A polyoxometalate cluster-based single-atom catalyst for NH3 synthesis via an enzymatic mechanism

Talib, Shamraiz Hussain1; Yu, Xiaohu2; Lu, Zhansheng1; Ahmad, Khalil3; Yang, Tongtong4; Xiao, Hai4; Li, Jun4,5

2021-11-01

10.1039/d1ta07903d

Journal of Materials Chemistry A   影响因子和分区

2050-7488

2050-7496

NH3 synthesis by the electrochemical N-2 reduction reaction (eNRR) under mild conditions has attracted much attention. Here, by means of the first principles calculations, we propose a new strategy using a transition metal single-atom catalyst (SAC) anchored on a phosphomolybdic acid (PMA) cluster as a heterogeneous catalyst for the eNRR. We have systematically studied three reaction mechanisms, i.e., distal, alternating, and enzymatic pathways, respectively, for the eNRR on a Mo-1/PMA SAC via a six-proton and six-electron process, and found that the preferred mechanism is the enzymatic pathway with the smallest overpotential (eta) of 0.19 V. N-2 is first strongly adsorbed on Mo-1/PMA and then dissociated by the subsequent protonation process. In addition, we found that Mo-1/PMA can impede the hydrogen evolution reaction (HER) process and thus promotes the eNRR selectivity. The high catalytic activity of Mo-1/PMA for the eNRR is attributed to the high spin density on Mo, enhanced N-2 adsorption, stabilization of the N2H* species, and the destabilization of the NH2* species. The present work is further extended to investigate the kinetics of the conversion of N-2 to ammonia on Mo-1/PMA via an enzymatic mechanism. Our results expose that the calculated activation energy barrier for the protonation of N-2 to form the N2H4* species is kinetically and thermodynamically more favorable compared with other elementary steps. These results provide valuable guidance for NH3 synthesis using SACs at ambient temperature with high efficiency and low cost.

SCI ; EI

英语

通讯

Natural Science Basic Research Program of Shaanxi Province["S2020-JC-WT-0001","2019JM-226"] ; National Science Foundation of China[22033005] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Special Funding for Transformation of Scientific and Technological Achievements in Qinghai Province[2018-GX-101]

Chemistry ; Energy & Fuels ; Materials Science

Chemistry, Physical ; Energy & Fuels ; Materials Science, Multidisciplinary

WOS:000730767200001

ROYAL SOC CHEMISTRY

20221411912493

Activation energy ; Calculations ; Catalyst activity ; Protonation ; Transition metals

Metallurgy and Metallography:531 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Mathematics:921

Web of Science

1.Henan Normal Univ, Sch Phys, Xinxiang 453007, Henan, Peoples R China
2.Shaanxi Univ Technol, Sch Chem & Environm Sci, Shaanxi Key Lab Catalysis, Hanzhong 723000, Peoples R China
3.Mirpur Univ Sci & Technol MUST, Dept Chem, Mirpur 10250, Ajk, Pakistan
4.Tsinghua Univ, Dept Chem, Key Lab Organ Optoelect & Mol Engn, Minist Educ, Beijing 100084, Peoples R China
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Talib, Shamraiz Hussain,Yu, Xiaohu,Lu, Zhansheng,et al. A polyoxometalate cluster-based single-atom catalyst for NH3 synthesis via an enzymatic mechanism[J]. Journal of Materials Chemistry A,2021,10:6165-6177.

Talib, Shamraiz Hussain.,Yu, Xiaohu.,Lu, Zhansheng.,Ahmad, Khalil.,Yang, Tongtong.,...&Li, Jun.(2021).A polyoxometalate cluster-based single-atom catalyst for NH3 synthesis via an enzymatic mechanism.Journal of Materials Chemistry A,10,6165-6177.

Talib, Shamraiz Hussain,et al."A polyoxometalate cluster-based single-atom catalyst for NH3 synthesis via an enzymatic mechanism".Journal of Materials Chemistry A 10(2021):6165-6177.