Asymmetric Coordination of Single‐Atom Co Sites Achieves Efficient Dehydrogenation Catalysis. (15th August 2022)

• Record Type: Journal Article
• Authors: Liu, Hu; Lei, Qian; Miao, Ruoyan; Sun, Mingzi; Qin, Chuanjian; Zhang, Liang; Ye, Gan; Yao, Yao; Huang, Bolong; Ma, Zhenhui
• Is Part Of: Advanced functional materials. Volume 32:Number 43(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-15
• Subjects: asymmetric coordinations -- atomic Co -- formic acid dehydrogenation -- nitrogen‐doped carbon nanowires networks -- single‐atom sites; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.202207408
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: Tuning asymmetric coordination of metal single‐atom (SA) sites can provide a new opportunity for optimizing the electronic structure of catalysts to achieve efficient catalysis, however, achieving such controllable design remains a grand challenge. Herein, an asymmetrically coordinated Co‐N4 P SA site as a new catalyst system for achieving superior dehydrogenation catalysis of formic acid (HCOOH) is reported. The experimental results show that the Co atom is coordinated by four N atoms and one asymmetric P atom, forming the unique Co‐N4 P SA sites. The Co‐N4 P SA sites exhibit an impressive mass activity of 4285.6 mmol g –1 h –1 with 100% selectivity and outstanding stability for HCOOH dehydrogenation catalysis at 80 °C, which is 5.0, 25.5, and 23.1 times that of symmetrically coordinated Co‐N4 SA sites, commercial Pd/C and Pt/C, respectively. The in situ ATR‐IR analysis demonstrates the mono‐molecular H2 produced mechanism over Co‐N4 P SA sites, and theoretical calculations further reveal that the asymmetric P sites not only can boost the CH bond cleavage of HCOO* by largely reducing the energy barrier but also facilitate the proton adsorption to achieve the fast generation of H2 in Co‐N4 P SA sites. This study opens a new way for rationally designing novel SA sites to achieve efficient catalysis. Abstract : The coordination environments of atomically dispersed active sites are significant for modulating the activity and selectivity. A novel asymmetrically coordinated Co‐N4 P SA site is reported to achieve superior dehydrogenation catalysis of HCOOH with high activity, 100% selectivity, and outstanding stability under a mild condition. This work offers advanced insights into the design of efficient SA sites catalysts.