Electrochemical Potential-Driven Shift of Frontier Orbitals in M-N-C Single-Atom Catalysts Leading to Inverted Adsorption Energies

Liu, Jin-Cheng1,2; Luo, Feng1,2; Li, Jun3,4,5,6

2023-11-08

10.1021/jacs.3c08697

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Electronic structure is essential to understanding the catalytic mechanism of metal single-atom catalysts (SACs), especially under electrochemical conditions. This study delves into the nuanced modulation of "frontier orbitals" in SACs on nitrogen-doped graphene (N-C) substrates by electrochemical potentials. We observe shifts in Fermi level and changes of d-orbital occupation with alterations in electrochemical potentials, emphasizing a synergy between the discretized atomic orbitals of metals and the continuous bands of the N-C based environment. Using O-2 and CO2 as model adsorbates, we highlight the direct consequences of these shifts on adsorption energies, unveiling an intriguing inversion of adsorption energies on Co/N-C SAC under negative electrochemical potentials. Such insights are attributed to the role of the d(xz) and d(z)(2) orbitals, pivotal for stabilizing the pi* orbitals of O-2. Through this exploration, our work offers insights on the interplay between electronic structures and adsorption behaviors in SACs, paving the way for enhanced catalyst design strategies in electrochemical processes.

SCI ; EI

英语

NI论文

其他

National Key Research and Development Program of China[2021YFA1601004] ; National Key Research and Development Program of China[22JCQNJC01490] ; Tianjin Science and Technology Plan["2022YFA1503900","2022YFA1503000"] ; National Key R&D Program of China or National Key Research and Development Project[22033005]

Chemistry

Chemistry, Multidisciplinary

WOS:001108460200001

AMER CHEMICAL SOC

20234915144507

Adsorption ; Atoms ; Doping (additives) ; Electronic structure ; Quantum chemistry

Physical Chemistry:801.4 ; Chemical Operations:802.3 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Atomic and Molecular Physics:931.3

Web of Science

1.Nankai Univ, Ctr Rare Earth & Inorgan Funct Mat, Sch Mat Sci & Engn, Tianjin 300350, Peoples R China
2.Nankai Univ, Natl Inst Adv Mat, Tianjin 300350, Peoples R China
3.Tsinghua Univ, Minist Educ, Dept Chem, Beijing 100084, Peoples R China
4.Tsinghua Univ, Engn Res Ctr Adv Rare Earth Mat, Minist Educ, Beijing 100084, Peoples R China
5.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
6.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalyt Chem, Shenzhen 518055, Peoples R China

Liu, Jin-Cheng,Luo, Feng,Li, Jun. Electrochemical Potential-Driven Shift of Frontier Orbitals in M-N-C Single-Atom Catalysts Leading to Inverted Adsorption Energies[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023,145(46):25264-25273.

Liu, Jin-Cheng,Luo, Feng,&Li, Jun.(2023).Electrochemical Potential-Driven Shift of Frontier Orbitals in M-N-C Single-Atom Catalysts Leading to Inverted Adsorption Energies.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,145(46),25264-25273.

Liu, Jin-Cheng,et al."Electrochemical Potential-Driven Shift of Frontier Orbitals in M-N-C Single-Atom Catalysts Leading to Inverted Adsorption Energies".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145.46(2023):25264-25273.