How to unlock the true potential of biomolecular devices for solar-to-chemical conversion

Joanna Kargul^a

^aUniversity of Warsaw, Centre of New Technologies, Poland., Stefana Banacha, 2c, Warszawa, Poland

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)

#HOMHET - Bridging The Gap Between Homogeneous and Heterogeneous (Photo)-Electrocatalysis

Torremolinos, Spain, 2023 October 16th - 20th

Organizers: Idan Hod, Elena Mas Marzá and Menny Shalom

Invited Speaker, Joanna Kargul, presentation 228
DOI: https://doi.org/10.29363/nanoge.matsus.2023.228
Publication date: 18th July 2023

Making fuels and chemicals directly from the sun is a highly promising approach to provide high economic efficiency by complete integration of the working modules. Directions taken include both synthetic and biomolecular or biohybrid photoelectrochemical devices characterised by various degrees of integration. Implementation of the synthetic artificial photosynthetic systems (APS) is often hampered by the necessity to apply harsh conditions for the catalysis in each half-cell to occur efficiently, photocorrosion of electrode materials, often-limited product selectivity and catalyst instability [1]. Moreover, the best performing inorganic and molecular catalysts usually encompass rare/toxic elements, which precludes such APS systems from large-scale implementation. Therefore, the field of biomolecular and biohybrid artificial photosynthesis has emerged through combining the biotic components, which have been evolutionary optimised in their photocatalytic performance, and non-toxic and cost-effective synthetic materials for selective production of target chemicals at ambient conditions [1].

Here, I present the bottom-up rational design that can yield the increased solar conversion efficiency and stability in biomolecular systems based on the robust photoenzyme, photosystem I (PSI). The PSI biophotocatalyst in these devices is interfaced with various cost-efficient, transparent electrode materials for production of green electricity and fuel. The performance of PSI-based devices can be greatly improved by tailoring the structure of the organic conductive interface, based on pyrene-NTA, terpirydine or diazonium salt ligands, to ensure the generation of unidirectional electron flow and minimisation of wasteful back reactions [2-5]. Specifically, incorporating transitional metal redox centres together with plasmonic nanoparticles in the bio-organic molecular wires significantly improves not only the light-harvesting functionality of the PSI photoenzyme but also increases its photostability and the overall photoconversion performance [2-7]. Such rational design paves the way for generation of viable and sustainable technologies for solar energy conversion into fuel and other carbon-neutral chemicals.

References:

[1] Kargul J, Izzo M, Jacquet M (2022) Artificial photosynthesis for production of solar fuels and chemicals. In: Green Chemistry Series No. 74, Chemical Valorization of Carbon Dioxide, ed. G. Stefanidis and A. Stankiewicz, pp. 254–285. Royal Society of Chemistry, Cambridge, UK. Print ISBN: 978-1-83916-407-1, EPUB eISBN: 978-1-83916-765-2, ISSN: 1757-7039.

[2] Jacquet M, Izzo M, Osella S, Kozdra S, Michałowski PP, Gołowicz D, Kazimierczuk K, Gorzkowski MT, Lewera, A, Teodorczyk, M, Trzaskowski B, Jurczakowski R, Gryko DT, Kargul J (2021) Development of a universal conductive platform for anchoring photo- and electroactive proteins using organometallic terpyridine molecular wires. Nanoscale, 13, 9773–9787.

[3] Jacquet M, Osella S, Harputlu E, Pałys B, Kaczmarek M, Nawrocka E, Rajkiewicz AA, Kalek M, Michałowski PP, Trzaskowski B, Unlu CG, Lisowski W, Pisarek M, Kazimierczuk K, Ocakoglu K, Więckowska, Kargul J (2022) Diazonium-based covalent molecular wiring of single layer graphene leads to enhanced unidirectional photocurrent generation through p-doping effect. ACS Chem. Mater. 34, 3744–3758.

[4] Izzo M, Osella S, Jacquet M, Kiliszek M, Harputlu E, Starkowska A, Łasica A, Unlu CG, Uśpieński T, Niewiadomski P, Bartosik D, Trzaskowski B, Ocakoglu K, Kargul J (2021) Enhancement of direct electron transfer in graphene bioelectrodes containing novel cytochrome c553 variants with optimized heme orientation. Bioelectrochemistry, 140, 107818.

[5] Izzo M, Jacquet M, Fujiwara T, Harputlu E, Mazur R, Wróbel P, Góral T, Unlu CG, Ocakoglu K, Miyagishima S, Kargul J (2021) Development of a Novel Nanoarchitecture of the Robust Photosystem I from a Volcanic Microalga Cyanidioschyzon merolae on Single Layer Graphene for Improved Photocurrent Generation. Int. J. Mol. Sci., 22, 8396.

[6] Szalkowski M, Harputlu E, Kiliszek M, Unlu GC, Maćkowski S, Ocakoglu K, Kargul J, Kowalska D (2020) Plasmonic enhancement of photocurrent generation in Photosystem I–based hybrid electrode, J. Mater. Chem. C, 8, 5807–5814.

[7] Szalkowski M, Kowalska D, Janna Olmos JD, Kargul J, Maćkowski S (2022) Improving photostability of photosystem I-based nanodevice by plasmonic interactions with planar silver nanostructures. Int. J. Mol. Sci., 23, 2976.

Acknowledgements:

Support from the Polish National Science Centre (Solar-driven chemistry 2 SUNCOCAT grant no. 2022/04/Y/ST4/00107) and the European Horizon Europe Research and Innovation Programme (SUNER-C CSA, GA no. 101058481) is greatly acknowledged.

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