The promotion effect of π-π interactions in Pd NPs catalysed selective hydrogenation

Miao Guo; Sanjeevi Jayakumar; Mengfei Luo; Xiangtao Kong; Chunzhi Li; He Li; Jian Chen; Qihua Yang

doi:10.1038/s41467-022-29299-0

The promotion effect of π-π interactions in Pd NPs catalysed selective hydrogenation

Nat Commun. 2022 Apr 1;13(1):1770. doi: 10.1038/s41467-022-29299-0.

Authors

Miao Guo^#¹, Sanjeevi Jayakumar^#¹, Mengfei Luo², Xiangtao Kong³, Chunzhi Li^{1

4}, He Li¹, Jian Chen⁵, Qihua Yang^{6

7}

Affiliations

¹ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
² Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China. mengfeiluo@zjnu.cn.
³ College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, 455000, China.
⁴ University of Chinese Academy of Sciences, Beijing, 100039, China.
⁵ Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China.
⁶ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. yangqh@dicp.ac.cn.
⁷ Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China. yangqh@dicp.ac.cn.

^# Contributed equally.

Abstract

The utilization of weak interactions to improve the catalytic performance of supported metal catalysts is an important strategy for catalysts design, but still remains a big challenge. In this work, the weak interactions nearby the Pd nanoparticles (NPs) are finely tuned by using a series of imine-linked covalent organic frameworks (COFs) with different conjugation skeletons. The Pd NPs embedded in pyrene-COF are ca. 3 to 10-fold more active than those in COFs without pyrene in the hydrogenation of aromatic ketones/aldehydes, quinolines and nitrobenzene, though Pd have similar size and surface structure. With acetophenone (AP) hydrogenation as a model reaction, systematic studies imply that the π-π interaction of AP and pyrene rings in the vicinity of Pd NPs could significantly reduce the activation barrier in the rate-determining step. This work highlights the important role of non-covalent interactions beyond the active sites in modulating the catalytic performance of supported metal NPs.