DOI: 10.1016/j.scib.2020.03.032
论文题名: Selective photocatalytic CO2 reduction over Zn-based layered double hydroxides containing tri or tetravalent metals
作者: Xiong X. ; Zhao Y. ; Shi R. ; Yin W. ; Zhao Y. ; Waterhouse G.I.N. ; Zhang T.
刊名: Science Bulletin
ISSN: 20959273
出版年: 2020
卷: 65, 期: 12 起始页码: 987
结束页码: 994
语种: 英语
中文关键词: d band center
; Layered double hydroxide
; Photocatalytic CO2 reduction
; Selectivity
; Tri/tetravalent metal cations
英文关键词: Aluminum compounds
; Carbon dioxide
; Catalyst selectivity
; Density functional theory
; Fermi level
; Iron compounds
; Metals
; Positive ions
; Probability density function
; Titanium compounds
; Carbon-containing products
; CO2 reduction
; D-band centers
; Density function theory calculations
; Infrared measurements
; Layered double hydroxides
; Metal cation
; Product selectivities
; Zinc compounds
英文摘要: Photocatalytic CO2 reduction holds promise as a future technology for the manufacture of fuels and commodity chemicals. However, factors controlling product selectivity remain poorly understood. Herein, we compared the performance of a homologous series of Zn-based layered double hydroxide (ZnM-LDH) photocatalysts for CO2 reduction. By varying the trivalent or tetravalent metal cations in the ZnM-LDH photocatalysts (M = Ti4+, Fe3+, Co3+, Ga3+, Al3+), the product selectivity of the reaction could be precisely controlled. ZnTi-LDH afforded CH4 as the main reduction product; ZnFe-LDH and ZnCo-LDH yielded H2 exclusively from water splitting; whilst ZnGa-LDH and ZnAl-LDH generated CO. In-situ diffuse reflectance infrared measurements, valence band XPS and density function theory calculations were applied to rationalize the CO2 reduction selectivities of the different ZnM-LDH photocatalysts. The analyses revealed that the d-band center (εd) position of the M3+ or M4+ cations controlled the adsorption strength of CO2 and thus the selectivity to carbon-containing products or H2. Cations with d-band centers relatively close to the Fermi level (Ti4+, Ga3+ and Al3+) adsorbed CO2 strongly yielding CH4 or CO, whereas metal cations with d-band centers further from the Fermi level (Fe3+ and Co3+) adsorbed CO2 poorly, thereby yielding H2 only (from water splitting). Our findings clarify the role of trivalent and tetravalent metal cations in LDH photocatalysts for the selective CO2 reduction, paving new ways for the development of improved LDH photocatalyst with high selectivities to specific products. © 2020 Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/170103
Appears in Collections: 气候变化与战略
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作者单位: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academmy of Sciences, Beijing, 100190, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China; State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China; School of Physics and Electronic Science, Hunan University of Science and Technology, Xiangtan, 411201, China; School of Chemical Sciences, The University of Auckland, Auckland, 1142, New Zealand
Recommended Citation:
Xiong X.,Zhao Y.,Shi R.,et al. Selective photocatalytic CO2 reduction over Zn-based layered double hydroxides containing tri or tetravalent metals[J]. Science Bulletin,2020-01-01,65(12)