Singapore-Peking University Research Centre, Campus for Research Excellence &Technological Enterprise (CREATE), 138602, Singapore.
Institute of Modern Physics, Northwest University, Shaanxi Key Laboratory for Theoretical Physics Frontiers, Xi'an, 710069, China.
Sci Rep. 2017 Jan 18;7:40562. doi: 10.1038/srep40562.
An efficient conversion of CO into valuable fuels and chemicals has been hotly pursued recently. Here, for the first time, we have explored a series of Mx nano-cages (M = B, Al, Be, Mg; X = N, P, O) for catalysis of CO to HCOOH. Two steps are identified in the hydrogenation process, namely, H activation to 2H*, and then 2H* transfer to CO forming HCOOH, where the barriers of two H* transfer are lower than that of the H activation reaction. Among the studied cages, BeO is found to have the lowest barrier in the whole reaction process, showing two kinds of reaction mechanisms for 2H* (simultaneous transfer and a step-wise transfer with a quite low barrier). Moreover, the H activation energy barrier can be further reduced by introducing Al, Ga, Li, and Na to BN cage. This study would provide some new ideas for the design of efficient cluster catalysts for CO reduction.
最近，将 CO 高效转化为有价值的燃料和化学品受到了广泛关注。在此，我们首次探索了一系列 Mx 纳米笼（M = B、Al、Be、Mg；X = N、P、O）用于催化 CO 转化为 HCOOH。在加氢过程中确定了两个步骤，即 H 的活化生成 2H*，然后 2H转移到 CO 形成 HCOOH，其中两个 H转移的势垒低于 H 活化反应的势垒。在所研究的笼中，BeO 在整个反应过程中具有最低的势垒，表现出两种 2H*（同时转移和具有相当低势垒的逐步转移）转移的反应机制。此外，通过向 BN 笼中引入 Al、Ga、Li 和 Na，可以进一步降低 H 的活化能垒。本研究为设计高效的 CO 还原簇催化剂提供了一些新思路。
