CN109225273B - 一种硫化铜/硫化钨复合光催化剂及其制备方法 - Google Patents
一种硫化铜/硫化钨复合光催化剂及其制备方法 Download PDFInfo
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-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 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 235000013878 L-cysteine Nutrition 0.000 claims description 3
- 239000004201 L-cysteine Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 10
- 239000001569 carbon dioxide Substances 0.000 abstract description 7
- 238000001228 spectrum Methods 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
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- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
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- 229910021641 deionized water Inorganic materials 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- -1 transition metal chalcogenide Chemical class 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
本发明公开了一种硫化铜/硫化钨复合光催化剂及其制备方法,所述复合光催化剂是CuS/WS2复合物,其中WS2呈树叶状生长,CuS由纳米片组装而成分散在WS2周围。本发明的CuS/WS2复合光催化剂在紫外、可见及红外光范围内均显示了很好的光吸收,在全光谱照射下能够有效地光催化还原二氧化碳和重金属离子,降解有机苯系和染料等有机污染物。本发明的制备方法简单,操作方便,成本低廉,适合工业化生产。
Description
技术领域
本发明涉及光催化材料领域,具体涉及一种硫化铜/硫化钨复合光催化剂及其制备方法。
背景技术
1979年,Inoue等在Nature上报道多种半导体粉末TiO2,ZnO,CdS,GaP,SiC和WO3在水溶液中可以光催化还原CO2转化成甲酸、甲醛、甲醇和甲烷,认为太阳能光催化还原CO2技术是最佳CO2转化途径之一,是半导体光催化发展史上的一个里程碑。半导体TiO2具有高比表面积、优异化学和光电性能、无毒、低成本等特点,被认为是最具潜力的催化剂。但是,TiO2对太阳能的利用范围仅限于紫外光,同时催化活性很低。同时研究者开发了新型可见光催化剂,比如铋基半导体、硫化物、氧化物和Z体系催化剂等用于光催化还原CO2。但是,大多催化剂仅仅能够响应紫外光或部分可见光,红外光区域几乎未被利用,而且仍存在活性低和选择性差的问题。研制高效全光谱响应的光催化剂是半导体光催化领域需要解决的关键问题之一,也是实现国家中长期科学和技术发展规划,促进国家战略性新兴产业发展的迫切要求。
过渡金属硫族化合物具有类石墨烯结构,层内原子间以共价键结合,层间以较弱的范德华力结合,被用于电催化、光催化、摩擦润滑剂、锂/钠电池等领域。典型的过渡金属硫族化合物CuS是直接带隙半导体,能带宽度为1.2-2.0eV,具有独特的电子、光学和热学性能,被广泛用于锂离子电池、太阳能电池、超导体和非线性材料。特别是,CuS在可见光区域内低的反射率,红外光区域内高的反射率,使得它能够有效地利用太阳光,作为一种有潜力的光催化剂,用于还原CO2和降解有机污染物。但是,到目前为止,对于CuS及其复合物用于光催化还原CO2,还鲜有报道。
发明内容
本发明的目的是针对上述问题,提供其中WS2呈树叶状生长,CuS由纳米片组装而成分散在WS2周围。本发明的CuS/WS2复合光催化剂在全光谱范围内均展现了良好的光吸收,能够有效地还原二氧化碳和重金属离子,去除苯系和染料等有机污染物。本发明的制备方法简单,操作方便,成本低,适用于工业化生产。
为了实现上述目的,本发明提供的技术方案是:
一种硫化铜/硫化钨复合光催化剂,由CuS与WS2复合而成,其中WS2呈树叶状生长,CuS由纳米片组装而成分散在WS2周围。
所述的光催化剂中CuS与WS2的质量比为5%~15%。
上述的硫化铜/硫化钨复合光催化剂的制备方法,包括以下步骤:
第一步,将铜源、钨源和表面活性剂一起溶解于水中,超声分散,得到均匀混合液A;
第二步,将硫源溶解于水中,超声分散,得到溶液B;
第三步,将溶液B滴加到溶液A中,搅拌,得到混合液C,然后将混合液C转移到高压反应釜中,在150~180℃恒温下反应24h,清洗,干燥,得到CuS/WS2复合光催化剂。
上述技术方案中,所述的铜源通常为氯化铜、硝酸铜、硫酸铜、醋酸铜中的至少一种。
所述的硫源通常为硫化钠、硫脲、硫代乙酰胺、L-半胱氨酸中的至少一种。
所述的钨源通常为钨酸钠、钨酸铵中的至少一种。
所述的表面活性剂可以为十六烷基三甲基溴化铵。
所述的溶液A中,铜源浓度优选为0.14~0.28mol/L,表面活性剂的浓度优选为0.03~0.6mol/L。
所述的溶液B中,硫源浓度优选为0.35~0.52mol/L。
本发明的CuS/WS2复合光催化剂,能够用于全光谱范围内还原二氧化碳、或还原重金属离子、或降解苯系有机污染物、或降解染料,是一种有潜力的全光谱响应光催化剂。同时,本发明的制备方法容易,操作方便,成本低廉,易于实现工业化。
附图说明
图1为本发明实施例1中合成的CuS/WS2的扫描电镜图。
图2为本发明实施例1中合成的CuS/WS2的X射线衍射图。
图3为本发明实施例1中合成的CuS/WS2的光吸收谱图。
图4为本发明中实施例1中合成的CuS/WS2的光催化还原二氧化碳效率图。
图5为本发明中实施例2中合成的CuS/WS2的光催化还原Cr(VI)效率图。
具体实施方式
下面结合具体实施例方式,进行进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不是用于限制本发明的范围。此外,在阅读了本发明的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附后权利要求书限定的范围。
实施例1
将31.66mg钨酸钠,5mmol硝酸铜和1.0mmol十六烷基三甲基溴化铵加入到35ml去离子水中,超声分散,形成溶液A。将12.5mmol硫代乙酰胺加入到35ml去离子水中,超声分散,形成溶液B。随后将溶液B滴加到溶液A中,超声分散,搅拌60分钟,形成均匀分散的混合液C。然后,将混合液C放入高压反应釜中,在150℃下反应24h,清洗,干燥,得到CuS/WS2复合物。
图1为合成的CuS/WS2的扫描电镜图,其中(a)为相同方法合成的纯CuS形貌,其余为CuS/WS2形貌。从图中可以看到,该CuS/WS2复合物中WS2呈树叶结构生长,CuS由纳米片组装而成分散在WS2树叶周围。
图2为合成的CuS/WS2的X射线衍射图。
图3为合成的CuS/WS2的光吸收谱图。从图中可以看到,CuS/WS2在紫外、可见甚至红外区域都具有非常强的光吸收,可以作为一种高效的全光谱响应的复合光催化剂。
2)光催化实验
将10ml水和制备好的上述光催化剂(100mg)均匀混合后形成悬浮液,采用丝网印刷的方法将悬浮液涂覆在ITO玻璃上,形成光催化剂薄膜。将催化剂薄膜和1g碳酸氢钠同时放入100ml的密封玻璃反应瓶中,抽真空,随后将5ml硫酸溶液滴加到玻璃反应瓶中反应产生二氧化碳气体。打开氙灯光源,进行光催化反应。每隔一段时间采用气相色谱在线分析产物的含量。
图4为合成的CuS/WS2的光催化效率图。图中显示了CuS/WS2光催化还原二氧化碳的效果图。从图中可看出,随着光照时间增加,产物甲烷含量明显提高。甲烷的平均产率达到150μmol·h-1·g-1。
实施例2
1)光催化剂的制备
将63.33mg钨酸钠,5mmol醋酸铜和1.0mmol十六烷基三甲基溴化铵加入到35ml去离子水中,超声分散,形成溶液A。将12.5mmol硫脲加入到35ml去离子水中,超声分散,形成溶液B。随后将溶液B滴加到溶液A中,超声分散,搅拌60分钟,形成均匀分散的混合液C。然后,将混合液C放入高压反应釜中,在160℃下反应24h,清洗,干燥,得到CuS/WS2复合物。
2)光催化实验
将制备好的上述光催化剂(1g/L)放入浓度为80ppm的Cr(VI)溶液(50ml)中,在磁力搅拌条件下,暗反应30分钟后,打开高压汞灯(作为紫外光源)和氙灯光源,使用氙灯时放置截止波长为400nm(作为可见光源)和800nm(作为红外光源)的滤光片,分别进行光催化反应。每隔一段时间取一定量的Cr(VI)溶液,用紫外-可见分光光度计测试溶液的吸收光谱,通过吸收峰强度的变化可以计算出Cr(VI)的还原率。
图5为合成的CuS/WS2的光催化效率图。其中横坐标为光照时间,纵坐标为硝基苯溶液变化的归一化浓度。图中显示了CuS/WS2对Cr(VI)的还原率。随着光照时间的变化曲线。从图中可看出,随着光照时间增加,Cr(VI)的还原率有明显提高。在紫外、可见及红外光照射下,CuS/WS2对Cr(VI)的还原率均达到90%以上。
实施例3
将95mg钨酸钠,5mmol硫酸铜和1.0mmol十六烷基三甲基溴化铵加入到35ml去离子水中,超声分散,形成溶液A。将25mmol硫化钠加入到35ml去离子水中,超声分散,形成溶液B。随后将溶液B滴加到溶液A中,超声分散,搅拌60分钟,形成均匀分散的混合液C。然后,将混合液C放入高压反应釜中,在180℃下反应24h,清洗,干燥,得到CuS/WS2复合物。
采用实施例2所述的测试方法测试本例制得的光催化剂在紫外、可见及红外光照射下对苯酚的降解活性。其光催化性能见于表1。
实施例4
将63.33mg钨酸钠,5mmol氯化铜和1.0mmol十六烷基三甲基溴化铵加入到35ml去离子水中,超声分散,形成溶液A。将12.5mmol L-半胱氨酸加入到35ml去离子水中,超声分散,形成溶液B。随后将溶液B滴加到溶液A中,超声分散,搅拌60分钟,形成均匀分散的混合液C。然后,将混合液C放入高压反应釜中,在170℃下反应24h,清洗,干燥,得到CuS/WS2复合物。
采用实施例2所述的测试方法测试本例制得的光催化剂在紫外、可见及红外光照射下对甲基橙的降解活性。其光催化性能见于表1。
实施例5
将63.33mg钨酸钠,5mmol硝酸铜和1.0mmol十六烷基三甲基溴化铵加入到35ml去离子水中,超声分散,形成溶液A。将25mmol硫脲加入到35ml去离子水中,超声分散,形成溶液B。随后将溶液B滴加到溶液A中,超声分散,搅拌60分钟,形成均匀分散的混合液C。然后,将混合液C放入高压反应釜中,在150℃下反应24h,清洗,干燥,得到CuS/WS2复合物。
采用实施例2所述的测试方法测试本例制得的光催化剂在紫外、可见及红外光照射下对抗生素的降解活性。其光催化性能见于表1。
此外,利用直接购买获得的WS2作为对比(商品WS2),该WS2形貌为片状结构,将其与采用本发明方法制得的纯CuS按5%比例(CuS与WS2的质量比)直接混合(简称混合例),采用实施例2所述的测试方法测试其在紫外、可见及红外光照射下Cr(VI)的光催化还原活性,其光催化性能见于表1。结果表明:此光催化剂的催化活性明显低于水热法一步合成的硫化铜/硫化钨复合光催化剂。同直接物理混合法相比,本发明水热法制备的复合光催化剂具有很好的接触界面,这将有利于光生载流子的转移和分离,能够有效地抑制其复合,进而达到增强光催化性能的目的。
表1
紫外光催化活性 | 可见光催化活性 | 红外光催化活性 | |
实施例2 | 93% | 95% | 98% |
实施例3 | 95% | 92% | 94% |
实施例4 | 91% | 96% | 94% |
实施例5 | 92% | 94% | 93% |
混合例 | 68% | 71% | 53% |
可见,本发明的CuS/WS2能够作为一种复合光催化剂,在全光谱范围内显示出良好的催化活性,被用于还原二氧化碳、或还原重金属离子、或降解苯系有机污染物、或降解染料。本发明的制备方法容易,反应条件温和,操作方便,成本低廉,适合于大规模生产。
以上为对本发明实施案例的描述,通过对所公开的实施案例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施案例的多种修改对本领域技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施案例中实现。因此本发明不会被限制于本文所示的这些实施案例中,而是要符合与本文所公开的原理和新颖等特点相一致的最宽范围。
Claims (9)
1.一种硫化铜/硫化钨复合光催化剂,其特征在于,该光催化剂由CuS与WS2复合而成,其中WS2呈树叶状生长,CuS由纳米片组装而成分散在WS2周围。
2.根据权利要求1所述的硫化铜/硫化钨复合光催化剂,其特征在于,所述的光催化剂中CuS与WS2的质量比为5%~15%。
3.如权利要求1所述的硫化铜/硫化钨复合光催化剂的制备方法,其特征在于,其制备方法包括以下步骤:
第一步,将铜源、钨源和表面活性剂一起溶解于水中,超声分散,得到均匀混合液A;
第二步,将硫源溶解于水中,超声分散,得到溶液B;
第三步,将溶液B滴加到溶液A中,搅拌,得到混合液C,然后将混合液C转移到高压反应釜中,在150~180℃恒温下反应24h,清洗,干燥,得到CuS/WS2复合光催化剂。
4.根据权利要求3所述的硫化铜/硫化钨复合光催化剂的制备方法,其特征在于,所述的铜源为氯化铜、硝酸铜、硫酸铜、醋酸铜中的至少一种。
5.根据权利要求3所述的硫化铜/硫化钨复合光催化剂的制备方法,其特征在于,所述的硫源为硫化钠、硫脲、硫代乙酰胺、L-半胱氨酸中的至少一种。
6.根据权利要求3所述的硫化铜/硫化钨复合光催化剂的制备方法,其特征在于,所述的钨源为钨酸钠、钨酸铵中的至少一种。
7.根据权利要求3所述的硫化铜/硫化钨复合光催化剂的制备方法,其特征在于,所述的表面活性剂为十六烷基三甲基溴化铵。
8.根据权利要求3所述的硫化铜/硫化钨复合光催化剂的制备方法,其特征在于,所述的溶液A中,铜源浓度为0.14~0.28mol/L,表面活性剂的浓度为0.03~0.6mol/L。
9.根据权利要求3所述的硫化铜/硫化钨复合光催化剂的制备方法,其特征在于,所述的溶液B中,硫源浓度为0.35~0.52mol/L。
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