1 + 1′ > 2: Heteronuclear Biatom Catalyst Outperforms Its Homonuclear Counterparts for CO Oxidation

Abstract

By means of density functional theory (DFT) computations, the CO/O2 adsorption and CO oxidation pathways on the biatom catalyst, namely the heteronuclear Fe1Cu1@C2N, in comparison with its homonuclear counterparts Fe2@C2N and Cu2@C2N are systemically investigated. The reactions of O2 dissociation and CO oxidization with preadsorbed CO or O2 are comparably studied. The computations find that the heteronuclear species Fe1Cu1@C2N possesses high stabilities and is feasible to be synthesized experimentally. More importantly, the heteronuclear Fe1Cu1@C2N catalyst has even better catalytic activity toward CO oxidation than its homonuclear counterparts, especially, without suffering the CO‐poisoning problem. Considering the myriad of unexplored heteronuclear dimers that can be potentially anchored at appropriate supports, this work opens a new avenue and provides a useful guideline for further developing bimetal‐based nanocatalysts.

Breaking scaling relations for efficient CO2 electrochemical reduction through dual-atom catalysts

“…41 Particularly, the 0.83 nm sized holes terminated by sp 2 -bonded nitrogen atoms provide the conditions for anchoring two transition-metal atoms, which offers the opportunity for construction of multiple active sites. 42,43 Alloying different metal species is a general strategy to achieve multiple active sites tuning the binding strength of the targeted intermediates. [42][43][44][45] With regard to the CO 2 RR, in order to reduce the high free energy change of the potential determining step (Fig.…”

“…42,43 Alloying different metal species is a general strategy to achieve multiple active sites tuning the binding strength of the targeted intermediates. [42][43][44][45] With regard to the CO 2 RR, in order to reduce the high free energy change of the potential determining step (Fig. 1a), additional O-binding sites are required to stabilize the oxygen-containing intermediates.…”

Densely Populated Single Atom Catalysts

“…In addition to the electrocatalytic reactions mentioned above, SACs have also been reported to be used in other catalytic reactions, including NRR, [105,148] WGSR, [106,149,150] methane reforming, [111,151,152] methanol steam reforming, [153] CO oxidation, [22,52,[154][155][156] benzene oxidation, [58] acetylene hydrogenation, [96] and so on. Shan et al [111] reported an atomically dispersed Rh on the zeolite (Rh/ZSM-5) catalyst, which can convert methane into methanol or acetic acid in liquid phase mild oxidation at 150 °C.…”

“…The metal atoms can be homonuclear [115,157,158] or heteronuclear. [154,159,160] Experimental measurements [56,61,67,121,161] and density functional theory (DFT) calculations [162,163] showed that the dimer or trimer catalyst could achieve attractive catalytic performance, even better than that of SACs (Figure 10), especially the heteronuclear dimer atom catalyst. Although the synthesis of dimer or trimer atoms catalysts is not yet mature, the recently reports showed excellent catalytic performance of dimer or trimer atoms catalysts, suggesting their great potential for certain applications.…”

Density functional study on the CO oxidation reaction mechanism on MnN2-doped graphene

“…S2 †). The lowest activation energy of O 2 decomposition is 0.854 eV (MnN 2 C 2 -opp) among the three structures, the CO oxidation process is difficult to perform at room temperature when the energy barrier is greater than 0.8 eV, 43 this means that the kinetics are not conducive to O 2 dissociation and O 2 adsorbed on MnN 2 C 2 can be effectively activated without decomposition at room temperature. Aer adsorbing O 2 , there will be three cases of CO adsorption.…”