Journal
ACS CATALYSIS
Volume 10, Issue 1, Pages 751-761Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.9b04221
Keywords
surface active-site engineering; electrocatalytic CO2 reduction; host-guest chemistry; supramolecular catalysis
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Funding
- Christian Doppler Research Association
- Austrian Federal Ministry for Digital and Economic Affairs
- National Foundation for Research, Technology and Development
- OMV Group
- EU ERC Consolidator grant MatEnSAP [68283]
- EU ERC Starting Grant BioNet [757850]
- Royal Society Newton International Fellowship [NF160054]
- European Commission [658360, 701192, 706425]
- EPSRC [EP/R013012/1, EP/L027151/1, EP/N020669/1, EP/P020194/1]
- DFG, Deutsche Forschungsgemeinschaft/German Research Foundation
- Germany's Excellence Strategy - EXC -2008/1 (UniSysCat) [390540038]
- EPSRC [EP/L027151/1, EP/R013012/1, EP/P020194/1, EP/N020669/1] Funding Source: UKRI
- Marie Curie Actions (MSCA) [706425, 701192] Funding Source: Marie Curie Actions (MSCA)
- European Research Council (ERC) [757850] Funding Source: European Research Council (ERC)
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The rational control of forming and stabilizing reaction intermediates to guide specific reaction pathways remains to be a major challenge in electrocatalysis. In this work, we report a surface active-site engineering approach for modulating electrocatalytic CO2 reduction using the macrocycle cucurbit[6]uril (CB[6]). A pristine gold surface functionalized with CB[6] nanocavities was studied as a hybrid organic inorganic model system that utilizes host-guest chemistry to influence the heterogeneous electrocatalytic reaction. The combination of surface-enhanced infrared absorption (SEIRA) spectroscopy and electrocatalytic experiments in conjunction with theoretical calculations supports capture and reduction of CO2 inside the hydrophobic cavity of CB[6] on the gold surface in aqueous KHCO3 at negative potentials. SEIRA spectroscopic experiments show that the decoration of gold with the supramolecular host CB[6] leads to an increased local CO2 concentration close to the metal interface. Electrocatalytic CO2 reduction on a CB[6]-coated gold electrode indicates differences in the specific interactions between CO2 reduction intermediates within and outside the CB[6] molecular cavity, illustrated by a decrease in current density from CO generation, but almost invariant H-2 production compared to unfunctionalized gold. The presented methodology and mechanistic insight can guide future design of molecularly engineered catalytic environments through interfacial host-guest chemistry.
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