Design, identification and evolution of surface ruthenium (II/III) single‐site for CO activation

DOI: 10.1002/anie.202008370

Authors: Liqun Kang (University College London) , Bolun Wang (University College London) , Adam Thetford (The University of Manchester) , Ke Wu (Peking University) , Mohsen Danaie (Diamond Light Source) , Qian He (National University of Singapore) , Emma Gibson (University of Glasgow) , Ling-Dong Sun (Peking University) , Hiroyuki Asakura (Kyoto University) , Richard Catlow (Cardiff University) , Feng Ryan Wang (University College London)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie International Edition

State: Published (Approved)
Published: September 2020
Diamond Proposal Number(s): 16966 , 17559 , 18909 , 19246 , 19318 , 20643 , 20847 , 17377 , 15151 , 14239

Abstract: Ru(II) compounds are widely used in catalysis, photocatalysis and medical applications. They are usually obtained in reductive environment as molecular O 2 can oxidize Ru(II) to Ru(III) and Ru(IV). Here we report the design, identification and evolution of an air‐stable surface ‐[bipy‐Ru(II)(CO) 2 Cl 2 ] site that is covalently mounted onto a polyphenylene framework. Such Ru(II) site was obtained by reduction of ‐[bipy‐Ru(III)Cl 4 ] ‐ with simultaneous ligand exchange from Cl ‐ to CO. This structural evolution was witnessed by a combination of in situ X‐ray and infrared spectroscopy studies. The ‐[bipy‐Ru(II)(CO) 2 Cl 2 ] site enables oxidation of CO with a turnover frequency of 0.73 × 10 ‐2 s ‐1 at 462 K, while the Ru(III) site is completely inert. This work contributes to the studies of structure‐activity relationship by demonstrating a practical control over both geometric and electronic structures of single‐site catalysts at molecular level, which can be further applied in other single site catalyst researches.

Journal Keywords: heterogeneous catalysis; Ruthenium (II) complex; Surface coordination chemistry; Single-site; X-ray Absorption Spectroscopy

Subject Areas: Chemistry

Diamond Offline Facilities: Electron Physical Sciences Imaging Centre (ePSIC)
Instruments: B18-Core EXAFS , E01-JEM ARM 200CF , E02-JEM ARM 300CF

Other Facilities: BL6N1 beamline at Aichi Synchrotron Radiation Center; ISISS beamline at BESSY II

Added On: 28/09/2020 09:52

Documents:
anie.202008370.pdf

Discipline Tags:

Catalysis Chemical Engineering Physical Chemistry Engineering & Technology Chemistry

Technical Tags:

Microscopy Spectroscopy Electron Microscopy (EM) X-ray Absorption Spectroscopy (XAS) Transmission Electron Microscopy (TEM) Extended X-ray Absorption Fine Structure (EXAFS)