CN111203239B - 一种钨酸铋/硫化铋/二硫化钼异质结三元复合材料及其制备方法和应用 - Google Patents
一种钨酸铋/硫化铋/二硫化钼异质结三元复合材料及其制备方法和应用 Download PDFInfo
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- CN111203239B CN111203239B CN202010124370.1A CN202010124370A CN111203239B CN 111203239 B CN111203239 B CN 111203239B CN 202010124370 A CN202010124370 A CN 202010124370A CN 111203239 B CN111203239 B CN 111203239B
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- bismuth
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- molybdenum disulfide
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 57
- 239000011206 ternary composite Substances 0.000 title claims abstract description 41
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 39
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 39
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 35
- 239000002135 nanosheet Substances 0.000 claims abstract description 13
- -1 transition metal sulfide Chemical class 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000004065 semiconductor Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 12
- 239000012362 glacial acetic acid Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 10
- 229920003081 Povidone K 30 Polymers 0.000 claims description 10
- 238000004729 solvothermal method Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 5
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011232 storage material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 6
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- 239000000243 solution Substances 0.000 description 35
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- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- 241001198704 Aurivillius Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
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- 238000009713 electroplating Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种钨酸铋/硫化铋/二硫化钼异质结三元复合材料及其制备方法和应用。以钨酸铋/硫化铋/二硫化钼的有序层级组成，Bi2WO6为正交晶系，Bi2S3为P型半导体，位于(130)晶面，MoS2为层状过渡金属硫化物，位于(002)晶面，复合材料整体为球状结构，表面不光滑，外层均匀生长一层纳米片，平均粒径为2.4‑2.6μm。本发明制备的球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料对Cr(VI)具有良好的吸附和可见光催化还原能力。
Description
技术领域
本发明属于光催化材料的合成技术领域，具体涉及一种钨酸铋/硫化铋/二硫化钼异质结三元复合材料及其制备方法和应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
目前，重金属离子污染日趋严重。与其他污染物不同的是，重金属污染可通过食物链传播，具有难降解、易富集的特点，是世界环境治理的重大难题之一。其中，皮革鞣制、电镀、色素合成和铬酸盐工业废水中的Cr(VI)污染尤为严重，它具有高毒性、潜在致癌性和不可生物降解性，对生态环境、人体健康都有很大危害。现有去除水中Cr(VI)的方法有吸附法、离子交换法、生物修复法、光催化还原法及化学沉淀法。其中，光催化还原Cr(VI)被认为是一种简单、绿色、高效的方法。
Bi2WO6是一种典型的Aurivillius氧化物，具有钙钛矿层状结构，为常见的窄带隙n型半导体。因其安全无毒、结构形貌易于调节、光催化性能优良以及物理化学性质稳定等特点而被广泛应用于光催化。然而，光生电子空穴对的快速复合和较弱的表面吸附能力使得Bi2WO6的光催化效率较低。
发明内容
针对上述现有技术中存在的问题，本发明的目的是提供一种钨酸铋/硫化铋/二硫化钼异质结三元复合材料及其制备方法和应用。本发明通过调整钨酸铋(Bi2WO6)的形貌，有利于光催化剂对光的吸收利用，提高对Cr(VI)的吸附和降解能力，有利于提高Cr(VI)的去除效果。
为了解决以上技术问题，本发明的技术方案为：
第一方面，一种钨酸铋/硫化铋/二硫化钼异质结三元复合材料，以钨酸铋/硫化铋/二硫化钼的有序层级组成，Bi2WO6为正交晶系，Bi2S3为P型半导体，位于(130)晶面，MoS2为层状过渡金属硫化物，位于(002)晶面，复合材料整体为球状结构，表面不光滑，外层均匀生长一层纳米片，平均粒径为2.4-2.6μm。
本发明的三元复合材料中钨酸铋(Bi2WO6)、硫化铋(Bi2S3)、二硫化钼(MoS2)相互配合形成一种特殊的结构，三种物质形成异质结的结构，首先钨酸铋的纳米片的球状结构有利于光催化剂对光的吸收，增加入射光在催化剂内部的反射路径，从而增强材料对光的吸收利用性能，达到提高材料光催化性能的目的。P型半导体Bi2S3具有窄带隙(1.2eV-1.7eV)和出色的稳定性。MoS2是一种典型的层状过渡金属硫化物，具有三层堆叠原子层(S-Mo-S)的特殊夹层结构。将球状Bi2WO6与窄带隙半导体Bi2S3、MoS2进行复合可增强Bi2WO6表面吸附能力、拓宽光谱响应范围和减缓光生电子空穴对的复合。
本发明在提供一种结构不同的钨酸铋/硫化铋/二硫化钼异质结三元复合材料之外，同时这种复合材料能够有效光催化还原Cr(VI)。
第二方面，上述钨酸铋/硫化铋/二硫化钼异质结三元复合材料的制备方法，所述方法为制备球状钨酸铋，然后将球状钨酸铋分散在水中，加入Na2MoO4·2H2O和硫脲，将混合液进行水热反应，得到反应产物Bi2WO6/Bi2S3/MoS2异质结三元复合材料。
球状钨酸铋的制备方法：将表面活性剂PVP K30在水、无水乙醇、冰乙酸的混合溶液中进行分散，然后加入铋源和钨源进行溶剂热处理制备出由纳米片自组装而成的Bi2WO6微球。这种微球具有较高的结构稳定性以及较好的可见光响应，本发明的制备方法相比于现有的球状钨酸铋制备方法，得到的球状钨酸铋球状结构不同，本发明的球状结构紧密，片状结构成圆环形排列；制备方法也不同，本发明的制备方法原理为，将PVP K30、铋源和钨源分散在水、无水乙醇、冰乙酸的混合溶液中，然后进行溶剂热反应。在该反应过程中，PVPK30起到模板剂的作用，促使溶液中的纳米粒子通过定向聚集重组和自组装成纳米片，这些纳米片会在随后的生长过程中进一步组装成微球。
在本发明的一些实施方式中，球状钨酸铋的制备方法为五水合硝酸铋(Bi(NO3)3·5H2O)和PVP K30加入到水、无水乙醇、冰乙酸的混合溶液中得到混合溶液A；
将二水合钨酸钠的水溶液B和混合溶液A混合，得到混合溶液b，混合溶液b进行溶剂热反应得到球状钨酸铋。
在本发明的一些实施方式中，五水合硝酸铋与PVP K30的质量比为0.2-0.25:1。
在本发明的一些实施方式中，水、无水乙醇、冰乙酸的混合溶液中水、无水乙醇、冰乙酸的体积比为2-4:1:1。
在本发明的一些实施方式中，混合溶液b中Bi(NO3)3·5H2O和Na2WO4·2H2O的摩尔比为1.5-2.5:1。
在本发明的一些实施方式中，溶剂热反应的温度为150-200℃，反应的时间为15-20h。
异质结三元复合材料的制备方法：
在本发明的一些实施方式中，球状Bi2WO6、Na2MoO4·2H2O、硫脲的投料比为200:0.075～0.30:0.15～0.60，mg:g:g；优选为200:0.20:0.40，mg:g:g。在该投料比下制得的Bi2WO6/Bi2S3/MoS2异质结三元复合材料具有最佳的光催化性能。投料比影响得到的球状的异质结三元复合材料的表面结构。
在本发明的一些实施方式中，水热反应的条件为180-220℃，反应的时间为22-26h。
第三发明，上述的钨酸铋/硫化铋/二硫化钼异质结三元复合材料在催化材料、传感材料、光电材料、磁性材料、电子材料、能源存储材料中的应用。
附图说明
图1是本发明实施例3制备的球状Bi2WO6及球状Bi2WO6/Bi2S3/MoS2的X射线衍射(XRD)图；
图2(a)是本发明实施例3制备的球状Bi2WO6的扫描电子显微镜(SEM)图；
图2(b)是本发明实施例3制备的球状Bi2WO6的透射电子显微镜(TEM)图；
图3(a)是本发明实施例3制备的球状Bi2WO6/Bi2S3/MoS2的扫描电子显微镜(SEM)图；
图3(b)是本发明实施例3制备的球状Bi2WO6/Bi2S3/MoS2的透射电子显微镜(TEM)图；
图4是本发明实施例3制备的球状Bi2WO6/Bi2S3/MoS2的高分辨透射电子显微镜(HRTEM)图；
图5为本发明实施例1、实施例2、实施例3、实施例4制得样品可见光下去除40mg L- 1Cr(VI)(基于K2Cr2O7)的效果图(催化剂用量为0.4g L-1)。
本发明的有益效果：
1.本发明球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料的制备方法工艺简单，易操作，成本低廉。
2.本发明制备的球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料中Bi2WO6、Bi2S3、MoS2三者之间的协同作用增强了光吸收、延缓了光生电子空穴对的复合。
3.本发明制备的球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料对Cr(VI)具有良好的吸附和可见光催化还原能力。
4.本发明与现有技术相比，提供了一种安全、高效还原Cr(VI)的新方法，其方法简单，操作方便，成本低，光催化还原效率高，无需向光催化还原反应体系中添加其它化学物质，无二次污染。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
实施例1
(1)球状Bi2WO6的制备
在球状Bi2WO6前驱体的合成中，制备了溶液A和溶液B。溶液A，将2mmol Bi(NO3)3·5H2O和4g PVP K30加入到50mL水、无水乙醇、冰乙酸(体积比为3:1:1)的混合溶液中，在室温下搅拌至溶液澄清。溶液B，在20mL H2O中加入1mmol Na2WO4·2H2O，超声作用30min。再将溶液B滴加至溶液A中，搅拌60min，得到均匀悬浮液，将其转移至100mL聚四氟乙烯内衬的高压反应釜中，于180℃下溶剂热反应18h，自然冷却至室温后，通过离心、洗涤、干燥，研磨，得到淡黄色的Bi2WO6粉末。
(2)球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料的制备
通过超声处理将200mg Bi2WO6粉末分散至40mL水中，加入0.075g Na2MoO4·2H2O和0.15g硫脲，搅拌1h，将得到的均匀悬浮液转移至100mL聚四氟乙烯内衬的高压反应釜中，于200℃下水热反应24h，自然冷却至室温后，通过离心、洗涤、干燥，研磨，得到球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料，为方便描述将该投料比下得到的产物命名为BBM-20。
实施例2
(1)球状Bi2WO6的制备
在球状Bi2WO6前驱体的合成中，制备了溶液A和溶液B。溶液A，将2mmol Bi(NO3)3·5H2O和4g PVP K30加入到50mL水、无水乙醇、冰乙酸(体积比为3:1:1)的混合溶液中，在室温下搅拌至溶液澄清。溶液B，在20mL H2O中加入1mmol Na2WO4·2H2O，超声作用30min。再将溶液B滴加至溶液A中，搅拌60min，得到均匀悬浮液，将其转移至100mL聚四氟乙烯内衬的高压反应釜中，于180℃下溶剂热反应18h，自然冷却至室温后，通过离心、洗涤、干燥，研磨，得到淡黄色的Bi2WO6粉末。
(2)球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料的制备
通过超声处理将200mg Bi2WO6粉末分散至40mL水中，加入0.13g Na2MoO4·2H2O和0.26g硫脲，搅拌1h，将得到的均匀悬浮液转移至100mL聚四氟乙烯内衬的高压反应釜中，于200℃下水热反应24h，自然冷却至室温后，通过离心、洗涤、干燥，研磨，得到球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料，为方便描述将该投料比下得到的产物命名为BBM-30。
实施例3
(1)球状Bi2WO6的制备
在球状Bi2WO6前驱体的合成中，制备了溶液A和溶液B。溶液A，将2mmol Bi(NO3)3·5H2O和4g PVP K30加入到50mL水、无水乙醇、冰乙酸(体积比为3:1:1)的混合溶液中，在室温下搅拌至溶液澄清。溶液B，在20mL H2O中加入1mmol Na2WO4·2H2O，超声作用30min。再将溶液B滴加至溶液A中，搅拌60min，得到均匀悬浮液，将其转移至100mL聚四氟乙烯内衬的高压反应釜中，于180℃下溶剂热反应18h，自然冷却至室温后，通过离心、洗涤、干燥，研磨，得到淡黄色的Bi2WO6粉末。
(2)球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料的制备
通过超声处理将200mg Bi2WO6粉末分散至40mL水中，加入0.20g Na2MoO4·2H2O和0.40g硫脲，搅拌1h，将得到的均匀悬浮液转移至100mL聚四氟乙烯内衬的高压反应釜中，于200℃下水热反应24h，自然冷却至室温后，通过离心、洗涤、干燥，研磨，得到球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料，为方便描述将该投料比下得到的产物命名为BBM-40。
经XRD、SEM、TEM及HRTEM对所制备样品的形貌及结构进行了表征，如图1、图2、图3和图4所示。
图1为实施例3制备的球状Bi2WO6和球状Bi2WO6/Bi2S3/MoS2的XRD图。纯Bi2WO6的衍射峰出现在2θ为28.299°、32.790°、47.138°、55.990°、58.538°、68.754°、76.075°、78.534°处，其晶面衍射为(131)、(200)、(202)、(133)、(262)、(400)、(2102)、(204)，与JCPDS 39-0256标准卡片相吻合，属于正交晶系。对于球状Bi2WO6/Bi2S3/MoS2，25°的衍射峰对应于Bi2S3的(130)晶面，32°的衍射峰可以归因于MoS2的(100)晶面。XRD结果表明，成功制备出纯相球状Bi2WO6以及球状Bi2WO6/Bi2S3/MoS2三元复合材料。
图2(a)为实施例3制备的球状Bi2WO6的SEM图，(b)为实施例3制备的球状Bi2WO6的TEM图。如图所示，单一Bi2WO6是由纳米片自组装而成的球状结构，粒径约为2.5μm。
图3(a)为实施例3制备的球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料的SEM图，(b)为实施例3制备的球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料的TEM图。如图所示，Bi2WO6/Bi2S3/MoS2为球状结构，与Bi2WO6相比粒径未发生显著变化、外层均匀生长一层纳米片。通过对比观察图2(a)和图3(a)可发现：不同于纯Bi2WO6,，复合材料表面的纳米片卷曲且厚度较薄，故此可知在Bi2WO6微球表面上生长了其他物质。
图4是本发明实施例3制备的球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料的HRTEM图。由图可知，成功制备了Bi2WO6/Bi2S3/MoS2异质结三元复合材料。
实施例4
(1)球状Bi2WO6的制备
在球状Bi2WO6前驱体的合成中，制备了溶液A和溶液B。溶液A，将2mmol Bi(NO3)3·5H2O和4g PVP K30加入到50mL水、无水乙醇、冰乙酸(体积比为3:1:1)的混合溶液中，在室温下搅拌至溶液澄清。溶液B，在20mL H2O中加入1mmol Na2WO4·2H2O，超声作用30min。再将溶液B滴加至溶液A中，搅拌60min，得到均匀悬浮液，将其转移至100mL聚四氟乙烯内衬的高压反应釜中，于180℃下溶剂热反应18h，自然冷却至室温后，通过离心、洗涤、干燥，研磨，得到淡黄色的Bi2WO6粉末。
(2)球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料的制备
通过超声处理将200mg Bi2WO6粉末分散至40mL水中，加入0.30g Na2MoO4·2H2O和0.60g硫脲，搅拌1h，将得到的均匀悬浮液转移至100mL聚四氟乙烯内衬的高压反应釜中，于200℃下水热反应24h，自然冷却至室温后，通过离心、洗涤、干燥，研磨，得到球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料，为方便描述将该投料比下得到的产物命名为BBM-50。
实施例5
球状Bi2WO6/Bi2S3/MoS2异质结三元复合材料作为光催化材料的光催化性能以可见光下还原Cr(VI)评估。过程如下：将催化剂(0.4g L-1)加入到Cr(VI)溶液中(40mg L-1，基于K2Cr2O7溶液中的Cr(VI))。然后，使用1M HCl溶液将初始溶液的pH值调节至2，后超声处理4min。辐射前，将悬浮液置于黑暗处搅拌60min，以建立吸附-解吸平衡。在氙灯(300W，λ>400nm)照射期间，以固定的时间间隔从反应容器中取3mL悬浮液，离心(9000r min-1，10min)后用0.22μm的滤膜注射器收集上清液，以除去残留的颗粒。最后，使用二苯卡巴肼(DPC)方法测定了不同时间下540nm处的吸光度，进而得出Cr(VI)的浓度。
图5为本发明实施例5(样品Bi2WO6、BBM-20、BBM-30、BBM-40、BBM-50)可见光下去除40mg L-1Cr(VI)的效果图。由图可知，BBM-40具有最佳的光催化性能。
对上述实施例中的产物进行测试，随着Na2MoO4·2H2O和硫脲加入量的增大，Bi2WO6微球上生长的材料形貌由纳米粒子转变为纳米片。当加入0.20g Na2MoO4·2H2O和0.40g硫脲时，Bi2WO6表面均匀生长着一层纳米片。然而，当Mo源、S源加入量进一步增加，在样品表面能够清晰地观察到MoS2聚集体的出现。同时，随着Na2MoO4·2H2O和硫脲加入量的增大，复合材料光催化还原Cr(VI)的能力呈现出先增强后减弱的趋势。通过探究一系列影响因素，发明人得出本发明的实施例3的实验条件为最优条件，产物的形貌规则且具有较好的光催化还原能力。
申请公布号CN 105753054 A(申请号201610082396.8)的中国专利公开了一种微球状三维分级微纳结构钨酸铋光催化材料及其制备方法。该方法以二水钨酸钠和五水硝酸铋为原料，制备过程中需用硝酸调节溶液pH＝1，实验过程比较繁琐、耗能高、反应后会产生大量强酸性废液从而造成环境污染。相比于该专利，本发明的实验过程更为简单、易操作、安全无污染。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (8)
1.一种钨酸铋/硫化铋/二硫化钼异质结三元复合材料，其特征在于：以钨酸铋/硫化铋/二硫化钼的有序层级组成，Bi2WO6为正交晶系，Bi2S3为P型半导体，位于(130)晶面，MoS2为层状过渡金属硫化物，位于(002)晶面，复合材料整体为球状结构，表面不光滑，外层均匀生长一层纳米片，平均粒径为2.4-2.6μm；所述钨酸铋/硫化铋/二硫化钼异质结三元复合材料的制备方法包括制备球状钨酸铋，然后将球状钨酸铋分散在水中，加入Na2MoO4·2H2O和硫脲，将混合液进行水热反应，得到反应产物Bi2WO6/Bi2S3/MoS2异质结三元复合材料；
球状Bi2WO6、Na2MoO4·2H2O、硫脲的投料比为200:0.075～0.30:0.15～0.60，mg:g:g；
水热反应的条件为180-220℃，反应的时间为22-26h。
2.根据权利要求1所述的钨酸铋/硫化铋/二硫化钼异质结三元复合材料，其特征在于：球状钨酸铋的制备方法为五水合硝酸铋(Bi(NO3)3·5H2O)和PVP K30加入到水、无水乙醇、冰乙酸的混合溶液中得到混合溶液A；
将二水合钨酸钠的水溶液B和混合溶液A混合，得到混合溶液b，混合溶液b进行溶剂热反应得到球状钨酸铋。
3.根据权利要求2所述的钨酸铋/硫化铋/二硫化钼异质结三元复合材料，其特征在于：五水合硝酸铋与PVP K30的质量比为0.2-0.25:1。
4.根据权利要求2所述的钨酸铋/硫化铋/二硫化钼异质结三元复合材料，其特征在于：水、无水乙醇、冰乙酸的混合溶液中水、无水乙醇、冰乙酸的体积比为2-4:1:1。
5.根据权利要求2所述的钨酸铋/硫化铋/二硫化钼异质结三元复合材料，其特征在于：混合溶液b中Bi(NO3)3·5H2O和Na2WO4·2H2O的摩尔比为1.5-2.5:1。
6.根据权利要求2所述的钨酸铋/硫化铋/二硫化钼异质结三元复合材料，其特征在于：溶剂热反应的温度为150-200℃，反应的时间为15-20h。
7.根据权利要求1所述的钨酸铋/硫化铋/二硫化钼异质结三元复合材料，其特征在于：球状Bi2WO6、Na2MoO4·2H2O、硫脲的投料比为200:0.20:0.40，mg:g:g。
8.权利要求1所述的钨酸铋/硫化铋/二硫化钼异质结三元复合材料在催化材料、传感材料、光电材料、磁性材料、电子材料、能源存储材料中的应用。
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