School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.
Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha, 410082, China.
Angew Chem Int Ed Engl. 2023 Feb 20;62(9):e202218115. doi: 10.1002/anie.202218115. Epub 2023 Jan 24.
It is highly desired to achieve controllable product selectivity in CO hydrogenation. Herein, we report light-induced switching of reaction pathways of CO hydrogenation towards CH OH production over actomically dispersed Co decorated Pt@UiO-66-NH . CO, being the main product in the reverse water gas shift (RWGS) pathway under thermocatalysis condition, is switched to CH OH via the formate pathway with the assistance of light irradiation. Impressively, the space-time yield of CH OH in photo-assisted thermocatalysis (1916.3 μmol g h ) is about 7.8 times higher than that without light at 240 °C and 1.5 MPa. Mechanism investigation indicates that upon light irradiation, excited UiO-66-NH can transfer electrons to Pt nanoparticles and Co sites, which can efficiently catalyze the critical elementary steps (i.e., CO -to-*HCOO conversion), thus suppressing the RWGS pathway to achieve a high CH OH selectivity.
在 CO 加氢反应中，实现可控的产物选择性是人们所期望的。在此，我们报道了在原子分散的 Co 修饰的 Pt@UiO-66-NH 上，光诱导 CO 加氢反应途径向 CH OH 生成的切换。在热催化条件下，CO 是逆水气变换（RWGS）途径中的主要产物，在光照射的辅助下，通过甲酸盐途径转化为 CH OH。令人印象深刻的是，在光辅助热催化（1916.3 μmol g-1 h-1）中，CH OH 的时空收率在 240°C 和 1.5 MPa 下比没有光照时高约 7.8 倍。机理研究表明，在光照射下，受激的 UiO-66-NH 可以将电子转移到 Pt 纳米粒子和 Co 位点，从而有效地催化关键的基元步骤（即 CO 到 *HCOO 的转化），从而抑制 RWGS 途径以实现高 CH OH 选择性。
