Host-guest Chemistry Meets Electrocatalysis: Cucurbit[6]uril on a Au Surface as Hybrid System in CO2 Reduction

Andreas Wagner^a, Khoa Ly^a^,^g, Nina Heidary^a^,^h, István Szabó^b, Tamás Földes^b, Khaleel Assaf^c, Steven Barrow^d^,ⁱ, Kamil Sokołowski^d^,^e, Nikolay Kornienko^a^,^h, Moritz Kuehnel^j^,^a, Edina Rosta^b, Ingo Zebger^f, Werner Nau^c, Oren Scherman^d, Erwin Reisner^a

^aChristian Doppler Laboratory for Sustainable SynGas Chemistry, Department of Chemistry, University of Cambridge, Lensfield Road, United Kingdom

^bDepartment of Chemistry, King's College London, United Kingdom, Trinity Street, 7, London, United Kingdom

^cDepartment of Life Sciences and Chemistry, Jacobs University Bremen, Germany, Campus Ring, 1, Bremen, Germany

^dMelville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge - UK, Lensfield Road, United Kingdom

^eInstitute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland, Kasprzaka, 44/52, Warszawa, Poland

^fTechnical University of Berlin (TU), Straße des 17. Juni, Berlin, Germany

^gFakultät für Chemie und Lebensmittelchemie, Technische Universität Dresden, Dresden, Germany

^hUniversity of Montreal, Department of Chemistry, Montreal, Canada

ⁱSchool of Applied Chemistry and Environmental Science, RMIT University, Melbourne, Australia, Melbourne Victoria 3000, Australia, Melbourne, Australia

^jSwansea University, Department of Chemistry, Singleton Park, Swansea SA2 8PP, UK, Swansea, United Kingdom

Materials for Sustainable Development Conference (MATSUS)
Proceedings of nanoGe Fall Meeting19 (NFM19)

#SolCat19. (Photo)electrocatalysis for sustainable carbon utilization: mechanisms, methods, and reactor development

Berlin, Germany, 2019 November 3rd - 8th

Organizer: Matthew Mayer

Oral, Andreas Wagner, presentation 070
DOI: https://doi.org/10.29363/nanoge.nfm.2019.070
Publication date: 18th July 2019

A major challenge in electrocatalysis is the rational control of forming and stabilizing reaction intermediates to guide specific reaction pathways. In this work, we present a model system introducing the concept of surface-bound host-guest chemistry in CO₂ electrocatalysis. The functionalization of pristine gold (Au) with cucurbit[6]uril (CB[6]) nanocavities was studied as a hybrid organic-inorganic model system that utilizes host-guest chemistry to influence heterogeneous electrocatalytic reactions.

The combination of surface-enhanced infrared absorption (SEIRA) spectroscopy and electrocatalytic experiments in conjunction with theoretical calculations support 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 gold 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 CO current density, but almost invariant H₂ production.

Based on the obtained results, design criteria of molecular cavities that allow to overcome current limitations in heterogeneous CO₂ electrocatalysis are discussed. We believe that the methodology and molecular insights in the presented work will provide fruitful basis for future design concepts of molecularly engineered catalytic environments through interfacial host-guest chemistry.

Acknowledgements:

We gratefully acknowledge financial support by the Christian Doppler Research Association, the Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research, Technology and Development, the OMV Group (to A.W., M.F.K., Er.R.), an EU ERC Consolidator grant ‘MatEnSAP’ (68283 to N.H., Er.R.) and Starting Grant ‘BioNet’ (757850 to Ed.R.), a Royal Society Newton International Fellowship (NF160054 to N.K.), European Commission for Marie Curie Fellowships (NANOSPHERE, 658360 to S.J.B.; VSHER, 701192 to K.H.L.; ESTIMABLeNANO, 706425 to K.S.), the EPSRC (EP/R013012/1 and EP/N020669/1 to Ed.R. and EP/L027151/1 for O.A.S.) and the DFG, Deutsche Forschungsgemeinschaft/German Research Foundation, (to K.I.A. and W.M.N.) as well as for funding under Germany´s Excellence Strategy – EXC 2008/1 (UniSysCat) – 390540038, (i.a. to I.Z.). We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1).

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