Design of Hollow Nanoreactors for Size- and Shape-Selective Catalytic Semihydrogenation Driven by Molecular Recognition

Yutong Pi; Linxia Cui; Wenhao Luo; Haitao Li; Yanfu Ma; Na Ta; Xinyao Wang; Rui Gao; Dan Wang; Qihua Yang; Jian Liu

doi:10.1002/anie.202307096

Design of Hollow Nanoreactors for Size- and Shape-Selective Catalytic Semihydrogenation Driven by Molecular Recognition

Angew Chem Int Ed Engl. 2023 Oct 23;62(43):e202307096. doi: 10.1002/anie.202307096. Epub 2023 Jul 17.

Authors

Yutong Pi^{1

2}, Linxia Cui³, Wenhao Luo³, Haitao Li¹, Yanfu Ma¹, Na Ta¹, Xinyao Wang^{1

2}, Rui Gao³, Dan Wang^{4

5}, Qihua Yang⁶, Jian Liu^{1

3

7}

Affiliations

¹ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, 116023, Dalian, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, 100049, Beijing, China.
³ School of Chemistry and Chemical Engineering, Inner Mongolia University, 235 West University Street, 010021, Hohhot, China.
⁴ State Key Laboratory of Biochemical Engineering, Key Laboratory of Science and Technology on Particle Materials, Institute of Process Engineering, Chinese Academy of Sciences, 100190, Beijing, China.
⁵ China University of Chinese Academy of Sciences, 100049, Beijing, China.
⁶ 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, 321004, Jinhua, China.
⁷ DICP-Surrey Joint Centre for Future Materials, Department of Chemical and Process Engineering, University of Surrey, GU2 7XH, Guildford, Surrey, UK.

PMID: 37394778
DOI: 10.1002/anie.202307096

Abstract

Mimicking the structures and functions of cells to create artificial organelles has spurred the development of efficient strategies for production of hollow nanoreactors with biomimetic catalytic functions. However, such structure are challenging to fabricate and are thus rarely reported. We report the design of hollow nanoreactors with hollow multishelled structure (HoMS) and spatially loaded metal nanoparticles. Starting from a molecular-level design strategy, well-defined hollow multishelled structure phenolic resins (HoMS-PR) and carbon (HoMS-C) submicron particles were accurately constructed. HoMS-C serves as an excellent, versatile platform, owing to its tunable properties with tailored functional sites for achieving precise spatial location of metal nanoparticles, internally encapsulated (Pd@HoMS-C) or externally supported (Pd/HoMS-C). Impressively, the combination of the delicate nanoarchitecture and spatially loaded metal nanoparticles endow the pair of nanoreactors with size-shape-selective molecular recognition properties in catalytic semihydrogenation, including high activity and selectivity of Pd@HoMS-C for small aliphatic substrates and Pd/HoMS-C for large aromatic substrates. Theoretical calculations provide insight into the pair of nanoreactors with distinct behaviors due to the differences in energy barrier of substrate adsorption. This work provides guidance on the rational design and accurate construction of hollow nanoreactors with precisely located active sites and a finely modulated microenvironment by mimicking the functions of cells.

Keywords: Hollow Structure; Hydrogenation; Nanoreactor; Polymer; Supported Catalyst.

Grants and funding

22279139/National Natural Science Foundation of China