CN110983362B - 一种MOFs包覆的OV-BiVO4复合光阳极及其制备方法和应用 - Google Patents
一种MOFs包覆的OV-BiVO4复合光阳极及其制备方法和应用 Download PDFInfo
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- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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Abstract
本发明公开了一种MOFs均匀包覆的OV‑BiVO4复合光阳极的制备方法，包括如下步骤：(1)通过电化学沉积‑热处理的方法制备BiVO4纳米阵列；(2)将步骤(1)得到的BiVO4纳米片阵列置于含氢气气氛中灼烧得到OV‑BiVO4；(3)将步骤(2)得到的OV‑BiVO4进行表面阴离子化处理后，通过水热法将MOFs包覆到OV‑BiVO4表面。本发明通过溶剂热法将MOFs包覆在经表面阴离子化处理后的OV‑BiVO4的表面，MOFs的表面包覆一方面可以快速转移其与OV‑BiVO4界面的空穴，实现高效的电荷分离；另外，可以保护氧空位，增强稳定性。
Description
技术领域
本发明涉及纳米材料制备和光电催化技术领域，具体涉及一种MOFs包覆的OV-BiVO4复合光阳极及其制备方法和在光电催化分解水中的应用。
背景技术
随着工业的飞速发展，一方面能源消耗巨大，人类面临着能源短缺的威胁；另一方面，化石能源的使用造成了严重的环境污染。因此开发和利用新型能源成为各国科学家的研究焦点。其中，氢气具有能量密度高，来源广，环境友好的特点，被认为未来替代化石能源的潜在能源材料。光电催化分解水制氢技术的应用被认为是解决能源问题的一种有效途径。 BiVO4作为一种新型的可见光响应光催化剂，具有独特的电子结构、较窄的禁带宽度和合适的能带位置，并具有较高的热稳定性和化学稳定性，被广泛的应用于光电催化分解水的研究。但其光生电子和空穴的快速复合较为严重，并且对水的氧化能力不足制约了BiVO4的实际应用。研究者采用了大量的方法对BiVO4进行了改性研究，其中包括元素掺杂(Mo[1]，W[2])，氧空位的引入[3]，助催化剂表面修饰[4]等。元素掺杂能够促进BiVO4的导电性，进而促进光生电子-空穴的分离。但是元素掺杂通常需要复杂的制备过程，并且需要引入其他金属，增加制备成本，不利于大规模应用。氧空位的引入一方面能够增强BiVO4的导电性，另一方面氧空位具有较强的对水分子的吸附和活化作用。但是具有氧空位的BiVO4在光电水氧化过程中表现出较差的稳定性[5]。这是由于水氧化过程中产生大量的氧气，氧气可以填充到氧空位中使其失去活性，因此氧空位的稳定是保持其活性的关键。另外，助催化剂的表面修饰是促进电子-空穴分离和提高产氧动力学的有效方法。但是文献报道的多数助催化剂以颗粒的形式负载到BiVO4的表面，助催化剂与BiVO4接触面较小，不利于电子-空穴的高效分离[1]。另外，BiVO4与电解质接触时会造成溶解，使其活性降低。核壳结构的设计能够实现高效的电子传输，提高光阳极的活性和稳定性[6]。但是目前制备核壳结构光阳极的方法较为单一，主要是光沉积法[7]，表面活性剂辅助的溶剂热法[6]。上述两种方法存在较大问题，其中光沉积法只适用于几类核壳结构的制备，普适性较差。另外，表面活性剂作为表面配位基团合成的核壳结构光阳极的稳定性较差。
参考文献
[1]Y.Shi,Y.Yu,Y.Yu,Y.Huang,B.Zhao,B.Zhang,BoostingPhotoelectrochemical Water Oxidation Activity and Stability of Mo-Doped BiVO4through the Uniform Assembly Coating of NiFe–Phenolic Networks,ACS EnergyLetters,3(2018)1648-1654.
[2]J.-S.Ma,L.-Y.Lin,Y.-S.Chen,Facile solid-state synthesis forproducing molybdenum and tungsten co-doped monoclinic BiVO4 as thephotocatalyst for photoelectrochemical water oxidation,International Journalof Hydrogen Energy,44(2019)7905-7914.
[3]J.-W.Jang,D.Friedrich,S.Müller,M.Lamers,H.Hempel,S.Lardhi,Z.Cao,M.Harb,L.Cavallo,R.Heller, R.Eichberger,R.van de Krol,F.F.Abdi,EnhancingCharge Carrier Lifetime in Metal Oxide Photoelectrodes through Mild HydrogenTreatment,Advanced Energy Materials,7(2017).
[4]D.K.Lee,K.-S.Choi,Enhancing long-term photostability of BiVO4photoanodes for solar water splitting by tuning electrolyte composition,Nature Energy,3(2017)53-60.
[5]R.Zhang,Y.-C.Zhang,L.Pan,G.-Q.Shen,N.Mahmood,Y.-H.Ma,Y.Shi,W.Jia,L.Wang,X.Zhang,W. Xu,J.-J.Zou,Engineering Cobalt Defects in Cobalt Oxide forHighly Efficient Electrocatalytic Oxygen Evolution, ACS Catalysis,8(2018)3803-3811.
[6]Y.-J.Dong,J.-F.Liao,Z.-C.Kong,Y.-F.Xu,Z.-J.Chen,H.-Y.Chen,D.-B.Kuang,D.Fenske,C.-Y.Su, Conformal coating of ultrathin metal-organicframework on semiconductor electrode for boosted photoelectrochemical wateroxidation,Applied Catalysis B:Environmental,237(2018)9-17.
[7]B.Zhang,L.Wang,Y.Zhang,Y.Ding,Y.Bi,Ultrathin FeOOH Nanolayers withAbundant Oxygen Vacancies on BiVO4 Photoanodes for Efficient Water Oxidation,Angewandte Chemie,57(2018)2248-2252.
发明内容
为了解决现有技术中存在的问题，本发明的目的是在于提供了一种MOFs均匀包覆的 OV-BiVO4复合光阳极的制备方法，通过溶剂热法将MOFs包覆在经表面阴离子化处理后的OV-BiVO4的表面，MOFs的表面包覆一方面可以快速转移其与OV-BiVO4界面的空穴，实现高效的电荷分离；另外，可以保护氧空位，增强稳定性。
为了实现上述技术目的，本发明提供了一种MOFs包覆的OV-BiVO4复合光阳极的制备方法，包括如下步骤：
(1)通过电化学沉积-阴离子交换的方法制备BiVO4纳米片阵列；
(2)将步骤(1)得到的BiVO4纳米片阵列置于含氢气气氛中灼烧得到OV-BiVO4；
(3)将步骤(2)得到的OV-BiVO4进行表面阴离子化处理后，通过水热法将MOFs包覆到OV-BiVO4表面。
本发明中的BiVO4纳米阵列可参照现有技术制得，具体制备过程为：将0.97g Bi(NO3)3·5H2O溶于50ml 0.4M KI溶液中，搅拌10min，超声20min，加入浓硝酸调pH至1.6～1.7；再加入20ml 0.23M对苯醌乙醇溶液，搅拌5min；以FTO为工作电极，Ag/AgCl 为参比电极，Pt为对电极，分别施加-0.1V的电压，电沉积时间为300s，然后再沉积300s， 80℃干燥12h得到BiOI光电极备用；将0.2ml 0.2M乙酰丙酮氧钒(Vo(acac)2)的二甲基亚砜(DMSO)溶液滴加到BiOI光电极上，450℃处理2h(升温速率为2℃/min)，最后用1M NaOH除去电极表面残余的V2O5，80℃干燥12h后得到BiVO4纳米阵列。
优选的，步骤(2)中，所述含氢气气氛为H2气氛或H2/Ar混合气气氛，灼烧温度为300℃，灼烧时间为10min。
优选的，步骤(3)中，将OV-BiVO4浸泡在含有邻位酚羟基的羧酸醇溶液中，静置进行表面阴离子化处理，所述含有邻位酚羟基的羧酸为单宁酸、咖啡酸或没食子酸，所述醇为甲醇或乙醇，羧酸醇溶液的浓度为2～10mg/ml。
优选的，步骤(3)中，所述MOFs为单金属-有机骨架或双金属-有机骨架，单金属为钴、铁或镍；双金属为镍铁或钴铁。
更优选的，所述MOFs为双金属-有机骨架，镍铁的摩尔比为0.5～2：1，优选为1：1；钴铁的摩尔比为0.5～2：1，优选为1：1。发明人发现，与单金属MOF相比，双金属MOF 具有更好的导电性和更丰富的活性位点。
本发明中通过溶剂热法将MOFs包覆到OV-BiVO4表面可参照现有技术制得，先制得MOFs的前驱体溶液，再将OV-BiVO4置于前驱体溶液中，于120℃溶剂热处理20h，经水洗、干燥后即得MOFs包覆的OV-BiVO4复合光阳极。
优选的，步骤(3)中，所述MOFs包覆的OV-BiVO4复合光阳极是以OV-BiVO4为“核”，MOFs为“壳”的“核壳结构”，MOFs的包覆厚度为10-20nm。
本发明还提供了上述MOFs包覆的OV-BiVO4复合光阳极的应用，将其用于光电催化分解水。
本发明采用含有邻位酚羟基的羧酸(单宁酸、咖啡酸和没食子酸)为表面配位基团，构筑了MOFs/Ov-BiVO4。基于邻羟基与Ov-BiVO4的配位作用，单宁酸、咖啡酸或没食子酸能够牢牢地锚定在Ov-BiVO4的表面。同时Ni2+、Fe3+或者Co2+与单宁酸、咖啡酸或没食子酸上的羧基配位，在溶剂热条件下，可以形成均匀的MOFs/Ov-BiVO4核壳结构光阳极。MOFs的表面包覆一方面可以快速转移其与OV-BiVO4界面的空穴，实现高效的电荷分离；另外，可以保护氧空位，增强稳定性。Fe，Ni或者Co作为活性位点能够有效地促进水的氧化，提高水分解速率。
与现有技术相比，本发明的优点：
本发明首先以简单的电化学沉积-阴离子交换法制备了BiVO4纳米阵列，有效防止了BiVO4的片层堆积，并且在含氢气气氛中灼烧引入氧空位，提高BiVO4导电性。然后采用含有邻位酚羟基的羧酸(单宁酸、咖啡酸和没食子酸)作为表面修饰剂，基于邻位酚羟基与BiVO4的配位作用以及羧基与金属离子的配位作用，采用溶剂热法在OV-BiVO4表面均匀包覆MOFs。MOFs的厚度在10-20nm之间，一方面有效防止OV-BiVO4在电解质溶液中发生溶解，进一步保护氧空位；另一方面有效转移界面的空穴，提高电荷转移效率；同时金属元素(Co、Ni、Fe元素)作为活性位点能够有效促进水的氧化，增强光电催化水分解活性。
附图说明
图1为实施例1(a)、实施例8(b)和实施例9(c)制得的样品B1,B 2,MOB-0的TEM图；
图2为实施例1制得的BiOI、BiVO4、Ov-BiVO4和MOB-0样品的XRD图；
图3为实施例1制得的BiVO4、Ov-BiVO4、MOB-0样品、实施例8制得的B1样品和实施例9制得的B2样品的光电流-电压(J-V)曲线。
图4为实施例1制得的BiVO4、Ov-BiVO4、MOB-0样品、实施例8制得的B1样品和实施例9制得的B2样品的交流阻抗(EIS)谱。
如图1所示，NiFe-MOF均匀地包覆在Ov-BiVO4的表面形成核壳结构，与单宁酸和没食子酸相比，以咖啡酸为表面改性剂制备的NiFe-MOF/Ov-BiVO4界面更加紧密。
如图2所示，电沉积法制备的BiOI为四方晶型，然后在高温条件下BiOI与乙酰丙酮钒(VO(acac)2)反应生成单斜晶型BiVO4。与BiVO4相比，Ov-BiVO4的谱图中没有出现其他特征衍射峰，说明含氢气气氛下热处理没有改变BiVO4的晶型，NiFe-MOF/Ov-BiVO4中没有观察到NiFe-MOF的特征衍射峰，说明表面包覆的NiFe-MOF为无定型结构。
如图3所示，氧空位的引入有效提高了BiVO4的光电催化活性，与BiVO4相比，Ov-BiVO4光电催化分解水的起始电位下降了200mV。表面包覆NiFe-MOF以后，Ov-BiVO4的活性进一步提高。其中，以咖啡酸为表面改性剂制备的NiFe-MOF/Ov-BiVO4具有最佳的光电催化活性，1.23V vs RHE电压下电流密度达到5.3mA cm-2。
如图4所示，与未处理的BiVO4相比，Ov-BiVO4的阻抗明显变小，NiFe-MOF/Ov-BiVO4表现出更加的导电性，与其光电催化活性一致。说明NiFe-MOF与Ov-BiVO4界面形成的异质结能够有效促进电子-空穴的转移。
具体实施方式
下面结合实施例对本发明做进一步详细说明，但本发明的保护范围并不局限于这些实施例。
本发明通过光电催化分解水来评价MOFs/OV-BiVO4的活性，所用的电解质溶液为pH＝8.5的0.5M混合硼酸钾溶液；光源采用300W氙灯配有AM 1.5滤光片和匀光器，通过控制光源与光阳极的距离，使光强为100mW/cm2；外加电源通过辰华660E电化学工作站提供。反应产生的氢气和氧气采用气相色谱定量。
实施例1
本发明以改变NiFe-MOF中金属元素比例,表面改性剂浓度及其种类在OV-BiVO4表面的包覆MOFs，制备复合光阳极：
BiVO4纳米阵列的制备：将0.97g Bi(NO3)3·5H2O溶于50ml 0.4M KI溶液中，搅拌10 min，超声20min，用浓硝酸将上述混合液的pH调为1.6～1.7。然后再将20ml 0.23M对苯醌乙醇溶液滴加到上述混合液，搅拌5min。首先采用电沉积法制备BiOI光电极：以FTO 为工作电极，Ag/AgCl为参比电极，Pt为对电极，分别施加-0.1V的电压，电沉积时间为300s，然后再沉积300s，得到BiOI光电极。之后将BiOI光电极在80℃真空干燥箱中干燥12h。将0.2ml0.2M乙酰丙酮氧钒(Vo(acac)2)的二甲基亚砜(DMSO)溶液滴加到BiOI电极上，450℃处理2h(升温速率为2℃/min)。然后，用1M NaOH出去电极表面残余的V2O5， 80℃干燥12h；
氧空位的形成：将制备的BiVO4光阳极置于管式炉中，在H2/Ar-6％混合气气氛中300℃热处理10min，管式炉的升温速率为5℃/min，所制备的样品记为Ov-BiVO4。
Ov-BiVO4表面处理：将Ov-BiVO4光阳极置于5mg/ml咖啡酸乙醇溶液中，浸泡3h，然后用无水乙醇冲洗一次，备用。
核壳结构NiFe-MOF/Ov-BiVO4的制备：将133mg对苯二甲酸，86.4mg六水三氯化铁(FeCl3·6H2O)和92.1mg六水合硝酸镍(Ni(NO3)2·6H2O)溶解于20ml N,N-二甲基甲酰胺(DMF)中。搅拌30min后，将上述混合液转移至40ml聚四氟乙烯晶化釜。然后将咖啡酸处理过的Ov-BiVO4光阳极置于上述晶化釜中(FTO导电面向下)，放入烘箱中保温处理120℃ 20h。之后，将晶化釜自然冷却至室温，用去离子水冲洗三次后，置于烘箱中80℃干燥12h，所得样品记为MOB-0。
以光电催化分解水为模型反映考察所制备的光催化剂的催化活性：
所用的电解质溶液为PH＝8.5的0.5M硼酸钾溶液。光源采用300W氙灯配有AM 1.5滤光片和匀光器，通过控制光源与光阳极的距离，使照射到光阳极的光强为100mW/cm2，光照时间为2h。外加电源通过辰华660E电化学工作站提供。每光照30min，通过进样环将产生的部分氢气和氧气打入气相色谱(GC2010，热导检测器，安捷伦公司产)定量。外加偏压为1.0V vs RHE，光照2小时氢气和氧气的产生速率分别为35.2μmol h-1和17.8 μmol h-1。
实施例2～4
对NiFe-MOF中Ni：Fe不同摩尔比的NiFe-MOF/OV-BiVO4复合光催化剂，操作步骤同实施例1，只改变溶剂热过程中FeCl3·6H2O与Ni(NO3)2·6H2O加入的量，其余条件均不变，并把样品编号为MOB-1、MOB-2、MOB-3，其结果见如表1所示。
表1 Ni：Fe不同摩尔比的NiFe-MOF/OV-BiVO4复合光阳极的反应结果
由表1可知，在不同Ni、Fe摩尔比下得到不同的水分解速率，其中Ni、Fe摩尔比为1：1时产氢速率为35.2μmol h-1，产氧速率为17.8μmol h-1，光催化效果最好。
实施例5～7
按照效果最优的的实施例1的步骤，其余条件不变(Ni:Fe的摩尔比为1:1)，只改变咖啡酸的浓度，分别变为2mg/ml、7mg/ml、10mg/ml，并将其样品编号为A1、A2、 A3，其结果见如表2所示。
表2不同咖啡酸浓度所得NiFe-MOFs/OV-BiVO4复合光阳极的反应结果
由表2可得，在不同的咖啡酸浓度修饰下得到催化活性不同的光阳极材料，咖啡酸的浓度为5mg/ml时所制备的光阳极具有最佳的光电催化分解水效果。
实施例8～9
同实施例1，只改变表面改性剂的种类为单宁酸和没食子酸，并把其样品编号为B1、B2，其结果见如表3所示。
表3不同表面改性剂种类的NiFe-MOFs/OV-BiVO4复合光阳极的反应结果
由表3可得，采用不同的表面改性剂所制备的光阳极具有不同的产氢产氧速率，咖啡酸作为表面改性剂制备的光阳极具有最高的产氢产氧速率，光电催化分解水效果最佳。
对比例1
以聚乙烯吡咯烷酮(PVP K30)作为表面改性剂制备NiFe-MOF/Ov-BiVO4光阳极。具体操作如下：将实施例1中所制备的Ov-BiVO4光阳极置于5mg/ml PVP K30乙醇溶液中，浸泡3h。然后用无水乙醇冲洗一次，备用。将133mg对苯二甲酸，86.4mg六水三氯化铁 (FeCl3·6H2O)和92.1mg六水合硝酸镍(Ni(NO3)2·6H2O)溶解于20ml N,N-二甲基甲酰胺 (DMF)中。搅拌30min后，将上述混合液转移至40ml聚四氟乙烯晶化釜。然后将PVP K30 处理过的Ov-BiVO4光阳极置于上述晶化釜中(FTO导电面向下)，放入烘箱中保温处理120℃ 20h。之后，将晶化釜自然冷却至室温，用去离子水冲洗三次后，置于烘箱中80℃干燥12h，所得样品命名为NiFe-MOF/Ov-BiVO4(PV)。活性评价方法与实施例1一致，外加偏压为 1.0V vs RHE，光照2小时氢气和氧气的产生速率分别为25.4μmol h-1和13.7μmol h-1。
对比例2
钒酸铋粉末的制备方法：取3.65g硝酸铋溶于30mL 4M硝酸溶液中，剧烈搅拌10min后加入0.18g十二烷基苯磺酸钠混合形成溶液A；将0.87g钒酸铵溶解于30ml 2M 氢氧化钠溶液中，搅拌10min后形成溶液B。将溶液B逐滴滴加到溶液A中，继续搅拌 30min，得到溶液C。然后将所得的溶液C转移至聚四氟乙烯反应釜中，200℃晶化4小时。冷却至室温后，将晶化液过滤分离，用去离子水和乙醇洗涤三次，于80℃干燥12小时即可得钒酸铋粉末。
将1g钒酸铋粉末置于管式炉中，H2/Ar-6％气氛中285℃热处理15min(升温速率为5℃/min),所的样品命名为OV-BiVO4(PO)。
将0.5g OV-BiVO4(P)分散到30ml 5mg/ml咖啡酸乙醇溶液中，超声处理15min，然后浸泡3小时。将133mg对苯二甲酸，86.4mg六水三氯化铁(FeCl3·6H2O)和92.1mg六水合硝酸钴(Co(NO3)2·6H2O)溶解于20ml N,N-二甲基甲酰胺(DMF)中。将处理过的OV-BiVO4(P) 分散到上述混合液中，搅拌30min后将上述混合液转移至40ml聚四氟乙烯晶化釜，120℃晶化20小时。冷却至室温后，将晶化液过滤分离，用去离子水和乙醇洗涤三次，于80℃干燥12小时即可得钒酸铋粉末MOFs/OV-BiVO4(P)。将50mg MOFs/OV-BiVO4(P)粉末分散到1ml 1％全氟磺酸乙醇溶液中，充分研磨后，将混合液均匀涂在1×1cm2 FTO导电面上，置于80℃烘箱中，干燥6h,得到光阳极。活性评价方法与实施例1一致，外加偏压为 1.0V vs RHE，光照2小时氢气和氧气的产生速率分别为17.3μmol h-1和9.1μmol h-1。
对比例3
将1g市售钒酸铋粉末置于管式炉中，H2/Ar-6％气氛中285℃热处理15min(升温速率为5℃/min),所的样品命名为OV-BiVO4(SP)。
将0.5g OV-BiVO4(SP)分散到30ml 5mg/ml咖啡酸乙醇溶液中，超声处理15min，然后浸泡3小时。将133mg对苯二甲酸，86.4mg六水三氯化铁(FeCl3·6H2O)和92.1mg六水合硝酸镍(Ni(NO3)2·6H2O)溶解于20ml N,N-二甲基甲酰胺(DMF)中。将处理过的OV- BiVO4(P)分散到上述混合液中，搅拌30min后将上述混合液转移至40ml聚四氟乙烯晶化釜，120℃晶化20小时。冷却至室温后，将晶化液过滤分离，用去离子水和乙醇洗涤三次，于80℃干燥12小时即可得钒酸铋粉末MOFs/OV-BiVO4(SP)。将50mg MOFs/OV-BiVO4(SP) 粉末分散到1ml 1％全氟磺酸乙醇溶液中，充分研磨后，将混合液均匀涂在1×1cm2 FTO导电面上，置于80℃烘箱中，干燥6h,得到复合光阳极。活性评价方法与实施例1一致，外加偏压为1.0V vs RHE，光照2小时氢气和氧气的产生速率分别为13.8μmol h-1和7.3μmol h-1。
Claims (8)
1.一种MOFs包覆的OV-BiVO4复合光阳极的制备方法，其特征在于，包括如下步骤：
(1)通过电化学沉积-热处理的方法制备BiVO4纳米阵列；
(2)将步骤(1)得到的BiVO4纳米阵列置于含氢气气氛中灼烧得到OV-BiVO4；
(3)将步骤(2)得到的OV-BiVO4浸泡在含有单宁酸、咖啡酸或没食子酸的醇溶液中进行表面阴离子化处理后，通过水热法将MOFs包覆到OV-BiVO4表面。
2.根据权利要求1所述的一种MOFs包覆的OV-BiVO4复合光阳极的制备方法，其特征在于：步骤(2)中，所述含氢气气氛为H2气氛或H2/Ar混合气气氛，灼烧温度为300℃，灼烧时间为10min。
3.根据权利要求1所述的一种MOFs包覆的OV-BiVO4复合光阳极的制备方法，其特征在于：步骤(3)中，所述醇为甲醇或乙醇，含有单宁酸、咖啡酸或没食子酸的醇溶液的浓度为2～10mg/ml。
4.根据权利要求1所述的一种MOFs包覆的OV-BiVO4复合光阳极的制备方法，其特征在于：步骤(3)中，所述MOFs为单金属-有机骨架或双金属-有机骨架，单金属为钴、铁或镍；双金属为镍铁或钴铁。
5.根据权利要求4所述的一种MOFs包覆的OV-BiVO4复合光阳极的制备方法，其特征在于：所述MOFs为双金属-有机骨架，双金属为镍铁或钴铁，镍铁的摩尔比为0.5～2：1；钴铁的摩尔比为0.5～2：1。
6.根据权利要求1所述的一种MOFs包覆的OV-BiVO4复合光阳极的制备方法，其特征在于：步骤(3)中，所述MOFs包覆的OV-BiVO4复合光阳极是以OV-BiVO4为“核”，MOFs为“壳”的“核壳结构”，MOFs的包覆厚度为10-20nm。
7.权利要求1-6任一项所述的制备方法制得的MOFs包覆的OV-BiVO4复合光阳极。
8.权利要求7所述的MOFs包覆的OV-BiVO4复合光阳极的应用，其特征在于：将其用于光电催化分解水。
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