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Details of Grant 

EPSRC Reference: EP/T013079/1
Title: Surface Engineered Nanocrystals: EPR Radical Detection of Photoactivity
Principal Investigator: Richards, Dr E
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department: Chemistry
Organisation: Cardiff University
Scheme: New Investigator Award
Starts: 12 October 2020 Ends: 11 October 2023 Value (£): 304,043
EPSRC Research Topic Classifications:
Catalysis & Applied Catalysis
EPSRC Industrial Sector Classifications:
No relevance to Underpinning Sectors
Related Grants:
Panel History:
Panel DatePanel NameOutcome
24 Oct 2019 EPSRC Physical Sciences - October 2019 Announced
Summary on Grant Application Form
Environmental air and water remediation by nanocrystalline semiconductor photocatalysts has become increasingly important in recent years. TiO2 remains the most popular material for these applications due to its low cost, abundance, high activity, and stability under a variety of conditions, however its wide range utilisation is restricted due to limited efficiencies, absorbing only 3% of available solar energy (in the UV region). Commercial advancements require enhanced visible-light induced quantum yields of photogenerated charge carriers. Lattice doping of TiO2 with (non)metal ions is a highly promising approach for increasing photocatalytic efficiencies through modification of bandgap and band-edge potentials, which are intricately linked to resulting surface reactions. This utilises earth-abundant metals and is a step-change from modifying oxide materials with expensive noble metals.

The advent of synthetic strategies for controllable fabrication of TiO2 with specific morphologies and crystal facets has emerged as a promising way to improve charge-carrier quantum yield. This proposal aims at combining these tactics to develop a library of novel nanocrystalline materials, produced via readily scalable methodologies. This works seeks to build on our recent results. We have identified that co-doped titania catalysts (W,N-TiO2) are effective for improving the nitrate selectivity of the photocatalytic oxidation of NOx to nitrates. We have also identified specific oxygen-vacancy sites on the titania surface that act as preferential sites for catalysis. By combining these technologies, this could open new and exciting avenues in semiconductor photocatalysis for environmental remediation technologies in which the optimization of molecular oxygen reduction, together with the pollutant species to be oxidized, becomes a central element of the catalyst design without relying on the use of rare and expensive PGMs.

The novel materials will be characterised by a combination of advanced spectroscopic techniques. Primarily, Electron Paramagnetic Resonance (EPR) spectroscopy will directly probe the photo-induced paramagnetic charge carriers, determining the position of highly reactive lattice sites. Advanced hyperfine structure measurements will elucidate an atomic-level structural description and access the electronic properties of lattice dopants through unique spectral fingerprints. The nature of surface reactions will subsequently be explored through state-of-the-art Attenuated Total Reflectance spectroscopy, utilising pulsed lasers to obtain reaction dynamics on fs timescales. Target applications will be selective decomposition of volatile organic compounds and nitrogen oxides (NOx), both common airborne pollutants which are damaging to human health and implicated in climate change.

Our research program will have immediate impact on UK science, with academic beneficiaries within the chemical and materials sciences. The project will provide interdisciplinary training for the EPSRC PDRA and Cardiff University funded PhD student. The combination of multiple advanced spectroscopies will shed light on fundamental redox processes, which will have longer-term benefits in photovoltaics, organic synthesis and selective transformations of bulk chemicals. This New Investigator Grant will allow Dr Richards to develop an independent research programme investigating light-induced electron transfer processes, and provide a team of highly skilled researchers vital to advance her academic career.

Success in this programme will combine the results of synthesis, characterization and catalytic activity to guide the rational design of selective visible-light activated semiconductor photocatalysts.

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Organisation Website: http://www.cf.ac.uk