Enhanced Proximity of Rh1,2-Rhn Ensembles Encaged in UiO-67 Boosting Catalytic Conversion of Syngas to Oxygenates
© 2024 Wiley‐VCH GmbH..
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.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - year:2024 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - (2024) vom: 20. März, Seite e202401568 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Yu, Jun [VerfasserIn] |
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| Links: |
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| Themen: |
Dual Active Sites |
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| Anmerkungen: |
Date Revised 09.04.2024 published: Print-Electronic Citation Status Publisher |
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| doi: |
10.1002/anie.202401568 |
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| funding: |
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| PPN (Katalog-ID): |
NLM36995789X |
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| 520 | |a © 2024 Wiley‐VCH GmbH. | ||
| 520 | |a 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 | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Dual Active Sites | |
| 650 | 4 | |a Enhanced Proximity | |
| 650 | 4 | |a Monometallic Rh Catalyst | |
| 650 | 4 | |a Syngas Conversion to Oxygenates | |
| 650 | 4 | |a UiO-67 | |
| 700 | 1 | |a Liu, Tingting |e verfasserin |4 aut | |
| 700 | 1 | |a Gu, Qingqing |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Jia |e verfasserin |4 aut | |
| 700 | 1 | |a Han, Ying |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Gonghui |e verfasserin |4 aut | |
| 700 | 1 | |a Guo, Qiangsheng |e verfasserin |4 aut | |
| 700 | 1 | |a Gu, Ye |e verfasserin |4 aut | |
| 700 | 1 | |a Wu, Xinping |e verfasserin |4 aut | |
| 700 | 1 | |a Gong, Xueqing |e verfasserin |4 aut | |
| 700 | 1 | |a Yang, Bing |e verfasserin |4 aut | |
| 700 | 1 | |a Mao, Dongsen |e verfasserin |4 aut | |
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