General Synthesis of a Diatomic Catalyst Library via a Macrocyclic Precursor-Mediated Approach

Abstract

Heterogeneous catalysts containing diatomic sites are often hypothesized to have distinctive reactivity due to synergistic effects, but there are limited approaches that enable the convenient production of diatomic catalysts (DACs) with diverse metal combinations. Here, we present a general synthetic strategy for constructing a DAC library across a wide spectrum of homonuclear (Fe 2 , Co 2 , Ni 2 , Cu 2 , Mn 2 , and Pd 2 ) and heteronuclear (Fe−Cu, Fe−Ni, Cu−Mn, and Cu−Co) bimetal centers. This strategy is based on an encapsulation−pyrolysis approach, wherein a porous material-encapsulated macrocyclic complex mediates the structure of DACs by preserving the main body of the molecular framework during pyrolysis. We take the oxygen reduction reaction (ORR) as an example to show that this DAC library can provide great opportunities for electrocatalyst development by unlocking an unconventional reaction pathway. Among all investigated sites, Fe−Cu diatomic sites possess exceptional high durability for ORR because the Fe−Cu pairs can steer elementary steps in the catalytic cycle and suppress the troublesome Fenton-like reactions.

Dual‐Atomic‐Site Catalysts for Molecular Oxygen Activation in Heterogeneous Thermo‐/Electro‐catalysis

“…The mechanical ball-milling and calcination treatment of porous material-encapsulated macrocyclic dual-metal complexes may be a promising general and largescale synthesis approach of DASCs. [47] Second, the characterization of atomic interactions in DASCs is still hard to achieve. Structural variables such as atomic size and local coordination environment make the characterization of DASCs more complex than that of the traditional metal catalysts in the form of single atoms, nanoclusters, and nanoparticles.…”

Machine-Learning-Accelerated Screening of Double-Atom/Cluster Electrocatalysts for the Oxygen Reduction Reaction

“…Note that, in an experimental study, Chu et al 92 reported that the Fe−Ce DAC has a much higher ORR catalytic activity than Fe−N 4 , which agrees with the above calculations. Similarly, Co−Ni-1, 93 Fe−Ni-1, 94 Mn−Cu-0, 12 and Mn−Zn-0, 95 The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpcc.3c05753.…”

Dual Atom Catalysts for Energy and Environmental Applications

“…There has been abundant data in the ever‐evolving field of DACs. Pioneering works have already established standardized library of databases [28, 97] . These outstanding examples provide soild experimental database for the next generation of high‐throughput catalyst exploration and screening with ML and AI.…”