Engineering a Cu‐Pd Paddle‐Wheel Metal–Organic Framework for Selective CO<sub>2</sub> Electroreduction

Optimizing the binding energy between the intermediate and the active site is a key factor for tuning catalytic product selectivity and activity in the electrochemical carbon dioxide reduction reaction. Copper active sites are known to reduce CO<sub>2</sub> to hydrocarbons and oxygenates, but suffer from poor product selectivity due to the moderate binding energies of several of the reaction intermediates. Here, we report an ion exchange strategy to construct Cu-Pd paddle wheel dimers within Cu-based metal-organic frameworks (MOFs), [Cu<sub>3-x</sub>Pd<sub>x</sub>(BTC)<sub>2</sub>] (BTC=benzentricarboxylate), without altering the overall MOF structural properties. Compared to the pristine Cu MOF ([Cu<sub>3</sub>(BTC)<sub>2</sub>], HKUST-1), the Cu-Pd MOF shifts CO<sub>2</sub> electroreduction products from diverse chemical species to selective CO generation. In situ X-ray absorption fine structure analysis of the catalyst oxidation state and local geometry, combined with theoretical calculations, reveal that the incorporation of Pd within the Cu-Pd paddle wheel node structure of the MOF promotes adsorption of the key intermediate COOH* at the Cu site. This permits CO-selective catalytic mechanisms and thus advances our understanding of the interplay between structure and activity toward electrochemical CO<sub>2</sub> reduction using molecular catalysts.

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Publication Details

Journal
Angewandte Chemie International Edition
Published
2024-10-25
DOI
https://doi.org/10.1002/anie.202414600
Citations
10
Primary Topic
CO2 Reduction Techniques and Catalysts
Type
article
Field-Weighted Citation Impact
1.02

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article

Engineering a Cu‐Pd Paddle‐Wheel Metal–Organic Framework for Selective CO2 Electroreduction

Xinqi Qiu, Martin Dierolf, Juanjuan Huang, Julien Warnan et al.
10 citations
Angewandte Chemie International Edition
CO2 Reduction Techniques and Catalysts
1.02
article

Engineering a Cu‐Pd Paddle‐Wheel Metal–Organic Framework for Selective CO2 Electroreduction

Xinqi Qiu, Martin Dierolf, Juanjuan Huang, Julien Warnan, Hana Bunzen, Franz Pfeiffer, Roland A. Fischer, Pan Ding, Klaus Achterhold, Shelly D. Kelly, Weijin Li, Mian Zahid Hussain, Ian D. Sharp, Yan Liu, Yun Chen, Ruirui Zhang
article en
10 citations

Abstract

Optimizing the binding energy between the intermediate and the active site is a key factor for tuning catalytic product selectivity and activity in the electrochemical carbon dioxide reduction reaction. Copper active sites are known to reduce CO<sub>2</sub> to hydrocarbons and oxygenates, but suffer from poor product selectivity due to the moderate binding energies of several of the reaction intermediates. Here, we report an ion exchange strategy to construct Cu-Pd paddle wheel dimers within Cu-based metal-organic frameworks (MOFs), [Cu<sub>3-x</sub>Pd<sub>x</sub>(BTC)<sub>2</sub>] (BTC=benzentricarboxylate), without altering the overall MOF structural properties. Compared to the pristine Cu MOF ([Cu<sub>3</sub>(BTC)<sub>2</sub>], HKUST-1), the Cu-Pd MOF shifts CO<sub>2</sub> electroreduction products from diverse chemical species to selective CO generation. In situ X-ray absorption fine structure analysis of the catalyst oxidation state and local geometry, combined with theoretical calculations, reveal that the incorporation of Pd within the Cu-Pd paddle wheel node structure of the MOF promotes adsorption of the key intermediate COOH* at the Cu site. This permits CO-selective catalytic mechanisms and thus advances our understanding of the interplay between structure and activity toward electrochemical CO<sub>2</sub> reduction using molecular catalysts.

Angewandte Chemie International EditionVol. 63(51)
Argonne National Laboratory (US), Schott (Germany) (DE), University of Augsburg (DE), Fischer (Germany) (DE), Anhui Normal University (CN), Technical University of Munich (DE)
U.S. Department of Energy, Salt Science Research Foundation, Deutsche Forschungsgemeinschaft, National Natural Science Foundation of China, China Scholarship Council, University of Science and Technology of China, National Synchrotron Radiation Laboratory, Office of Science, Chinese Government Scholarship, Basic Energy Sciences, Argonne National Laboratory
Openalex Percentile: Top 27%
CO2 Reduction Techniques and Catalysts
1.02
DOIOpen Access PDFOpenAlex
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