1. Enhanced Proximity of Rh1,2‐Rhn Ensembles Encaged in UiO‐67 Boosting Catalytic Conversion of Syngas to Oxygenates.
- Author
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Yu, Jun, Liu, Tingting, Gu, Qingqing, Wang, Jia, Han, Ying, Li, Gonghui, Guo, Qiangsheng, Gu, Ye, Wu, Xinping, Gong, Xueqing, Yang, Bing, and Mao, Dongsen
- Subjects
SYNTHESIS gas ,CATALYSIS ,CATALYSTS ,DIMERS ,ATOMS ,RHODIUM catalysts ,BIMETALLIC catalysts - Abstract
Maintaining high conversion under the premise of high oxygenates selectivity in syngas conversion is important but a formidable challenge in Rh catalysis. Monometallic Rh catalysts provide poor oxygenate conversion efficiency, and efforts have been focused on constructing adjacent polymetallic sites; however, the one‐pass yields of C2+ oxygenates over the reported Rh‐based catalysts were mostly <20 %. In this study, we constructed a monometallic Rh catalyst encapsulated in UiO‐67 (Rh/UiO‐67) with enhanced proximity to dual‐site Rh1,2‐Rhn ensembles. Unexpectedly, this catalyst exhibited high efficacy for oxygenate synthesis from syngas, giving a high oxygenate selectivity of 72.0 % with a remarkable CO conversion of 50.4 %, and the one‐pass yield of C2+ oxygenates exceeded 25 %. The state‐of‐the‐art characterizations further revealed the spontaneous formation of an ensemble of Rh single atoms/dimers (Rh1,2) in the proximity of ultrasmall Rh clusters (Rhn) confined within the nanocavity of UiO‐67, providing adjacent Rh+‐Rh0 dual sites dynamically during the reaction that promote the relay of the undissociated CHO species to the CHx species. Thus, our results open a new route for designing highly efficient Rh catalysts for the conversion of syngas to oxygenates by precisely tuning the ensemble and proximity of the dual active sites in a confined space. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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