Enriching surface- ordered defects on WO3 for photocatalytic CO2-to-CH4 conversion by water

被引:20
作者
Xue, Sikang [1 ,2 ]
Wei, Changgeng [1 ]
Shen, Min [1 ]
Liang, Xiaocong [1 ]
Wang, Jiali [1 ]
Yang, Can [1 ]
Xing, Wandong [1 ]
Wang, Sibo [1 ]
Lin, Wei [1 ]
Yu, Zhiyang [1 ]
Hou, Yidong [1 ]
Yu, Jimmy C. [1 ,3 ]
Wang, Xinchen [1 ,2 ]
机构
[1] Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou 350108, Peoples R China
[2] Fuzhou Univ, Coll Chem Engn, Fujian Sci & Technol Innovat Lab Chem Engn China, Quanzhou 362114, Peoples R China
[3] Chinese Univ Hong Kong, Dept Chem, Shatin, Hong Kong 999077, Peoples R China
基金
中国国家自然科学基金; 中国博士后科学基金;
关键词
surface- ordered defects; unsaturated coordination; induced polarization; photocatalysis; CO; 2; conversion; SELECTIVE CO2 PHOTOREDUCTION; TOTAL-ENERGY CALCULATIONS; CARBON-DIOXIDE; REDUCTION; EFFICIENT; ACTIVATION; SITES; PAIRS; TIO2;
D O I
10.1073/pnas.2319751121
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Defect engineering has been widely applied in semiconductors to improve photocatalytic properties by altering the surface structures. This study is about the transformation of inactive WO 3 nanosheets to a highly effective CO 2 - to - CH 4 conversion photocatalyst by introducing surface - ordered defects in abundance. The nonstoichiometric WO 3 - x samples were examined by using aberration - corrected electron microscopy. Results unveil abundant surface - ordered terminations derived from the periodic {013} stacking faults with a defect density of 20.2%. The {002} surface - ordered line defects are the active sites for fixation CO 2 , transforming the inactive WO 3 nanosheets into a highly active catalyst (CH 4 : O 2 = 8.2: 16.7 mu mol h -1 ). We believe that the formation of the W - O - C - W - O species is a critical step in the catalytic pathways. This work provides an atomic - level comprehension of the structural defects of catalysts for activating small molecules.
引用
收藏
页数:8
相关论文
共 54 条
[1]   CO2 Activation over Catalytic Surfaces [J].
Alvarez, Andrea ;
Borges, Marta ;
Jose Corral-Perez, Juan ;
Giner Olcina, Joan ;
Hu, Lingjun ;
Cornu, Damien ;
Huang, Rui ;
Stoian, Dragos ;
Urakawa, Atsushi .
CHEMPHYSCHEM, 2017, 18 (22) :3135-3141
[2]   Polaron mobility in oxygen-deficient and lithium-doped tungsten trioxide [J].
Bondarenko, N. ;
Eriksson, O. ;
Skorodumova, N. V. .
PHYSICAL REVIEW B, 2015, 92 (16)
[3]   Photosynthetic semiconductor biohybrids for solar-driven biocatalysis [J].
Cestellos-Blanco, Stefano ;
Zhang, Hao ;
Kim, Ji Min ;
Shen, Yue-xiao ;
Yang, Peidong .
NATURE CATALYSIS, 2020, 3 (03) :245-255
[4]   CO2 photo-reduction: insights into CO2 activation and reaction on surfaces of photocatalysts [J].
Chang, Xiaoxia ;
Wang, Tuo ;
Gong, Jinlong .
ENERGY & ENVIRONMENTAL SCIENCE, 2016, 9 (07) :2177-2196
[5]   Linear response approach to the calculation of the effective interaction parameters in the LDA+U method [J].
Cococcioni, M ;
de Gironcoli, S .
PHYSICAL REVIEW B, 2005, 71 (03)
[6]   Defect-Rich Bi12O17Cl2 Nanotubes Self-Accelerating Charge Separation for Boosting Photocatalytic CO2 Reduction [J].
Di, Jun ;
Zhu, Chao ;
Ji, Mengxia ;
Duan, Meilin ;
Long, Ran ;
Yan, Cheng ;
Gu, Kaizhi ;
Xiong, Jun ;
She, Yuanbin ;
Xia, Jiexiang ;
Li, Huaming ;
Liu, Zheng .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (45) :14847-14851
[7]   Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2 [J].
Favaro, Marco ;
Xiao, Hai ;
Cheng, Tao ;
Goddard, William A., III ;
Yano, Junko ;
Crumlin, Ethan J. .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2017, 114 (26) :6706-6711
[8]   Surface chemistry of carbon dioxide [J].
Freund, HJ ;
Roberts, MW .
SURFACE SCIENCE REPORTS, 1996, 25 (08) :225-273
[9]   A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper [J].
Gattrell, M. ;
Gupta, N. ;
Co, A. .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 2006, 594 (01) :1-19
[10]   Photoexcited Surface Frustrated Lewis Pairs for Heterogeneous Photocatalytic CO2 Reduction [J].
Ghuman, Kulbir Kaur ;
Hoch, Laura B. ;
Szymanski, Paul ;
Loh, Joel Y. Y. ;
Kherani, Nazir P. ;
E-Sayed, Mostafa A. ;
Ozin, Geoffrey A. ;
Singh, Chandra Veer .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (04) :1206-1214