TM3 (TM = V, Fe, Mo, W) single-cluster catalyst confined on porous BN for electrocatalytic nitrogen reduction. (10th May 2022)

• Record Type: Journal Article
• Authors: Gao, Shuaishuai; Ma, Zuju; Xiao, Chengwei; Cui, Zhitao; Du, Wei; Sun, Xueqin; Li, Qiaohong; Sa, Rongjian; Sun, Chenghua
• Is Part Of: Journal of materials science & technology. Volume 108(2022)
• Page Start: 46
• Page End: 53
• Publication Date: 2022-05-10
• Subjects: Electrocatalytic N2 reduction -- Density functional theory -- Single-cluster -- Porous boron nitride; Metals -- Periodicals; Materials science -- Periodicals; Materials science; Metals; Periodicals; 620.1105
• DOI: 10.1016/j.jmst.2021.08.052
• Languages: English
• ISSNs: 1005-0302

Abstract

Highlights: Confined metal clusters in the triplet form as sub-nanometer reactors for NRR. Mo3 @p-BN exhibits excellent catalytic activity and selectivity. A rather low limiting potential (−0.34 V) was obtained. Mo atoms act as "cache" to accelerate electron transfer. Synergistic effect makes the "donation–backdonation" mechanism more efficient. Abstract: Confined metal clusters as sub-nanometer reactors for electrocatalytic N2 reduction reaction (eNRR) have received increasing attention due to the unique metal-metal interaction and higher activity than single-atom catalysts. Herein, the inspiration of the superior capacitance and unique microenvironment with regular surface cavities of the porous boron nitride (p-BN) nanosheets, we systematically studied the catalytic activity for NRR of transition-metal single-clusters in the triplet form (V3, Fe3, Mo3 and W3 ) confined in the surface cavities of the p-BN sheets by spin-polarized density functional theory (DFT) calculations. After a two-step screening strategy, Mo3 @p-BN was found to have high catalytic activity and selectivity with a rather low limiting potential (–0.34 V) for the NRR. The anchored Mo3 single-cluster can be stably embedded on the surface cavities of the substrate preventing the diffusion of the active Mo atoms. More importantly, the Mo atoms in the Mo3 single-cluster would act as "cache" to accelerate electron transfer between active metal centers and nitrogen-containing intermediates via the intimate Mo-Mo interactions. The cooperation of Mo atoms can also provide a large number of occupied and unoccupied d orbitals to make the "donation–backdonation" mechanism more effective. This work not only provides a quite promising electrocatalyst for NRR, but also brings new insights into the rational design of triple-atom NRR catalysts.