局部表面等离子体共振可调的MoO3-x-TiO2纳米复合物用于提高可见光下光催化还原CO2的性能

引用本文: 谢顺吉, 张海坤, 刘国栋, 吴雪娇, 林锦池, 张庆红, 王野. 局部表面等离子体共振可调的MoO_3-x-TiO₂纳米复合物用于提高可见光下光催化还原CO₂的性能[J]. 催化学报, 2020, 41(7): 1125-1131. doi: 10.1016/S1872-2067(20)63566-5 shu

Citation: Shunji Xie, Haikun Zhang, Guodong Liu, Xuejiao Wu, Jinchi Lin, Qinghong Zhang, Ye Wang. Tunable localized surface plasmon resonances in MoO_3-x-TiO₂ nanocomposites with enhanced catalytic activity for CO₂ photoreduction under visible light[J]. Chinese Journal of Catalysis, 2020, 41(7): 1125-1131. doi: 10.1016/S1872-2067(20)63566-5 shu

局部表面等离子体共振可调的MoO_3-x-TiO₂纳米复合物用于提高可见光下光催化还原CO₂的性能

厦门大学化学化工学院, 固体表面物理化学国家重点实验室, 能源材料化学协同创新中心, 醇醚酯化工清洁生产国家工程实验室, 福建厦门 361005
基金项目:
国家重点研发计划（2017YFB0602201）；国家自然科学基金（21433008，91545203，21503176）；中国博士后基金（2015M570555，2016T90597）.

摘要: 利用太阳能光催化还原CO₂和H₂O到燃料和化学品是一条极具吸引力但又充满挑战性的转化途径.迄今为止,只有非常有限的光催化剂已经被报道可以在可见光照射下光催化还原CO₂.局部表面等离子体共振(LSPR)现象可以被用作一种有效的开发可见光催化剂的策略.贵金属Au,Ag,Pt等的LSPR现象已经被较为广泛的研究,并应用于光催化、光热、气敏等多种领域.而低价态金属自掺杂的金属氧化物,如MoO_3-x和WO_3-x,也被证明具有LSPR现象,可用于开发更加廉价的可见光催化剂.本文通过简单的溶剂热法成功合成了低价态Mo自掺杂的MoO_3-x纳米片催化剂,并在合成过程中原位加入TiO₂纳米颗粒(TiO₂-NP)和TiO₂纳米棒(TiO₂-NT),构建了MoO_3-x-TiO₂纳米复合物.电镜表征显示,MoO_3-x-TiO₂-NT纳米复合物中,MoO_3-x纳米片和TiO₂纳米管的结合更为紧密.UV-vis光谱显示,TiO₂的复合不仅可以增强MoO_3-x可见区的吸收强度,同时吸收峰的位置也发生了蓝移.XPS表征显示,TiO₂复合后,MoO_3-x中Mo⁵⁺的比例明显增加,从而提高了MoO_3-x中自由电子的浓度,进而增强了LSPR现象和LSPR吸光能力,且TiO₂纳米管相对TiO₂纳米颗粒具有更好的促进效果.MoO_3-x纳米片具有在可见光照射下光催化还原CO₂的性能,CO的生成速率为2.8 µmol g-1 h-1.复合TiO₂纳米颗粒后,MoO_3-x-TiO₂-NP纳米复合物上,CO的生成速率提高到6.8 µmol g-1 h-1.当复合TiO₂纳米管时,光催化性能显著提高,在MoO_3-x-TiO₂-NT纳米复合物上,CO的生成速率可达12 µmol g-1 h-1,约为MoO_3-x纳米片的四倍,此外还可观测到CH₄的生成.当我们将反应气氛由CO₂替换成N₂后,CO和CH₄的生成量几乎为零,证明CO和CH₄的生成主要来自CO₂的光催化还原.此外,我们还考察了MoO_3-x-TiO₂-NT纳米复合物光催化还原CO₂的催化性能稳定性,以12 h反应时间为一个循环,经3个循环反应后,催化剂的活性基本保持不变,证明该催化剂具有较好的稳定性.综上,我们通过MoO_3-x纳米片和TiO₂复合的策略,增强了MoO_3-x纳米片的LSPR效应,提升了催化剂对可见光的吸收能力,进而提高了MoO_3-x-TiO₂-NT纳米复合物光催化还原CO₂的性能.MoO_3-x-TiO₂-NT纳米复合物是一种具有发展潜力的光催化还原CO₂的可见光催化剂,且该纳米复合物调变LSPR效应的策略还有望用于增强其他LSPR光催化材料的光催化性能.

关键词:

English

Tunable localized surface plasmon resonances in MoO_3-x-TiO₂ nanocomposites with enhanced catalytic activity for CO₂ photoreduction under visible light

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China
Received Date: 24 September 2019
Fund Project:
This work was supported by the National Key Research and Development Program of Ministry of Science and Technology (2017YFB0602201), the National Natural Science Foundation of China (21433008, 91545203, 21503176), and the China Postdoctoral Science Foundation (2015M570555, 2016T90597).

Abstract: The photocatalytic reduction of CO₂ with H₂O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes. Thus far, only a very limited number of photocatalysts has been reported to be capable of catalyzing the photocatalytic reduction of CO₂ under visible light. The utilization of the localized surface plasmon resonance (LSPR) phenomenon is an attractive strategy for developing visible-light photocatalysts. Herein, we have succeeded in synthesizing plasmonic MoO_3-x-TiO₂ nanocomposites with tunable LSPR by a simple solvothermal method. The well-structured nanocomposite containing two-dimensional (2D) molybdenum oxide (MoO_3-x) nanosheets and one-dimensional (1D) titanium oxide nanotubes (TiO₂-NT) showed LSPR absorption band in the visible-light region, and the incorporation of TiO₂-NT significantly enhanced the LSPR absorption band. The MoO_3-x-TiO₂-NT nanocomposite is promising for application in the photocatalytic reduction of CO₂ with H₂O under visible light irradiation.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

局部表面等离子体共振可调的MoO_3-x-TiO₂纳米复合物用于提高可见光下光催化还原CO₂的性能

English

Tunable localized surface plasmon resonances in MoO_3-x-TiO₂ nanocomposites with enhanced catalytic activity for CO₂ photoreduction under visible light

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