Heterogeneous Fe3 single-cluster catalyst for ammonia synthesis via an associative mechanism

被引：609
作者：
Liu, Jin-Cheng
Ma, Xue-Lu
Li, Yong
Wang, Yang-Gang
Xiao, Hai
Li, Jun [1 ]
机构：
[1] Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
来源：
NATURE COMMUNICATIONS | 2018年 / 9卷
基金：
中国国家自然科学基金; 中国博士后科学基金; 北京市自然科学基金;
关键词：
N-2; REDUCTION; IRON COMPLEXES; NITROGEN REDUCTION; AMBIENT CONDITIONS; ELECTRO-CATALYSTS; SCALING RELATIONS; FE-N-2; COMPLEX; VOLCANO CURVE; CO OXIDATION; DINITROGEN;
D O I：
10.1038/s41467-018-03795-8
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：
The current industrial ammonia synthesis relies on Haber-Bosch process that is initiated by the dissociative mechanism, in which the adsorbed N-2 dissociates directly, and thus is limited by Bronsted-Evans-Polanyi (BEP) relation. Here we propose a new strategy that an anchored Fe-3 cluster on the theta-Al2O3(010) surface as a heterogeneous catalyst for ammonia synthesis from first-principles theoretical study and microkinetic analysis. We have studied the whole catalytic mechanism for conversion of N-2 to NH3 on Fe-3/theta-Al2O3(010), and find that an associative mechanism, in which the adsorbed N-2 is first hydrogenated to NNH, dominates over the dissociative mechanism, which we attribute to the large spin polarization, low oxidation state of iron, and multi-step redox capability of Fe-3 cluster. The associative mechanism liberates the turnover frequency (TOF) for ammonia production from the limitation due to the BEP relation, and the calculated TOF on Fe-3/theta-Al2O3(010) is comparable to Ru B5 site.
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页数：9
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