Role of Water and Carbonates in Photocatalytic Transformation of CO2 to CH4 on Titania

被引：417

作者：

Dimitrijevic, Nada M. ^{[1
,2
]}

Vijayan, Baiju K. ^{[4
]}

Poluektov, Oleg G. ^{[1
]}

Rajh, Tijana ^{[2
]}

Gray, Kimberly A. ^{[4
]}

He, Haiying ^{[3
]}

Zapol, Peter ^{[1
,3
]}

机构：

[1] Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA

[2] Argonne Natl Lab, Ctr Nanoscale Mat, Argonne, IL 60439 USA

[3] Argonne Natl Lab, Div Mat Sci, Argonne, IL 60439 USA

[4] Northwestern Univ, Dept Civil & Environm Engn, Evanston, IL 60208 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 11期

关键词：

ELECTRON-SPIN RESONANCE; TIO2; NANOPARTICLES; VISIBLE-LIGHT; SEMICONDUCTOR PHOTOCATALYSIS; AQUEOUS SUSPENSIONS; GAMMA-IRRADIATION; MAGNESIUM-OXIDE; AB-INITIO; REDUCTION; PHOTOREDUCTION;

D O I：

10.1021/ja108791u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and (OH)-O-center dot radicals (oxidation product) from water, and CO3- radical anions (oxidation product) from carbonates, was detected in CO2-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, (OCH3)-O-center dot, and methyl, (CH3)-C-center dot, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO2 on the surface of TiO2 is supported by the results of first-principles calculations.

引用

页码：3964 / 3971

页数：8

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