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Nano Research 2020, 13(4): 939-946 https://doi.org/10.1007/s12274-020-2719-7
Research Article | Issue | Published: 09 March 2020

Experimental and mechanistic understanding of photo-oxidation of methanol catalyzed by CuO/TiO2-spindle nanocomposite: Oxygen vacancy engineering

Show Author's Information Quanquan Shi1,§,  Zhaoxian Qin3,§,  Changlin Yu2,  Ammara Waheed3,  Hui Xu1,  Yong Gao1,  Hadi Abroshan4( ),  Gao Li3( )
College of Science, Inner Mongolia Key Laboratory of Soil Quality and Nutrient Resource, Inner Mongolia Agricultural University, Hohhot 010018, China
School of Chemical Engineering, Key Laboratory of Petrochemical Pollution Process and Control, Guangdong Province, Guangdong University of Petrochemical Technology, Maoming 525000, China
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, USA

§ Quanquan Shi and Zhaoxian Qin contributed equally to this work.

Keywords:
oxygen vacancy, photocatalysis, methanol, CuO/TiO2 nanocomposite, methyl formate, in-situ attenuated total reflection infrared spectroscopy
Topics:
Catalysis Copper oxidesInfrared spectroscopyNanocompositesOxidationPhotocatalysisTitanium Dioxide
Cite this article:
Shi Q, Qin Z, Yu C, et al. Experimental and mechanistic understanding of photo-oxidation of methanol catalyzed by CuO/TiO2-spindle nanocomposite: Oxygen vacancy engineering. Nano Research, 2020, 13(4): 939-946. https://doi.org/10.1007/s12274-020-2719-7
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Abstract Full text Electronic supplementary material About this article

We report experimental and mechanistic understanding of methanol oxidation to produce methyl formate using CuO/TiO2-spindle composite as a promising photocatalyst under mild conditions with over 97% conversion and 83% selectivity. The catalysts are obtained via precise depositing of CuO nanoclusters (size: ~ 3.5 nm) at the {101} facet of the TiO2 to optimally tune exciton recombination through oxygen vacancies generation, evidenced by photoluminescence and Raman spectroscopy measurements. The turnover frequency (TOF) and the apparent quantum efficiency (AQE) of the 7%CuO/TiO2-spindle composites reach up to 23.8 molmethanol·gcat-1·h-1 and 55.2% at 25 °C, respectively, which are substantially higher than these previously reported photocatalysts. Further, the in-situ attenuated total reflection infrared spectroscopy analysis reveals that the methanol oxidation most likely takes place through the conversion of adsorbed methoxy (CH3O*) to formaldehyde (CHO*) intermediate, a subject of major debate for a long time. The adsorbed formaldehyde (CHO*) thus produced reacts with another CH3O* species in its close proximity to form the final product of methyl formate. Results of this study provide insights into the reaction mechanism, and offer guidelines to systematically develop and apply photocatalysts for methanol conversion and related reactions via surface engineering.


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Electronic supplementary material
About this article

Experimental and mechanistic understanding of photo-oxidation of methanol catalyzed by CuO/TiO2-spindle nanocomposite: Oxygen vacancy engineering

Show Author's information Quanquan Shi1,§, Zhaoxian Qin3,§, Changlin Yu2, Ammara Waheed3, Hui Xu1, Yong Gao1, Hadi Abroshan4( ), Gao Li3( )
College of Science, Inner Mongolia Key Laboratory of Soil Quality and Nutrient Resource, Inner Mongolia Agricultural University, Hohhot 010018, China
School of Chemical Engineering, Key Laboratory of Petrochemical Pollution Process and Control, Guangdong Province, Guangdong University of Petrochemical Technology, Maoming 525000, China
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, USA

§ Quanquan Shi and Zhaoxian Qin contributed equally to this work.

Abstract

We report experimental and mechanistic understanding of methanol oxidation to produce methyl formate using CuO/TiO2-spindle composite as a promising photocatalyst under mild conditions with over 97% conversion and 83% selectivity. The catalysts are obtained via precise depositing of CuO nanoclusters (size: ~ 3.5 nm) at the {101} facet of the TiO2 to optimally tune exciton recombination through oxygen vacancies generation, evidenced by photoluminescence and Raman spectroscopy measurements. The turnover frequency (TOF) and the apparent quantum efficiency (AQE) of the 7%CuO/TiO2-spindle composites reach up to 23.8 molmethanol·gcat-1·h-1 and 55.2% at 25 °C, respectively, which are substantially higher than these previously reported photocatalysts. Further, the in-situ attenuated total reflection infrared spectroscopy analysis reveals that the methanol oxidation most likely takes place through the conversion of adsorbed methoxy (CH3O*) to formaldehyde (CHO*) intermediate, a subject of major debate for a long time. The adsorbed formaldehyde (CHO*) thus produced reacts with another CH3O* species in its close proximity to form the final product of methyl formate. Results of this study provide insights into the reaction mechanism, and offer guidelines to systematically develop and apply photocatalysts for methanol conversion and related reactions via surface engineering.

Keywords: oxygen vacancy, photocatalysis, methanol, CuO/TiO2 nanocomposite, methyl formate, in-situ attenuated total reflection infrared spectroscopy

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Publication history
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Acknowledgements

Publication history

Received: 15 November 2019
Revised: 15 February 2020
Accepted: 16 February 2020
Published: 09 March 2020
Issue date: April 2020

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020

Acknowledgements

Q. Q. S. thanks the Postdoctoral Science Foundation of China (No. 223232), the Natural Science Foundation of Inner Mongolia Autonomous Region (No. 2018BS02004), the major special topics of Inner Mongolia science and technology department (No. 20181351), Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region (No. NJYT-20-B20), the Program of Higher-level Talents of Inner Mongolia Agricultural University (No. NDYB2016-03), LiaoNing Revitalization Talents Program (No. XLYC1807121) and Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2019) for financial support.

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