Behrendt Drew, Banerjee Sayan, Clark Cole, Rappe Andrew M
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, United States.
J Am Chem Soc. 2023 Mar 1;145(8):4730-4735. doi: 10.1021/jacs.2c13253. Epub 2023 Feb 16.
CO activation is an integral component of thermocatalytic and electrocatalytic CO conversion to liquid fuels and value-added chemicals. However, the thermodynamic stability of CO and the high kinetic barriers to activating CO are significant bottlenecks. In this work, we propose that dual atom alloys (DAAs), homo- and heterodimer islands in a Cu matrix, can offer stronger covalent CO binding than pristine Cu. The active site is designed to mimic the Ni-Fe anaerobic carbon monoxide dehydrogenase CO activation environment in a heterogeneous catalyst. We find that combinations of early transition metals (TMs) and late TMs embedded in Cu are thermodynamically stable and can offer stronger covalent CO binding than Cu. Additionally, we identify DAAs that have CO binding energies similar to Cu, both to avoid surface poisoning and to ensure attainable CO diffusion to Cu sites so that the C-C bond formation ability of Cu can be retained in conjunction with facile CO activation at the DAA sites. Machine learning feature selection reveals that the more electropositive dopants are primarily responsible for attaining the strong CO binding. We propose seven Cu-based DAAs and two single atom alloys (SAAs) with early TM late TM combinations, (Sc, Ag), (Y, Ag), (Y, Fe), (Y, Ru), (Y, Cd), (Y, Au), (V, Ag), (Sc), and (Y), for facile CO activation.
CO活化是热催化和电催化将CO转化为液体燃料和增值化学品的一个不可或缺的组成部分。然而，CO的热力学稳定性以及活化CO的高动力学势垒是重大瓶颈。在这项工作中，我们提出双原子合金（DAA），即Cu基体中的同二聚体和异二聚体岛，能够提供比原始Cu更强的共价CO键合。活性位点的设计旨在模拟非均相催化剂中Ni-Fe厌氧一氧化碳脱氢酶的CO活化环境。我们发现，嵌入Cu中的早期过渡金属（TM）和晚期TM的组合在热力学上是稳定的，并且能够提供比Cu更强的共价CO键合。此外，我们确定了具有与Cu相似的CO结合能的DAA，既能避免表面中毒，又能确保CO扩散到Cu位点，从而在DAA位点实现 facile CO活化的同时保留Cu的C-C键形成能力。机器学习特征选择表明，电正性更强的掺杂剂主要负责实现强CO键合。我们提出了七种基于Cu的DAA和两种具有早期TM与晚期TM组合的单原子合金（SAA），即(Sc, Ag)、(Y, Ag)、(Y, Fe)、(Y, Ru)、(Y, Cd)、(Y, Au)、(V, Ag)、(Sc)和(Y)，用于 facile CO活化。
