Design of semiconducting materials for water-splitting photocathodes

Lead Research Organisation: Imperial College London
Department Name: Dept of Chemistry


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.

Studentship Projects

Project Reference Relationship Related To Start End Student Name
EP/N509486/1 01/10/2016 30/09/2021
1822223 Studentship EP/N509486/1 01/10/2016 28/02/2021 Matthew William 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