Ir0/graphdiyne atomic interface for selective epoxidation

Zhiqiang Zheng; Lu Qi; Yaqi Gao; Xiaoyu Luan; Yurui Xue; Feng He; Yuliang Li

doi:10.1093/nsr/nwad156

Ir⁰/graphdiyne atomic interface for selective epoxidation

Natl Sci Rev. 2023 May 24;10(8):nwad156. doi: 10.1093/nsr/nwad156. eCollection 2023 Aug.

Authors

Zhiqiang Zheng¹, Lu Qi¹, Yaqi Gao¹, Xiaoyu Luan¹, Yurui Xue¹, Feng He², Yuliang Li^{1

2

3}

Affiliations

¹ Shandong Provincial Key Laboratory for Science of Material Creation and Energy Conversion, Science Center for Material Creation and Energy Conversion, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
² CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
³ School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China.

Abstract

The development of catalysts that can selectively and efficiently promote the alkene epoxidation at ambient temperatures and pressures is an important promising path to renewable synthesis of various chemical products. Here we report a new type of zerovalent atom catalysts comprised of zerovalent Ir atoms highly dispersed and anchored on graphdiyne (Ir⁰/GDY) wherein the Ir⁰ is stabilized by the incomplete charge transfer effect and the confined effect of GDY natural cavity. The Ir⁰/GDY can selectively and efficiently produce styrene oxides (SO) by electro-oxidizing styrene (ST) in aqueous solutions at ambient temperatures and pressures with high conversion efficiency of ∼100%, high SO selectivity of 85.5%, and high Faradaic efficiency (FE) of 55%. Experimental and density functional theory (DFT) calculation results show that the intrinsic activity and stability due to the incomplete charge transfer between Ir⁰ and GDY effectively promoted the electron exchange between the catalyst and reactant molecule, and realized the selective epoxidation of ST to SO. Studies of the reaction mechanism demonstrate that Ir⁰/GDY proceeds a distinctive pathway for highly selective and active alkene-to-epoxide conversion from the traditional processes. This work presents a new example of constructing zerovalent metal atoms within the GDY matrix toward selective electrocatalytic epoxidation.

Keywords: atom catalyst; atomic interface; graphdiyne; high-performance conversion; selective epoxidation.