Yu Fengyang, Jing Xu, Wang Yao, Sun Mingyang, Duan Chunying
Zhang Dayu College of Chemistry, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China.
Angew Chem Int Ed Engl. 2021 Nov 15;60(47):24849-24853. doi: 10.1002/anie.202108892. Epub 2021 Sep 17.
Metal-organic frameworks (MOFs) provide a platform to design new heterogeneous catalysts for catalytic CO reduction, but selective formation of C2 valuable liquid fuel products remains a challenge. Herein, we propose a strategy to synthesize composites by integrating MoS nanosheets into hierarchically porous defective UiO-66 (d-UiO-66) to form Mo-O-Zr bimetallic sites on the interfaces between UiO-66 and MoS . The active interfaces are favorable for the efficient transfer of photo-generated charge carriers and for promoting the activity, whereas, the synergy of the components at the interfaces achieves selectivity for C2 production. The d-UiO-66/MoS composite facilitates the photo-catalytic conversion of gas phase CO and H O to CH COOH under visible light irradiation without any other adducts. The evolution rate and selectivity of CH COOH reached 39.0 μmol g h and 94 %, respectively, without any C1 products, suggesting a new approach for the design of highly efficient photocatalysts of CO for C2 production. Theoretical calculations demonstrate the charge-polarized Zr-O-Mo aided the C-C coupling process with the largely reduced energy barrier.
金属有机框架(MOFs)为设计用于催化CO还原的新型多相催化剂提供了一个平台,但选择性形成C2有价值的液体燃料产品仍然是一个挑战。在此,我们提出了一种策略,通过将MoS纳米片整合到分级多孔缺陷UiO-66(d-UiO-66)中来合成复合材料,以在UiO-66和MoS之间的界面上形成Mo-O-Zr双金属位点。活性界面有利于光生电荷载流子的有效转移并促进活性,而界面处各组分的协同作用实现了C2产物的选择性。d-UiO-66/MoS复合材料在可见光照射下无需任何其他加合物即可促进气相CO和H2O光催化转化为CH3COOH。CH3COOH的生成速率和选择性分别达到39.0 μmol g-1 h-1和94%,且无任何C1产物,这为设计用于C2生产的高效CO光催化剂提供了一种新方法。理论计算表明,电荷极化的Zr-O-Mo有助于C-C偶联过程,且能大幅降低能垒。