Creation of Heterogeneous Single-Site Catalysts for RWGS Reaction: Ruthenium Complex on Porous Ionic Polymers via Electrostatic Interactions
Heterogeneous single-metal-site catalysts (HSMSCs) have been recognized as promising materials due to the advantages of evenly distributed active metal sites, easy separation, and recyclability. Herein, we construct a single-site Ru catalyst on porous ionic polymers (Ru/PIPs-IL3) via electrostatic interactions, which is a practical and useful strategy for synthesizing HSMSCs. The strong electrostatic interactions (Δ<i>H</i> = -73.4 and -83.5 kJ/mol for Ru-PPh<sub>4</sub> and Ru-P(vBn)(vPh)<sub>3</sub>, respectively) between the quaternary phosphonium cations and oxygen anions of the cyclopentadienyl ligand in Ru species were both consolidated by DFT calculation and X-ray crystallography. The XPS, ATR-IR, HAADF-STEM, and EXAFS analyses and ion exchange experiment were employed to characterize the structure of Ru/PIPs-IL3. These results provide compelling evidence that PIPs-IL3 can interact with Shvo's catalyst in a manner analogous to that observed with quaternary phosphonium (PPh<sub>4</sub>Cl), thereby anchoring the Ru through electrostatic interactions. Such heterogeneous single-site Ru catalyst Ru/PIPs-IL3 exhibited a twofold activity compared to the homogeneous catalyst with a TON<sub>CO</sub> of up to 545 and an excellent 98.5% CO selectivity in the low-temperature reverse water-gas shift reaction.
Authors
- Qihua Yang (ORCID: https://orcid.org/0000-0002-1118-3397)
- Qiongyao Chen
- Zhihong Wei (ORCID: https://orcid.org/0000-0002-9460-7908)
- Huanwang Jing (ORCID: https://orcid.org/0000-0003-3814-0087)
- Xuehua Zhang (ORCID: https://orcid.org/0000-0002-5929-4432)
- Lin He (ORCID: https://orcid.org/0000-0001-7437-1443)
- Xingsi Kang
- Zebang Liu
Institutions
- Shanxi University (CN)
- Xiamen University (CN)
- Chinese Academy of Sciences (CN)
- Lanzhou Institute of Chemical Physics (CN)
- Yancheng Teachers University (CN)
- Shanxi University of Traditional Chinese Medicine (CN)
- Collaborative Innovation Center of Chemistry for Energy Materials (CN)
- University of Chinese Academy of Sciences (CN)
- Lanzhou University (CN)
Publication Details
- Journal
- ACS Applied Materials & Interfaces
- Published
- 2025-02-24
- DOI
- https://doi.org/10.1021/acsami.4c18539
- Citations
- 6
- Primary Topic
- Carbon dioxide utilization in catalysis
- Type
- article
- Field-Weighted Citation Impact
- 4.23
Funders
- National Natural Science Foundation of China
- National Key Research and Development Program of China
- Science and Technology Program of Gansu Province