Design of semiconducting materials for water-splitting photocathodes
Lead Research Organisation:
Imperial College London
Department Name: Chemistry
Abstract
We will design and synthesise new classes of calamitic shaped small molecules to be employed as electron acceptors in bulk heterojunction blends for high reduction potential photocathodes. The design strategy will focus on creating conjugated aromatic semiconductors with discrete separation of electron rich and poor molecular sections, drawing on a symmetric monomer design template used in donor polymer synthesis. This has been an established and successful strategy to aid efficient materials optimisation and is a core area of expertise in the McCulloch group. In the intended application, it is necessary for the photocathode to exhibit a high reduction potential to maximize the overpotential, which enhances hydrogen generation. A prominent feature therefore of all molecular design considerations in this task is to facilitate high reduction potential heterojunctions through ensure that the acceptor LUMO is of high enough energy. This requires subtle destabilization of the LUMO through low levels of conjugation, out of plane orbital twisting, and the use of soft electron withdrawing groups. Building on this approach, we will explore conjugated systems that may additionally provide improved electron transport. A high photoelectrode overpotential will be facilitated by destabilisation of the LUMO through both steric twisting, conjugation blocking and limiting the strength of the electron withdrawing units. Importantly, the molecular design must ensure stability in aqueous environments both in the neutral and charged state. Water tolerant moieties will be identified and incorporated in the molecular design, while approaches to minimise water penetration at the film surface, and diffusion within the bulk will be pursued.
Organisations
Publications
Kosco J
(2020)
Enhanced photocatalytic hydrogen evolution from organic semiconductor heterojunction nanoparticles.
in Nature materials
Kosco J
(2018)
The Effect of Residual Palladium Catalyst Contamination on the Photocatalytic Hydrogen Evolution Activity of Conjugated Polymers
in Advanced Energy Materials
Wadsworth A
(2018)
Progress in Poly (3-Hexylthiophene) Organic Solar Cells and the Influence of Its Molecular Weight on Device Performance
in Advanced Energy Materials
Xie C
(2018)
Overcoming efficiency and stability limits in water-processing nanoparticular organic photovoltaics by minimizing microstructure defects.
in Nature communications
Studentship Projects
Project Reference | Relationship | Related To | Start | End | Student Name |
---|---|---|---|---|---|
EP/N509486/1 | 30/09/2016 | 30/03/2022 | |||
1822223 | Studentship | EP/N509486/1 | 30/09/2016 | 28/02/2021 | Matthew Bidwell |
Description | We have discovered a low-cost, robust and renewable process to generate green hydrogen from water and sunlight using a blend of organic polymer and small molecule semi-conductors nanoparticles. These materials have shown a record H2 evolution rate of over 60,000 µmol h-1 g-1 under 350 to 800 nm illumination (which is the region of maximum solar energy) and has out-performed many inorganic based technologies in this area. |
Exploitation Route | The outcomes of this funding can be taken forward within our group by applying this approach to CO2 reduction, N2 fixation and overall water splitting. Research scientists in the wider community will also be able to benefit from this work by applying these same principles to research fields such as bio-technology, chemical manufacturing and organic electronics. |
Sectors | Chemicals Electronics Energy Manufacturing including Industrial Biotechology Pharmaceuticals and Medical Biotechnology |
URL | https://www.nature.com/articles/s41563-019-0591-1 |