Ultrathin WO3·0.33H2O Nanotubes for CO2 Photoreduction to Acetate with High Selectivity

Songmei Sun; Motonori Watanabe; Ji Wu; Qi An; Tatsumi Ishihara

doi:10.1021/jacs.8b03316

Ultrathin WO₃·0.33H₂O Nanotubes for CO₂ Photoreduction to Acetate with High Selectivity

Songmei Sun, Motonori Watanabe, Ji Wu, Qi An, Tatsumi Ishihara

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

264 Citations (SciVal)

Abstract

Artificial photosynthesis from CO₂ reduction is severely hampered by the kinetically challenging multi-electron reaction process. Oxygen vacancies (Vo) with abundant localized electrons have great potential to overcome this limitation. However, surface Vo usually have low concentrations and are easily oxidized, causing them to lose their activities. For practical application of CO₂ photoreduction, fabricating and enhancing the stability of Vo on semiconductors is indispensable. Here we report the first synthesis of ultrathin WO₃·0.33H₂O nanotubes with a large amount of exposed surface Vo sites, which can realize excellent and stable CO₂ photoreduction to CH₃COOH in pure water under solar light. The selectivity for acetum generation is up to 85%, with an average productivity of about 9.4 μmol g^-1 h^-1. More importantly, Vo in the catalyst are sustainable, and their concentration was not decreased even after 60 h of reaction. Quantum chemical calculations and in situ DRIFT studies revealed that the main reaction pathway might be CO₂ → ^•COOH → (COOH)₂ → CH₃COOH.

Original language	English
Pages (from-to)	6474-6482
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	140
Issue number	20
DOIs	https://doi.org/10.1021/jacs.8b03316
Publication status	Published - 23 May 2018

Funding

This work received financial support from the World Premier International Research Center Initiative (WPI Initiative) on Carbon-Neutral Energy Research (I2CNER), MEXT (Japan), National Natural Science Foundation of China (No. 21671197), a research grant (No. 16ZR1440800) from Shanghai Science and Technology Commission, and a Grant-in-Aid for Specially Promoted Research (No. 16H06293) from MEXT, Japan. J.W. thanks the funding support from the JSPS, Japan, and the NSF, USA, under the JSPS-NSF Partnerships for International Research and Education (PIRE). The authors would also like to thank Aleksandar Staykov for performing the calculations.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.8b03316

Cite this

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title = "Ultrathin WO3·0.33H2O Nanotubes for CO2 Photoreduction to Acetate with High Selectivity",

abstract = "Artificial photosynthesis from CO2 reduction is severely hampered by the kinetically challenging multi-electron reaction process. Oxygen vacancies (Vo) with abundant localized electrons have great potential to overcome this limitation. However, surface Vo usually have low concentrations and are easily oxidized, causing them to lose their activities. For practical application of CO2 photoreduction, fabricating and enhancing the stability of Vo on semiconductors is indispensable. Here we report the first synthesis of ultrathin WO3·0.33H2O nanotubes with a large amount of exposed surface Vo sites, which can realize excellent and stable CO2 photoreduction to CH3COOH in pure water under solar light. The selectivity for acetum generation is up to 85%, with an average productivity of about 9.4 μmol g-1 h-1. More importantly, Vo in the catalyst are sustainable, and their concentration was not decreased even after 60 h of reaction. Quantum chemical calculations and in situ DRIFT studies revealed that the main reaction pathway might be CO2 → •COOH → (COOH)2 → CH3COOH.",

author = "Songmei Sun and Motonori Watanabe and Ji Wu and Qi An and Tatsumi Ishihara",

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AU - Sun, Songmei

AU - Watanabe, Motonori

AU - Wu, Ji

AU - An, Qi

AU - Ishihara, Tatsumi

PY - 2018/5/23

Y1 - 2018/5/23

N2 - Artificial photosynthesis from CO2 reduction is severely hampered by the kinetically challenging multi-electron reaction process. Oxygen vacancies (Vo) with abundant localized electrons have great potential to overcome this limitation. However, surface Vo usually have low concentrations and are easily oxidized, causing them to lose their activities. For practical application of CO2 photoreduction, fabricating and enhancing the stability of Vo on semiconductors is indispensable. Here we report the first synthesis of ultrathin WO3·0.33H2O nanotubes with a large amount of exposed surface Vo sites, which can realize excellent and stable CO2 photoreduction to CH3COOH in pure water under solar light. The selectivity for acetum generation is up to 85%, with an average productivity of about 9.4 μmol g-1 h-1. More importantly, Vo in the catalyst are sustainable, and their concentration was not decreased even after 60 h of reaction. Quantum chemical calculations and in situ DRIFT studies revealed that the main reaction pathway might be CO2 → •COOH → (COOH)2 → CH3COOH.

AB - Artificial photosynthesis from CO2 reduction is severely hampered by the kinetically challenging multi-electron reaction process. Oxygen vacancies (Vo) with abundant localized electrons have great potential to overcome this limitation. However, surface Vo usually have low concentrations and are easily oxidized, causing them to lose their activities. For practical application of CO2 photoreduction, fabricating and enhancing the stability of Vo on semiconductors is indispensable. Here we report the first synthesis of ultrathin WO3·0.33H2O nanotubes with a large amount of exposed surface Vo sites, which can realize excellent and stable CO2 photoreduction to CH3COOH in pure water under solar light. The selectivity for acetum generation is up to 85%, with an average productivity of about 9.4 μmol g-1 h-1. More importantly, Vo in the catalyst are sustainable, and their concentration was not decreased even after 60 h of reaction. Quantum chemical calculations and in situ DRIFT studies revealed that the main reaction pathway might be CO2 → •COOH → (COOH)2 → CH3COOH.

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