Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China.
College of Chemistry and Chemical Engineering, and Key Laboratory of Photonic and Electronic Bandgap Materials, Ministry of Education, Harbin Normal University, Harbin, 150025, China.
Nanoscale. 2019 Nov 21;11(43):20777-20784. doi: 10.1039/c9nr07559c. Epub 2019 Oct 25.
Photocatalytic reduction of carbon monoxide (CO), an increasingly available and low-cost feedstock that could benefit from CO reduction, to high value-added multi-carbon chemicals, is significant for desirable carbon cycling, as well as high efficiency conversion and high density storage of solar energy. However, developing low cost but highly active photocatalysts with long-term stability for CO coupling and reduction remains a great challenge. Herein, by density functional theory (DFT) computations and taking advantage of the frustrated Lewis pairs (FLPs) concept, we identified a complex consisting of single boron (B) atom decorated on the optically active CN monolayer (i.e., B/CN) as an efficient and stable photocatalyst for CO reduction. On the designed B/CN catalyst, CO can be efficiently reduced to ethylene (CH) and propylene (CH) both with a free energy increase of 0.22 eV for the potential-determining step, which greatly benefits from the pull-push function of the B-N FLPs composed of the decorating B atom and host N atoms. Moreover, the newly designed B/CN catalyst shows significant visible light absorption with a suitable band position for CO reduction to CH and CH. All these unique features make the B/CN photocatalyst an ideal candidate for visible light driven CO reduction to high value-added multi-carbon fuels and chemicals.
光催化还原一氧化碳（CO）是一项重要的研究领域，CO 是一种越来越易得且成本低廉的原料，如果将其转化为高附加值的多碳化学品，将有助于实现理想的碳循环，以及高效地转化和高密度存储太阳能。然而，开发具有长期稳定性和低成本但高活性的光催化剂，用于 CO 偶联和还原，仍然是一个巨大的挑战。在此，我们通过密度泛函理论（DFT）计算，并利用受阻路易斯对（FLPs）的概念，确定了由单个硼（B）原子修饰在光学活性的 CN 单层上的复合物（即 B/CN）作为 CO 还原的高效和稳定的光催化剂。在设计的 B/CN 催化剂上，CO 可以被高效地还原为乙烯（CH）和丙烯（CH），其决速步骤的自由能增加为 0.22 eV，这极大地受益于由修饰的 B 原子和主体 N 原子组成的 B-N FLPs 的推拉功能。此外，新设计的 B/CN 催化剂具有显著的可见光吸收能力，其能带位置适合 CO 还原为 CH 和 CH。所有这些独特的特点使得 B/CN 光催化剂成为可见光驱动 CO 还原为高附加值多碳燃料和化学品的理想候选者。
