Reactant enrichment in hollow void of Pt NPs@MnOx nanoreactors for boosting hydrogenation performance

Yanfu Ma; Liwei Wang; Wantong Zhao; Tianyi Liu; Haitao Li; Wenhao Luo; Qike Jiang; Wei Liu; Qihua Yang; Jun Huang; Riguang Zhang; Jian Liu; G Q Max Lu; Can Li

doi:10.1093/nsr/nwad201

Reactant enrichment in hollow void of Pt NPs@MnOx nanoreactors for boosting hydrogenation performance

Natl Sci Rev. 2023 Jul 20;10(10):nwad201. doi: 10.1093/nsr/nwad201. eCollection 2023 Oct.

Authors

Yanfu Ma¹, Liwei Wang^{1

2}, Wantong Zhao³, Tianyi Liu^{1

4}, Haitao Li¹, Wenhao Luo^{5

6}, Qike Jiang⁷, Wei Liu⁷, Qihua Yang⁸, Jun Huang⁹, Riguang Zhang³, Jian Liu^{1

2

4

6}, G Q Max Lu¹⁰, Can Li¹

Affiliations

¹ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, Dalian116023, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing100049, China.
³ State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan030024, China.
⁴ DICP-Surrey Joint Centre for Future Materials, Department of Chemical and Process Engineering, University of Surrey, GuildfordGU2 7XH, UK.
⁵ CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian116023, China.
⁶ School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot010021, China.
⁷ Division of Energy Research Resources, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian116023, China.
⁸ 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.
⁹ Laboratory for Catalysis Engineering, School of Chemical and Biomolecular Engineering, Sydney Nano Institute, The University of Sydney, Sydney2006, Australia.
¹⁰ University of Surrey, GuildfordGU2 7XH, UK.

Abstract

In confined mesoscopic spaces, the unraveling of a catalytic mechanism with complex mass transfer and adsorption processes such as reactant enrichment is a great challenge. In this study, a hollow nanoarchitecture of MnO_x-encapsulated Pt nanoparticles was designed as a nanoreactor to investigate the reactant enrichment in a mesoscopic hollow void. By employing advanced characterization techniques, we found that the reactant-enrichment behavior is derived from directional diffusion of the reactant driven through the local concentration gradient and this increased the amount of reactant. Combining experimental results with density functional theory calculations, the superior cinnamyl alcohol (COL) selectivity originates from the selective adsorption of cinnamaldehyde (CAL) and the rapid formation and desorption of COL in the MnO_x shell. The superb performance of 95% CAL conversion and 95% COL selectivity is obtained at only 0.5 MPa H₂ and 40 min. Our findings showcase that a rationally designed nanoreactor could boost catalytic performance in chemoselective hydrogenation, which can be of great aid and potential in various application scenarios.

Keywords: hollow nanostructure; mesoporous materials; nanoreactor effect; reactant enrichment; selective hydrogenation.