Low-Valence Metal Single Atoms on Graphdiyne Promotes Electrochemical Nitrogen Reduction via M-to-N-2 pi-Backdonation

Zou, Haiyuan1,2,3; Arachchige, Lakshitha Jasin4,5,6; Rong, Weifeng2,3; Tang, Chao2,3; Wang, Ranhao7; Tan, Sha8; Chen, Hong7; He, Dongsheng9; Hu, Junhui2,3; Hu, Enyuan8; Sun, Chenghua4,5,6; Duan, Lele2,3

2022-03-01

10.1002/adfm.202200333

ADVANCED FUNCTIONAL MATERIALS   影响因子和分区

1616-301X

1616-3028

The M-to-N-2 pi-backdonation weakens the triple bond of N-2 and shall promote the sluggish electrochemical nitrogen reduction reaction (ENRR). By using weak sigma- and pi-donating graphdiyne (GDY) as a supporting material, herein, a versatile approach is described to stabilize low-valence metal single atoms (SA) on GDY (M SA/GDY; M = Cr, Mo, W, Mn, and Re). Under the rigorous ENRR protocol, an activity trend of Re SA/GDY > Mo SA/GDY > Cr SA/GDY > W SA/GDY >> Mn SA/GDY (no activity) is delivered. Theoretical calculations reveal that the strong M-to-N-2 pi-backdonation of Re SA/GDY renders a low energy requirement of +0.39 eV for the reductive hydrogenation of *N-2 to *NNH, which is considered as the bottleneck of ENRR. A novel NH3 desorption mechanism through N-2 or H2O aided ligand exchange mechanism is proposed to facilitate the NH3 desorption from Re SA/GDY with a low energy input of +0.83 eV for the distal and mix pathways. This study expands the scope of low-valance SA with boosted pi-backdonation capacity and offers new mechanistic insights for ENRR.

electrochemical nitrogen reduction ligand exchange mechanism low-valence metal single-atom catalysts pi-backdonation

SCI ; EI

英语

NI期刊

通讯

National Natural Science Foundation of China[22179057] ; Shenzhen RD Fund[KQTD20180411143418361] ; Stable Support Plan Program of Shenzhen Natural Science Fund[20200925152742003] ; Educational Commission of Guangdong Province[2020KTSCX121] ; Guangdong Innovation Research Team for Higher Education[2017KCXTD030] ; Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. DOE through the Advanced Battery Materials Research (BMR) Program[DE-SC0012704] ; DOE Office of Science by Brookhaven National Laboratory[DE-SC0012704]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Multidisciplinary ; Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Applied ; Physics, Condensed Matter

WOS:000766951600001

WILEY-V C H VERLAG GMBH

20221111788796

Ammonia ; Atoms ; Desorption ; Electrolytic reduction ; Nitrogen

Ore Treatment:533.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Atomic and Molecular Physics:931.3

MATERIALS SCIENCE

Web of Science

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
4.Swinburne Univ Technol, Dept Chem & Biotechnol, Hawthorn, Vic 3122, Australia
5.Swinburne Univ Technol, Ctr Translat Atomat, FSET, Hawthorn, Vic 3122, Australia
6.Dongguan Univ Technol, Sch Chem Engn & Energy Technol, Dongguan 523808, Peoples R China
7.Southern Univ Sci & Technol, Sch Environm Sci & Engn, Shenzhen 518055, Peoples R China
8.Brookhaven Natl Lab, Chem Div, Upton, NY 11973 USA
9.Southern Univ Sci & Technol, Core Res Facil, Shenzhen 518055, Peoples R China

Zou, Haiyuan,Arachchige, Lakshitha Jasin,Rong, Weifeng,et al. Low-Valence Metal Single Atoms on Graphdiyne Promotes Electrochemical Nitrogen Reduction via M-to-N-2 pi-Backdonation[J]. ADVANCED FUNCTIONAL MATERIALS,2022,32.

Zou, Haiyuan.,Arachchige, Lakshitha Jasin.,Rong, Weifeng.,Tang, Chao.,Wang, Ranhao.,...&Duan, Lele.(2022).Low-Valence Metal Single Atoms on Graphdiyne Promotes Electrochemical Nitrogen Reduction via M-to-N-2 pi-Backdonation.ADVANCED FUNCTIONAL MATERIALS,32.

Zou, Haiyuan,et al."Low-Valence Metal Single Atoms on Graphdiyne Promotes Electrochemical Nitrogen Reduction via M-to-N-2 pi-Backdonation".ADVANCED FUNCTIONAL MATERIALS 32(2022).