Ball‐Milling Induced Debonding of Surface Atoms from Metal Bulk for Construing High‐Performance Dual‐Site Single‐Atom Catalysts

Abstract

One of the most pressing challenges in single‐atom catalysis is the manipulation of the coordination environment of central metals to maximize the catalyst performance. Herein, we fabricated a high‐performance catalyst (Co‐SNC) by introducing S into the neighboring position of the Co‐N4 coordination. The developed ball‐milling method enabled large‐scale synthesis, that over 4.7 g of Co‐SNC can be produced in one pot. In benzylamine coupling reaction, Co‐SNC exhibited the highest conversion of 97.5 % with 99 % selectivity toward N‐benzylidenebenzylamine in 10 h among various Co catalysts. Density functional theory calculations revealed the crucial role of S atoms, which serve as the active sites for O2 activation, leaving the Co atoms free to adsorb benzylamine. Consequently, the adsorption energies of O2 and benzylamine were significantly increased. Our strategy suggests a feasible approach to enhance catalytic performance by delicately integrating dual active sites into a single catalyst unit.

Strategies for boosting the activity of single-atom catalysts for future energy applications

“…During the synthesis, the substances undergo an ultrane grinding process and induce the debonding of the surface atoms for realizing the large-scale preparation of SACs. 47,55 The basic process is to use a highenergy mechanical force to grind metal-containing precursors. Then SACs could be obtained by thermal treatment.…”

“…2a). 47 Recently, our group proposed a top-down abrasion method to prepare a series of SACs (Fe, Co, Ni, and Cu). The method utilizes the mechanochemical forces Fig.…”

“…2 (a) M-N 4 -S materials obtained via the ball-milling strategy. 47 (b) Electrodeposition strategy. 46 (c) Rh-based SACs prepared by a host-guest route.…”

Recent Progress in Thermal Conversion of CO2 via Single‐Atom Site Catalysis

“…Large-scale and universal routes for fabricating SACs need to be developed. So far, strategies like mechanochemical approach (ball-milling) [111,112] and pyrolyzing coordinated polymer [113] have been reported, but most synthetic procedures are not suitable for multisubstrates or unpractically applied in batch production. Meanwhile, processing high loading of SACs can be another challenge toward industry.…”

Advances in the Development of Single‐Atom Catalysts for High‐Energy‐Density Lithium–Sulfur Batteries

“…Figure 6. a) Fabrication of Co-SNC via ball milling. Reproduced with permission [149]. Copyright 2021, Wiley-VCH.…”