Barhács Balázs, Janssens Ewald, Höltzl Tibor
Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szent Gellért tér 4, H-1111 Budapest, Hungary.
Quantum Solid-State Physics, KU Leuven, Celestijnenlaan 200D, BE-3001 Leuven, Belgium.
Phys Chem Chem Phys. 2022 Sep 14;24(35):21417-21426. doi: 10.1039/d2cp01316a.
A possible remedy for the increasing atmospheric CO concentration is capturing and reducing it into valuable chemicals like methane, methanol, ethylene, and ethanol. However, a suitable catalyst for this process is still under extensive research. Small sized copper clusters have gained attention in recent years due to their catalytic activity in the CO reduction reaction. Although C products have a higher economic value, the formation of C products was investigated most thoroughly. Graphene is a promising support for small copper clusters in the electrochemical reduction of CO. It exhibits good mechanical and electrical properties, but the weak interaction between copper and graphene is an issue. Our DFT computations reveal that small Cu clusters on the boron-doped graphene (BDG) support are promising catalysts for the electrochemical reduction of CO. We found facile reaction pathways towards various C (carbon-monoxide, formic acid, formaldehyde, methanol or methane) and C (ethanol or ethylene) products on Cu and Cu clusters on BDG. The reactivity is cluster-size tunable with Cu being the more reactive agent, while Cu shows a higher selectivity towards C products.
大气中二氧化碳浓度不断增加的一种可能解决办法是捕获并将其转化为甲烷、甲醇、乙烯和乙醇等有价值的化学品。然而，用于此过程的合适催化剂仍在广泛研究中。近年来，小尺寸铜簇因其在二氧化碳还原反应中的催化活性而受到关注。尽管含碳产物具有更高的经济价值，但对含碳产物形成的研究最为透彻。石墨烯是电化学还原二氧化碳过程中小铜簇的一种有前景的载体。它具有良好的机械和电学性能，但铜与石墨烯之间的弱相互作用是一个问题。我们的密度泛函理论计算表明，硼掺杂石墨烯（BDG）载体上的小铜簇是电化学还原二氧化碳的有前景的催化剂。我们发现，在BDG上的铜和铜簇上，存在通向各种含碳（一氧化碳、甲酸、甲醛、甲醇或甲烷）和含碳（乙醇或乙烯）产物的简便反应途径。反应活性可通过簇尺寸调节，铜是更具反应性的试剂，而铜对含碳产物表现出更高的选择性。
