共 21 条
Light-assistance in nitrogen fixation to ammonia by highly dispersed Cs-promoted Ru clusters supported on ZrO2
被引：9
|作者：
Peng, Yong
[1
]
Melillo, Arianna
[1
]
Shi, Run
[2
]
Forneli, Amparo
[1
]
Franconetti, Antonio
[3
]
Albero, Josep
[1
]
Garcia, Hermenegildo
[1
]
机构：
[1] Univ Politecn Valencia, Inst Univ Tecnol Quim CSIC UPV, Dept Quim, Avda Naranjos S-N, Valencia 46022, Spain
[2] Chinese Acad Sci, Key Lab Photochem Convers & Optoelect Mat, Tech Inst Phys & Chem, Beijing 100190, Peoples R China
[3] Univ Seville, Fac Quim, Dept Quim Organ, Seville 41012, Spain
来源：
关键词：
Metal clusters;
Photocatalysis;
N(2)fixation;
Ammonia;
MOF-derived photocatalyst;
Surface plasmonic resonance effects;
Hot electrons injection;
CATALYSTS;
NANOPARTICLES;
CO;
DFT;
D O I：
10.1016/j.apcatb.2023.123143
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ;
081704 ;
摘要：
Light-assisted N-2 fixation to NH3 under mild conditions is attracting massive attention to circumvent energy crisis and global warming. Herein, highly dispersed Cs-decorated Ru sub-nanometric clusters supported on ZrO2 NPs have been prepared by means of MOF-templated transformation method. The obtained catalyst exhibited N-2 hydrogenation activity of 1.6 mmolNH3 g(cat)(-1) h (-1) in the dark (350.C, 0.1 MPa). Remarkably this value increased by over 300 %, reaching 5.1 mmolNH3 g(cat)(-1) h (-1) (204 mmolNH3 g(Ru)(-1) h (-1)) under 1 Sun power illumination (1080 W/ m2) The influence of the incident light wavelength has been evaluated, revealing 81 % and 213 % enhancement in the NIR and visible region, respectively. DFT calculations were carried out to understand the static adsorption states of Ru sub-nanoclusters. Mechanistic studies have confirmed the co-existence of a photothermal and a nonthermal-hot electron mechanism. XPS, PXRD and FTIR analysis have determined that the Cs species block surface Zr4+ acidity, increasing the basicity of the ZrO2 support. Moreover, partially reduced Cs delta+ (0 <delta < 1) species surrounding the Ru active sites are donating electron density to the adjacent Ru sites, favoring N-2 adsorption and subsequent activation. Finally, this photocatalyst has shown an extended stability for 100 h irradiation under continuous flow.
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页数：10
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