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Small. 2018 Jan;14(2). doi: 10.1002/smll.201702928. Epub 2017 Nov 14.

Ni-Nanocluster Modified Black TiO2 with Dual Active Sites for Selective Photocatalytic CO2 Reduction.

Author information

1
Nano Science and Technology Program, Taiwan International Graduate Program, Academia Sinica, Taipei, 115, Taiwan.
2
Department of Engineering and System Science, National Tsing Hua University, Hsinchu, 30013, Taiwan.
3
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, 10617, Taiwan.
4
Center for Condensed Matter Sciences, National Taiwan University, Taipei, 10617, Taiwan.
5
Institute of Optoelectronic Science, National Taiwan Ocean University, Keelung, 202, Taiwan.
6
Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, Hsinchu, 300, Taiwan.
7
National Synchrotron Radiation Research Center, Hsinchu, 30076, Taiwan.
8
Graduate Institute of Electro-Optical Engineering, National Taiwan University, Taipei, 10617, Taiwan.

Abstract

One of the key challenges in artificial photosynthesis is to design a photocatalyst that can bind and activate the CO2 molecule with the smallest possible activation energy and produce selective hydrocarbon products. In this contribution, a combined experimental and computational study on Ni-nanocluster loaded black TiO2 (Ni/TiO2[Vo] ) with built-in dual active sites for selective photocatalytic CO2 conversion is reported. The findings reveal that the synergistic effects of deliberately induced Ni nanoclusters and oxygen vacancies provide (1) energetically stable CO2 binding sites with the lowest activation energy (0.08 eV), (2) highly reactive sites, (3) a fast electron transfer pathway, and (4) enhanced light harvesting by lowering the bandgap. The Ni/TiO2[Vo] photocatalyst has demonstrated highly selective and enhanced photocatalytic activity of more than 18 times higher solar fuel production than the commercial TiO2 (P-25). An insight into the mechanisms of interfacial charge transfer and product formation is explored.

KEYWORDS:

artificial photosynthesis; black TiO2; photocatalytic CO2 reduction; solar fuels

PMID:
29134759
DOI:
10.1002/smll.201702928

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