Artificial photosynthesis for CO2-to-ethylene conversion enabled by dye-sensitised carbon nitrides

Photoelectrochemical (PEC) cells are unique devices combining direct solar light conversion into chemical bonds with the compactness and catalytic tuneability of electrolysis. Photoelectrocatalysis is a promising solution for the scalable synthesis of solar fuels, i.e. chemicals with deliverable energetic content, and photoreforming, that is the light-driven conversion of waste into added-value products. On the cathodic side, solar-driven CO2 reduction to hydrocarbons and other organic molecules is a promising venue to solar fuels synthesis and strategy for decarbonisation. For the anodic reaction, glycerol has been proposed as excellent photoreforming substrate for its facile oxidation and its current overproduction as a byproduct of the synthesis of biodiesel. However, glycerol oxidation usually leads to a mixture of products, including glyceraldehyde and 1,3-dihydroxyacetone, with the latter being more valuable. The purpose of this Ph.D. project will be to design and fabricate a stand-alone PEC device comprising a photocathode for high-rate synthesis of C2-C3 hydrocarbons from CO2 and a photoanode for the selective photoreforming of glycerol to 1,3-dihydroxyacetone in acidic environment. The incorporation of a tandem perovskite solar cell in a copper-based photocathode will enable conversion of CO2 to hydrocarbons at very positive onset potentials and record-breaking photocurrents. On the other hand, different light-absorbing semiconductors, including polymeric carbon nitrides and perovskites, will be screened for the fabrication of a photoanode for glycerol oxidation. Selectivity of the anodic reaction will be achieved either by state-of-the-art Pt-Bi electrocatalysts or substrate-specific enzymes. Finally, the two electrodes will be combined in a stand-alone device for a bias-free, solar-driven complete redox cycle.

Our main impacts will be:
- a new generation of interdisciplinary nano researchers with expertise across science and innovation, fluent in the combination of approaches and technologies
- strategic developments in the study and control of nano-interfaces connecting complex architectures, for advances in emerging scientific grand challenges across vital areas of energy, health and ICT
- integration of new functional nanotechnologies together by harnessing nano-interfaces within larger application systems, and their translation into innovative products and services through our industry partners and student-led spin-outs
- a paradigm change of collaborative outlook in this science and technology
- a strong interaction with stakeholders including outreach and public engagement with cutting edge nano research
- improved use of interdisciplinary working tools including management, discipline bridging and IT

Economic impact of the new CDT is focused through our industrial engagement programme, as well as our innovation training. Our partner companies include - NPL, Hitachi, Oxford Nanopore, TWI, ARM, Eight19, Mursla, Britvic, Nokia Bell Labs, IBM, Merck, Oxford Instruments, Aixtron, Cambridge Display Technologies, Fluidic Analytics, Emberion, Schlumberger, Applied Materials and others. Such partnerships are crucial for the UK to revive high value manufacturing as the key pillar to lead for future technologies. We evidence this via the large number of CDT projects resulting in patents, with their exploitation supported by Cambridge Enterprise and our Industry Partners, and direct economic impact has also resulted from the large proportion of our students/alumni joining industry (a key outcome), or founding startups including: Echion Technologies (battery materials), Inkling Cambridge (Graphene inks and composites), HexagonFab (2D materials), Simprints (low-cost biometrics), Cortirio (rapid diagnosis of brain injury).

Training impact emerges through not just the vast array of Nano techniques and ideas that our cohorts and associated students are exposed to, but also the interdisciplinary experience that accrues to all the academics. In particular the younger researchers coming into the University are plugged into a thriving programme that connects their work to many other sciences, applications, and societal challenges. Interactions with external partners, including companies, are also strong and our intern programme will greatly strengthen training outcomes.

Academic impact is fostered by ensuring strong coherent plans for research in the early years, and also the strong focus of the whole CDT on study and control of nano-interfaces connecting complex architectures. Our track record for CDT student-led publications is already strong, including 4 Nature/Science, 6 Nature Chem/Nano/Mat, 13 Nat. Comm., with student publications receiving >6000 citations in total, including 16 papers with >100 citations each and high altmetric scores. Students have also given talks and posters at international conferences and won numerous awards/fellowships for research excellence.

Societal impacts arise from both the progression of our cohorts into their careers as well as their interaction with the media, public, and sponsors. We directly encourage a wide variety of engagement, including interaction with >5000 members of the public each year (mostly pre-university) through Nano exhibits during public events such as the Cambridge Science Festival and Royal Society Summer Science Exhibition, and also art-science collaborations to reach new audiences. We also run public policy and global challenges workshops, and will further develop this aspect with external partners. Our efforts to bring societal challenges to students' awareness frames their view of what a successful career looks like. Longer term societal impact comes directly from our engagement with partner companies creating jobs and know-how in the UK.