催化作用
材料科学
选择性
无定形固体
悬空债券
产量(工程)
法拉第效率
过渡金属
纳米技术
化学工程
密度泛函理论
化学物理
化学
物理化学
计算化学
结晶学
硅
电化学
有机化学
电极
冶金
工程类
作者
Meng Zhang,Wanping Xu,Chunlan Ma,Jianyong Yu,Yi‐Tao Liu,Bin Ding
出处
期刊:ACS Nano
[American Chemical Society]
日期:2022-03-10
卷期号:16 (3): 4186-4196
被引量:38
标识
DOI:10.1021/acsnano.1c10059
摘要
The electroreduction of N2 under ambient conditions has emerged as one of the most promising technologies in chemistry, since it is a greener way to make NH3 than the traditional Haber-Bosch process. However, it is greatly challenged with a low NH3 yield and faradaic efficiency (FE) because of the lack of highly active and selective catalysts. Inherently, transition (d-block) metals suffer from inferior selectivity due to fierce competition from H2 evolution, while post-transition (p-block) metals exhibit poor activity due to insufficient "π back-donation" behavior. Considering their distinct yet complementary electronic structures, here we propose a strategy to tackle the activity and selectivity challenge through the atomic dispersion of p-block metal on an all-amorphous transition-metal matrix. To address the activity issue, lotus-root-like amorphous TiO2 nanofibers are synthesized which, different from vacancy-engineered TiO2 nanocrystals reported previously, possess abundant intrinsic oxygen vacancies (VO) together with under-coordinated dangling bonds in nature, resulting in significantly enhanced N2 activation and electron transport capacity. To address the selectivity issue, well-isolated single atoms (SAs) of Ga are successfully synthesized through the confinement effect of VO, resulting in Ga-VO reactive sites with the maximum availability. It is revealed by density functional theory calculations that Ga SAs are favorable for the selective adsorption of N2 at the catalyst surface, while VO can facilitate N2 activation and reduction subsequently. Benefiting from this coupled activity/selectivity design, high NH3 yield (24.47 μg h-1 mg-1) and FE (48.64%) are achieved at an extremely low overpotential of -0.1 V vs RHE.
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