Rational approach to guest confinement inside MOF cavities for low-temperature catalysis

Tiesheng Wang; Lijun Gao; Jingwei Hou; Servann J A Herou; James T Griffiths; Weiwei Li; Jinhu Dong; Song Gao; Maria-Magdalena Titirici; R Vasant Kumar; Anthony K Cheetham; Xinhe Bao; Qiang Fu; Stoyan K Smoukov

doi:10.1038/s41467-019-08972-x

Rational approach to guest confinement inside MOF cavities for low-temperature catalysis

Nat Commun. 2019 Mar 22;10(1):1340. doi: 10.1038/s41467-019-08972-x.

Authors

Tiesheng Wang^{1

2

3}, Lijun Gao⁴, Jingwei Hou^{1

5}, Servann J A Herou^{6

7

8}, James T Griffiths¹, Weiwei Li¹, Jinhu Dong⁴, Song Gao⁵, Maria-Magdalena Titirici^{6

7

8}, R Vasant Kumar¹, Anthony K Cheetham^{1

9}, Xinhe Bao⁴, Qiang Fu¹⁰, Stoyan K Smoukov^{11

12

13

14}

Affiliations

¹ Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, CB3 0FS, UK.
² EPSRC Centre for Doctoral Training in Sensor Technologies and Applications, University of Cambridge, Cambridge, CB3 0AS, UK.
³ School of Chemistry, The University of Sydney, Sydney, NSW, 2006, Australia.
⁴ State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, People's Republic of China.
⁵ UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, The University of New South Wales, Sydney, NSW, 2052, Australia.
⁶ School of Engineering and Materials Science, Queen Mary University of London, London, E1 4NS, UK.
⁷ Materials Research Institute, Queen Mary University of London, London, E1 4NS, UK.
⁸ Department of Chemical Engineering, Imperial College London, London, SW7 2AZ, UK.
⁹ Department of Materials Science and Engineering, National University of Singapore, Singapore, 117574, Singapore.
¹⁰ State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, People's Republic of China. qfu@dicp.ac.cn.
¹¹ Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, CB3 0FS, UK. s.smoukov@qmul.ac.uk.
¹² School of Engineering and Materials Science, Queen Mary University of London, London, E1 4NS, UK. s.smoukov@qmul.ac.uk.
¹³ Materials Research Institute, Queen Mary University of London, London, E1 4NS, UK. s.smoukov@qmul.ac.uk.
¹⁴ Department of Chemical and Pharmaceutical Engineering, Faculty of Chemistry and Pharmacy, Sofia University, Sofia, 1164, Bulgaria. s.smoukov@qmul.ac.uk.

Abstract

Geometric or electronic confinement of guests inside nanoporous hosts promises to deliver unusual catalytic or opto-electronic functionality from existing materials but is challenging to obtain particularly using metastable hosts, such as metal-organic frameworks (MOFs). Reagents (e.g. precursor) may be too large for impregnation and synthesis conditions may also destroy the hosts. Here we use thermodynamic Pourbaix diagrams (favorable redox and pH conditions) to describe a general method for metal-compound guest synthesis by rationally selecting reaction agents and conditions. Specifically we demonstrate a MOF-confined RuO₂ catalyst (RuO₂@MOF-808-P) with exceptionally high catalytic CO oxidation below 150 °C as compared to the conventionally made SiO₂-supported RuO₂ (RuO₂/SiO₂). This can be caused by weaker interactions between CO/O and the MOF-encapsulated RuO₂ surface thus avoiding adsorption-induced catalytic surface passivation. We further describe applications of the Pourbaix-enabled guest synthesis (PEGS) strategy with tutorial examples for the general synthesis of arbitrary guests (e.g. metals, oxides, hydroxides, sulfides).

Publication types

Research Support, Non-U.S. Gov't