Synthesis and post-synthetic modification of Cu-based coordination polymers for CO2 electrocatalysis

Alexandre H. Martins^a, Nuno Bandeira^b, Telmo Nunes^c, Sara Realista^a

^aCentro de Química Estrutural, Institute of Molecular Sciences, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, Ed. C8, 1749-016 Lisboa, Portugal

^bBiosystems and Integrative Sciences Institute (BioISI), Departamento de Química e Bioquímica, Faculdade de Ciências Universidade de Lisboa, 8.5.53-C8 Campo Grande, 1749-016 Lisboa, Portugal

^cFCUL Microscopy Facility, Faculdade de Ciências, Universidade de Lisboa, 1749-016, Lisboa, Portugal

Proceedings of MATSUS Fall 2026 Conference (MATSUSFall26)

E4 Advances and Innovations in (Photo)Electrochemical CO2 and N2 Conversion and Water Splitting

Palma, Spain, 2026 October 26th - 30th

Organizer: Guillermo Díaz-Sainz

Oral, Alexandre H. Martins, presentation 236
Publication date: 22nd July 2026

Carbon dioxide (CO₂) conversion to produce fuels and chemicals is a promising route for reducing CO₂ emissions, thus the design of efficient and selective electrocatalysts for CO₂ reduction is essential to the development of sustainable energy conversion technologies.[1] In this work, copper-based metal–organic frameworks (Cu-MOFs)[2] were used as tuneable platforms for the design of advanced electrodes, focusing on the improvement of the catalytic performance through integration of conductive polymers. Cu-Adenine MOFs and a new Cu-Hypoxanthine coordination polymer were synthesised following the procedure described by Wang[3] and co-workers and characterised using infrared spectroscopy, X-ray diffraction and N₂ adsorption isotherms. Density functional theory (DFT) calculations were used to model the structure of the Cu-Hypoxanthine coordination polymer.

To improve electrical conductivity and catalytic activity, the synthesised materials were modified with polyaniline (PANI) via a mechanochemical approach to produce PANI-modified composites. The idea of this strategy is to enable contact between the conductive polymer and the synthesised materials while preserving their integrity.^[1] For the electrocatalytic application of these materials, it is necessary to integrate them into mechanically stable and electrically conductive electrodes. Electrophoretic deposition was used to deposit the pristine materials and the resulting PANI-modified materials onto carbon paper substrates producing uniform and adherent films. Those films were characterised by X-ray diffraction and Scanning electron microscopy.

Electrochemical performance was evaluated by linear sweep voltammetry (LSV) to assess stability and identify suitable operating potentials for CO₂ reduction.^[2] These studies provide insight into the effect of polymer incorporation on electrode activity and stability. Subsequent controlled potential electrolysis (CPE) experiments are being conducted to evaluate catalytic activity under specific conditions.

The liquid products formed during CPE were identified and quantified by ¹H NMR and liquid chromatography, while gaseous products were analysed by GC-TCD.

References:

[1] M. A. Shah, A. L. Shibiru, V. Kumar, V. C. Srivastava, Carbon dioxide conversion to value-added products and fuels: opportunities and challenges: a critical review, Int. J. Green Energy, 2025, 22:8, 1532-1551

[2] U. Nwosu, S. Siahrostami, Copper-based metal-organic frameworks for CO2 reduction: selectivity trends, design paradigms, and perspectives, Catal. Sci. Technol., 2023, 13, 3740-3761

[3] L. Wang, J. Lv, Q. Ye, Y. Luo, G. Y. Wang, L. H. Xie, Nanoporous Cu(II)-Adenine-Based Metal-Organic Frameworks for Selective Adsorption of C2H2 from C2H4 and CO2, ACS Appl. Nano Mater. 2023, 6, 22095–22103

[4] S. Yang, V. V. Karve, A. Justin, I. Kochetygov, J. Espín, M. Asgari, O. Trukhina, D. T. Sun, L. Peng, W. L. Queen, Enhancing MOF performance through the introduction of polymer guests, Coord Chem Rev, 2021, 427, 213525

[5] F. Yang, A. Chen, P. L. Deng, Y. Zhou, Z. Shahid, H. Liu, B. Y. Xia, Highly efficient electroconversion of carbon dioxide into hydrocarbons by cathodized copper-organic frameworks, Chem. Sci. 2019, 10, 7975–7981.

Acknowledgements:

Centro de Química Estrutural is a Research Unit funded by Fundação para a Ciência e a Tecnologia through projects UID/00100/2025 (10.54499/UID/00100/2025) and UID/PRR/00100/2025 (10.54499/UID/PRR/00100/2025). Institute of Molecular Sciences is an Associate Laboratory funded by Fundação para a Ciência e a Tecnologia through project LA/P/0056/2020 (10.54499/LA/P/0056/2020). AHM thanks for his scholarship under the project 2024.06795.RESTART. S.R. thanks FCT for the contract 2020.02134.CEECIND: 10.54499/2020.02134.CEECIND/CP1605/CT0002 and for the project 2024.06795.RESTART.

nanoGe is a prestigious brand of successful science conferences that are developed along the year in different areas of the world since 2009. Our worldwide conferences cover cutting-edge materials topics like perovskite solar cells, photovoltaics, optoelectronics, solar fuel conversion, surface science, catalysis and two-dimensional materials, among many others.

MATSUS

Previously nanoGe Spring Meeting (NSM) and nanoGe Fall Meeting (NFM), MATSUS is a multiple symposia conference focused on a broad set of topics of advanced materials preparation, their fundamental properties, and their applications, in fields such as renewable energy, photovoltaics, lighting, semiconductor quantum dots, 2-D materials synthesis, charge carriers dynamics, microscopy and spectroscopy semiconductors fundamentals, etc.

International Conference on Hybrid and Organic Photovoltaics

International Conference on Hybrid and Organic Photovoltaics (HOPV) is celebrated yearly in May. The main topics are the development, function and modeling of materials and devices for hybrid and organic solar cells. The field is now dominated by perovskite solar cells but also other hybrid technologies, as organic solar cells, quantum dot solar cells, and dye-sensitized solar cells and their integration into devices for photoelectrochemical solar fuel production.

Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and Optoelectronics

The main topics of the Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and Optoelectronics (IPEROP) are discussed every year in Asia-Pacific for gathering the recent advances in the fields of material preparation, modeling and fabrication of perovskite and hybrid and organic materials. Photovoltaic devices are analyzed from fundamental physics and materials properties to a broad set of applications. The conference also covers the developments of perovskite optoelectronics, including light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.

International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and Optoelectronics

The International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and Optoelectronics (NIPHO) is the best place to hear the latest developments in perovskite solar cells as well as on recent advances in the fields of perovskite light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.