Boosting Efficient Ammonia Synthesis over Atomically Dispersed Co-Based Catalyst via the Modulation of Geometric and Electronic Structures

Zhou，Yanliang1; Wang，Congying1; Peng，Xuanbei1; Zhang，Tianhua1; Wang，Xiuyun1; Jiang，Yafei2; Qi，Haifeng3; Zheng，Lirong4; Lin，Jianxin1; Jiang，Lilong1

2022-05-01

10.31635/ccschem.021.202100912

CCS Chemistry   Impact Factor & Quartile

2096-5745

Ammonia (NH) synthesis at mild conditions is of great significance, while the significant bottleneck of this process is the activation of N2 to realize the desired NHsynthesis performance, which requires deep insight and rational design of active sites at the atomic level. Here, were synthesized atomically dispersed Co-based catalysts with different Co-N coordination numbers (CNs) to explore the coordination-sensitive NHsynthesis reaction for the first time. Our studies showed that Co-based catalysts increased the NHsynthesis rate gradually with a decrease in CN. The Co-N2 catalyst exhibited the highest NHsynthesis rate of 85.3 mmol gCo -1 h-1 at 300°C and 1 MPa, which outperformed most of the previously reported Co-based catalysts. Various characterizations and theoretical calculations demonstrated that atomically dispersed Co catalyst with low CN could generate more unoccupied Co 3d charges and tetrahedral cobalt(II) sites. The unoccupied Co 3d charge, in turn, promoted the electron donation from the Co active center to the antibonding π-orbital (π*) of N2 and expedites N2 hydrogenation. Furthermore, the Co-N2 catalyst with more tetrahedral cobalt(II) sites could effectively facilitate the desorption of N-containing intermediate species (such as*NHand*N2H4) to obtain a high NHsynthesis rate.

ammonia synthesis coordination number electron transfer geometric structure intermediate species

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English

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WOS:000794318300028

2-s2.0-85132613386

Scopus

1.National Engineering Research Center of Chemical Fertilizer Catalyst,Fuzhou University,Fuzhou,Fujian,350002,China
2.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
3.Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,116023,China
4.Institute of High Energy Physics,Chinese Academy of Sciences,Beijing,100049,China

Zhou，Yanliang,Wang，Congying,Peng，Xuanbei,et al. Boosting Efficient Ammonia Synthesis over Atomically Dispersed Co-Based Catalyst via the Modulation of Geometric and Electronic Structures[J]. CCS Chemistry,2022,4(5):1758-1769.

Zhou，Yanliang.,Wang，Congying.,Peng，Xuanbei.,Zhang，Tianhua.,Wang，Xiuyun.,...&Jiang，Lilong.(2022).Boosting Efficient Ammonia Synthesis over Atomically Dispersed Co-Based Catalyst via the Modulation of Geometric and Electronic Structures.CCS Chemistry,4(5),1758-1769.

Zhou，Yanliang,et al."Boosting Efficient Ammonia Synthesis over Atomically Dispersed Co-Based Catalyst via the Modulation of Geometric and Electronic Structures".CCS Chemistry 4.5(2022):1758-1769.