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

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

doi:10.1002/anie.202414600

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

Journal Article · Thu Oct 24 00:00:00 EDT 2024 · Angewandte Chemie International Edition

DOI:https://doi.org/10.1002/anie.202414600· OSTI ID:2480592

Zhang, Ruirui ^[1]; Liu, Yan ^[2]; Ding, Pan ^[1]; Huang, Juanjuan ^[3]; Dierolf, Martin ^[1]; Kelly, Shelly D. ^[3]; Qiu, Xinqi ^[1]; Chen, Yishuo ^[1]; Hussain, Mian Zahid ^[1]; Li, Weijin ^[1]; Bunzen, Hana ^[4]; Achterhold, Klaus ^[1]; Pfeiffer, Franz ^[1]; Sharp, Ian D. ^[1]; Warnan, Julien ^[1]; ^[1]

Technische Univ. München, Garching (Germany)
Anhui Normal Univ., Wuhu (China)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Univ. of Augsburg (Germany)

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 CO₂ 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_3-xPd_x(BTC)₂] (BTC=benzentricarboxylate), without altering the overall MOF structural properties. Compared to the pristine Cu MOF ([Cu₃(BTC)₂], HKUST-1), the Cu−Pd MOF shifts CO₂ 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 CO₂ reduction using molecular catalysts.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2480592

Alternate ID(s):: OSTI ID: 2997156

Journal Information:: Angewandte Chemie International Edition, Journal Name: Angewandte Chemie International Edition Journal Issue: 51 Vol. 63; ISSN 1521-3773; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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