Dual atom catalysts for rapid electrochemical reduction of CO to ethylene

Reaction Mechanism of Rapid CO Electroreduction to Propylene and Cyclopropane (C3+) over Triple Atom Catalysts

“…We used the Vienna ab initio Simulation Package (VASP, version 6.1.0) software 53 with the Perdew−Burke−Ernzerhof (PBE) functional 54 to determine the mechanism. Although PBE is not perfect at predicting CO adsorption energies, it has been used for the prediction of CO 2 RR and CORR mechanisms, 36 which aligns with the experimental results reported in the literature. 15 The DFT-D3 method with the Becke-Johnson damping function was included to account for van der Waals (London dispersion) interactions.…”

“…In addition, weak CO binding leads to the desorption of CO from the surface before being reduced toward more valuable products. 36 Therefore, a catalyst that possesses poor H binding and simultaneously adsorbs CO firmly would result in high CORR selectivity. Figure 1c shows the values of the 3H binding energy versus 3CO binding energy.…”

“…Therefore, only Ir3N7, Fe3N7, Ni3N7, Co3N7, and Cu3N7 A high energy barrier for CO dimerization normally leads to the production of C 1 products such as methane (CH 4 ) or methanol (CH 3 OH). 36 Therefore, a low energy barrier for the dimerization of CO is a critical requirement in the CORR into C 3+ products. Figure 1d displays the first CO dimerization energies versus the 3CO binding energy.…”

“…30,35 For example, a series of phthalocyanine-based DACs were investigated for the rapid CO electroreduction toward ethylene (C 2 H 4 ) enabled by high CO adsorption energy and low CO dimerization energy. 36 Several DACs such as FeFe, RuRu, CoCo, IrIr, and IrCo were disclosed as the best candidates for converting CO to C 2 H 4 . 36 A separate study investigated CrCo and MnCo-DACs and reported small C−C coupling energy barriers of 0.52 and 0.57 eV, in addition to low limiting potentials of −0.20 and −0.34 V, respectively, for ethanol production.…”

“…36 Several DACs such as FeFe, RuRu, CoCo, IrIr, and IrCo were disclosed as the best candidates for converting CO to C 2 H 4 . 36 A separate study investigated CrCo and MnCo-DACs and reported small C−C coupling energy barriers of 0.52 and 0.57 eV, in addition to low limiting potentials of −0.20 and −0.34 V, respectively, for ethanol production. 37 The concept of multiatom catalysts such as triple atom catalysts (TACs) has begun to provide more opportunities for complex electrochemical reactions.…”