Soluble porous organic cages as homogenizers and electron-acceptors for homogenization of heterogeneous alloy nanoparticle catalysts with enhanced catalytic activity

Hele Guo; Yali Liu; Hongliang Dong; Wei Zong; Kaibin Chu; Weiwei Li; Zhongli Fan; Guanjie He; Yue-E Miao; Ivan P Parkin; Feili Lai; Tianxi Liu

doi:10.1016/j.scib.2022.11.010

Soluble porous organic cages as homogenizers and electron-acceptors for homogenization of heterogeneous alloy nanoparticle catalysts with enhanced catalytic activity

Sci Bull (Beijing). 2022 Dec 15;67(23):2428-2437. doi: 10.1016/j.scib.2022.11.010. Epub 2022 Nov 14.

Authors

Hele Guo¹, Yali Liu², Hongliang Dong³, Wei Zong⁴, Kaibin Chu⁵, Weiwei Li⁶, Zhongli Fan⁶, Guanjie He⁷, Yue-E Miao², Ivan P Parkin⁸, Feili Lai⁹, Tianxi Liu¹⁰

Affiliations

¹ Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, International Joint Research Laboratory for Nano Energy Composites, Jiangnan University, Wuxi 214122, China; State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China; Department of Chemistry, KU Leuven, Leuven 3001, Belgium.
² State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China.
³ Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, China. Electronic address: hongliang.dong@hpstar.ac.cn.
⁴ State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China; Christopher Ingold Laboratory, Department of Chemistry, University College London, London WC1H 0AJ, UK.
⁵ Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, International Joint Research Laboratory for Nano Energy Composites, Jiangnan University, Wuxi 214122, China; Department of Chemistry, KU Leuven, Leuven 3001, Belgium.
⁶ Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, China.
⁷ Department of Chemical Engineering, University College London, London WC1E 7JE, UK.
⁸ Christopher Ingold Laboratory, Department of Chemistry, University College London, London WC1H 0AJ, UK.
⁹ Department of Chemistry, KU Leuven, Leuven 3001, Belgium; Department of Molecular Spectroscopy, Max Planck Institute for Polymer Research, Mainz 55128, Germany. Electronic address: feili.lai@kuleuven.be.
¹⁰ Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, International Joint Research Laboratory for Nano Energy Composites, Jiangnan University, Wuxi 214122, China. Electronic address: txliu@jiangnan.edu.cn.

PMID: 36566066
DOI: 10.1016/j.scib.2022.11.010

Abstract

The creation of ultrafine alloy nanoparticles (<5 nm) that can maintain surface activity and avoid aggregation for heterogeneous catalysis has received much attention and is extremely challenging. Here, ultrafine PtRh alloy nanoparticles imprisoned by the cavities of reduced chiral covalent imine cage (PtRh@RCC3) are prepared successfully by an organic molecular cage (OMC) confinement strategy, while the soluble RCC3 can act as a homogenizer to homogenize the heterogeneous PtRh alloy in solution. Moreover, the X-ray absorption near-edge structure (XANES) results show that the RCC3 can act as an electron-acceptor to withdraw electrons from Pt, leading to the formation of higher valence Pt atoms, which is beneficial to improving the catalytic activity for the reduction of 4-nitrophenol. Attributed to the synergistic effect of Pt/Rh atoms and the unique function of the RCC3, the reaction rate constants of Pt₁Rh₁₆@RCC3 are 49.6, 8.2, and 5.5 times than those of the Pt₁Rh₁₆ bulk, Pt@RCC3 and Rh@RCC3, respectively. This work provides a feasible strategy to homogenize heterogeneous alloy nanoparticle catalysts in solution, showing huge potential for advanced catalytic application.

Keywords: 4-Nitrophenol reduction reaction; Heterogeneous catalysts; Soluble organic cage; Ultrafine alloy nanoparticle.

MeSH terms

Alloys / chemistry
Catalysis
Electrons*
Nanoparticles* / chemistry
Oxidants
Oxidation-Reduction
Porosity

Substances

Alloys
Oxidants