (zh) * | 2021-05-31 | 2021-09-10 | 深圳先进技术研究院 | 钒酸铋光阳极及其制备方法、光电化学器件 |
| WO2022016768A1 (zh) * | 2020-07-22 | 2022-01-27 | 南京理工大学 | 一种基于光激发空穴为电子受体的生物强化处理难降解有机污染物的方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988533A (zh) * | 2015-06-26 | 2015-10-21 | 湖北大学 | TiO2/BiVO4光阳极材料及其制备方法 |
-
2018
- 2018-05-23 CN CN201810498534.XA patent/CN108686645A/zh active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988533A (zh) * | 2015-06-26 | 2015-10-21 | 湖北大学 | TiO2/BiVO4光阳极材料及其制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| MIAO KAN等: "A highly efficient nanoporous BiVO4 photoelectrode with enhanced interface charge transfer Co-catalyzed by molecular catalyst", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| OLIVIER MONFORT等: "Production of hydrogen by water splitting in a photoelectrochemical cell using a BiVO4/TiO2 layered photoanode", 《ELECTROCHIMICA ACTA》 * |
| 杨保祥等: "《钒基材料制造》", 31 March 2014, 冶金工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022016768A1 (zh) * | 2020-07-22 | 2022-01-27 | 南京理工大学 | 一种基于光激发空穴为电子受体的生物强化处理难降解有机污染物的方法 |
| CN112391651A (zh) * | 2020-09-18 | 2021-02-23 | 厦门大学 | 含氧空穴的BiOBr/TiO2纳米管阵列复合电极及其制备方法和其光电催化固氮应用 |
| CN112391651B (zh) * | 2020-09-18 | 2021-10-26 | 厦门大学 | 含氧空穴的BiOBr/TiO2纳米管阵列复合电极及其制备方法和其光电催化固氮应用 |
| CN112538638A (zh) * | 2020-11-19 | 2021-03-23 | 中国科学院海洋研究所 | 一种高效的Bi2MoO6包覆BiVO4异质结光电极体系的制备方法 |
| CN112538638B (zh) * | 2020-11-19 | 2022-03-08 | 中国科学院海洋研究所 | 一种高效的Bi2MoO6包覆BiVO4异质结光电极体系的制备方法 |
| CN113373470A (zh) * | 2021-05-31 | 2021-09-10 | 深圳先进技术研究院 | 钒酸铋光阳极及其制备方法、光电化学器件 |
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