December 1 - 6, 2024
Boston, Massachusetts
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2024 MRS Fall Meeting & Exhibit
EN01.11.36

Size-Controlled and Localised Nanoparticles on Photoactive Covalent Organic Frameworks for Artificial Photosynthesis

When and Where

Dec 4, 2024
8:00pm - 10:00pm
Hynes, Level 1, Hall A

Presenter(s)

Co-Author(s)

Kathryn McCarthy1,Roberto Gonzalez Gomez1,Pau Farras1

University of Galway1

Abstract

Kathryn McCarthy1,Roberto Gonzalez Gomez1,Pau Farras1

University of Galway1
Concerning levels of CO2 in the atmosphere have urged researchers to develop technologies that can not only reduce its atmospheric concentration, but also use CO2 as a feedstock for producing carbon-based fuels and value-added chemicals. Solar irradiation, a renewable and abundant source of energy, can be used to drive these chemical transformations in a process known as artificial photosynthesis1. Recently, porous materials, such as covalent organic frameworks (COFs), have been explored as photo-responsive supports for catalysts due to their remarkable physical and chemical stability, structural diversity and large surface areas2. Furthermore, through careful selection of building blocks, a wider photo-absorption window can be targeted, while also tuning the bandgap to extend the lifetime of electron-hole pair separation, thus establishing a thermodynamically favourable process3.

The incorporation of metal catalysts, such as metal nanoparticles (MNPs), into these types of organic, photo-active supports creates a hybrid material which can facilitate redox reactions via an electron “donor-acceptor” type mechanism, i.e., electrons excited within the framework can be accepted by the MNP and subsequently used to carry out CO2 reduction3. Furthermore the use of another MNP co-catalyst allows for effective separation of charges within the framework, retaining the photogenerated holes and facilitating the oxidation of a sacrificial agent, such as water in this case4. MNPs are widely used for catalysis due to their high surface energy and quantum size effects; in particular, gold nanoparticles (Au NPs) are highly selective towards CO2 reduction to CO5. However, their aggregation can result in gradual loss of catalytic activity, therefore uniformly immobilising them on light-harvesting, porous supports is effective in extending their photocatalytic performance6. In addition, RuO2 nanoparticles, which are widely used in oxidation reactions, possess excellent affinity toward O2 gas with a favourable O2 binding energy, low overpotential, and high OER activity7.

In this work, a photo-absorbing porphyrin-perylene COF has been decorated with Au NP and RuO2 NPs, thus creating a novel, robust material for the purpose of artificial photosynthesis. The COF was functionalised with thiol groups to assist in localisation and stabilisation of the Au NPs, resulting in the formation of well-distributed and locally separated NPs anchored into the COF network. The size of the Au NPs has been modulated by adjusting the concentration of gold salt precursor vs. the number of thiol ligands. Previously synthesised RuO2 nanoparticles were incorporated into the COF unoccupied pores to produce the final MNP-COF hybrid material. NPs size effect and metal loading concentration have been evaluated to enhance the material performance. Results of their photocatalytic efficiency for the simultaneous photocatalytic CO2 reduction and water oxidation under visible light irradiation will be presented.


(1) Galushchinskiy, A.; González-Gómez, R.; McCarthy, K.; Farràs, P.; Savateev, Energy and Fuels 2022, 36 (9), 4625–4639
(2) Zhang, Y.; Liu, H.; Gao, F.; Tan, X.; Cai, Y.; Hu, B.; Huang, Q.; Fang, M.; Wang, X. EnergyChem. Elsevier B.V. July 1, 2022
(3) Li, J.; Yuan, H.; Zhang, W.; Jin, B.; Feng, Q.; Huang, J.; Jiao, Z. Carbon Energy 2022, 4 (3), 294–331
(4) Bai, S.; Yin, W.; Wang, L.; Li, Z.; Xiong, Y. RSC Advances. Royal Society of Chemistry 2016, pp 57446–57463
(5) Souza, M. L.; Lima, F. H. B. ACS Catal. 2021, 11, 19, 12208–12219
(6) Zhang, Q.-P.; Sun, Y.-L.; Cheng, G.; Wang, Z.; Ma, H.; Ding, S.-Y.; Tan, B.; Bu, J.-H.; Zhang, C. J. Chem. Eng. 2020, 391, 123471
(7) Sun, S. C.; Jiang, H.; Chen, Z. Y.; Chen, Q.; Ma, M. Y.; Zhen, L.; Song, B.; Xu, C. Y. Angewandte Chemie International Edition 2022, 61 (21), e202202519

Keywords

Au | nanoscale | polymer

Symposium Organizers

Virgil Andrei,
Rafael Jaramillo, Massachusetts Institute of Technology
Rajiv Prabhakar,
Ludmilla Steier, University of Oxford

Session Chairs

Virgil Andrei
Ludmilla Steier

In this Session