Main Group Element Based Catalysis for Photolytic HX-Splitting

As global populations increase and standards of living improve, so does humanity's dependence on fossil fuel reliant processes, which is accompanied by an unwanted increase in CO2 emissions. As such, much of modern science is unified by a common goal - to reduce global CO2 emissions by finding "green" alternatives to these fossil fuel-based processes. The dominant form of energy consumption is the generation of electricity, with alternatives such as wind and solar energy considered viable routes to do so in a sustainable manner. However, these approaches have their inherent drawbacks, mainly in the form of geographical constraints and intermittency of power output. Essentially: not all areas of the globe have equal wind and sun coverage, and even in those with plenty, these natural processes do not operate reliably at all times. Therefore, methods of maximising power output and efficiently storing such power must be developed to make these green approaches reliable on a large scale. Concerning the storage of renewable energy, one particular method has caught the attention of the scientific community - energy storage in chemical bonds. The chemical bond arises when two or more atoms share electrons with one another, resulting in these electrons existing somewhere in-between the bonded atoms. The formation of this bond results in energy being stored in the resulting molecule - we call this "Chemical Energy".
The question now is - what bonds do we use and how do we store the resulting molecule/fuel?
The obvious starting point is to only consider fuels which do not contribute to global warming - for example by scrapping those which contain carbon and opting instead for those which release non- polluting compounds upon both formation and combustion. For this reason, the use of hydrogen, H2, as a fuel has gained significant attention. The large-scale synthesis of hydrogen is already an established and widely implemented procedure, however it currently requires the use of a chemical process known as Methane Steam Reforming. As the name suggests, this method, which is responsible for 95% of hydrogen production in the United States, requires the use of methane (CH4, a.k.a natural gas) as the main chemical precursor and results in the release of CO2. Clearly, this route towards hydrogen is not viable when aiming to achieve net-zero carbon emissions. Therefore, a new route needs to be devised.
Efforts in this field have led to one particular approach emerging as most attractive - electrochemical water splitting. What this means is: splitting water (H2O) into its constituent parts - H2 and O2 - using electricity (itself sustainably generated). This process, however, suffers an intrinsic penalty as water- splitting is energetically unfavourable, requiring a large energy input to break strong O-H bonds. This issue may be simplified by using a different feedstock - the chemically more-straightforward hydrohalic acids, HX (X = F, Cl, Br, I). HX-splitting is a two-electron, two-proton reaction, thus reducing the complexities associated with the four-electron, four-proton water-splitting reaction. The focus of this project, which falls within the EPSRC Energy research theme, is to develop new phosphorous- containing compounds which enable the HX-splitting reaction to occur efficiently. Traditionally, research into this field focuses on the use of precious metals to provide a similar result, but by turning attention to the much more accessible and abundant phosphorous, this approach becomes more attractive for large scale adoption.

The primary impact of the OxICFM CDT will be the highly-trained world-class scientists that it delivers. This impact will encompass both the short term (during their doctoral studies), the medium term (subsequent employment) and ultimately the longer timescale defined by their future careers and consequent impact on science, engineering and policy in the UK.

The impact of OxICFM students during their doctoral studies will be measured by the culture change in graduate training that the Centre brings about - in working at the interface between inorganic synthesis and manufacturing, and fostering cross-sector industry/academia working practices. By embedding not only from larger companies, but also SMEs, we have developed a training regime that has broader relevance across the sector, and the potential for building bridges by fostering new collaborations spanning enormous diversity in scientific focus and scale. Moreover, at a broader level, OxICFM offers to play a unique role as a major focus (and advocate) for manufacturing engagement with academic inorganic synthetic science in the UK.

From a scientific perspective, OxICFM will be uniquely able to offer a broad training programme incorporating innovative and challenging collaborative projects spanning all aspects of fundamental and applied inorganic synthesis, both molecular and materials based (40+ faculty). These will address key challenges in areas such as energy provision/storage, catalysis, and resource provision/renewal necessary to enhance the capability and durability of UK plc in the medium term. To give some idea of perspective, the output from previous CDTs in Oxford's MPLS Division include two start-up companies and in excess of 30 patents.

It is not only in the industrial and scientific realms that students will have impact during their timeframe of their doctorate. Part of the training programme will be in public engagement: team-based challenges in resource development/training and outreach exercises/implementation will form part of the annual summer school. These in turn will constitute a key part of the impact derived from the CDT by its engagement with the public - both face-to-face and through electronic/web-based media. As the centre matures, our aspiration is that our students - from diverse backgrounds - will act as ambassadors for the programme and promote even higher levels of inclusion from all parts of society.

For our partners, and businesses both large and small in the manufacturing sector, it will be our students who are considered the ultimate output of the OxICFM CDT. Our programme has been shaped by the need of such companies (frequently expressed in preliminary discussions) to recruit doctoral graduates who can apply themselves to a broad spectrum of multi-disciplinary challenges in manufacturing-related synthesis. OxICFM's cohort-based training programme integrates significant industry-led training components and has been designed to deliver a much broader skill set than standard PhD schemes. The current lack of CDT training at the interface of inorganic chemistry and manufacturing (and the relevance of inorganic molecules/materials to numerous industrial sectors) heightens the need for - and the potential impact of - the OxICFM CDT. Our students will represent a tangible and valuable asset to meet the long-term skills demand for scientists to develop new materials and nanotechnology identified in the UK Government's 2013 Foresight report.

In the longer term, the broad and relevant training delivered by OxICFM, and the uniquely wide perspective of the manufacturing sector it will deliver, will allow our graduates to obtain (and thrive in) positions of significant responsibility in industry and in research facilities/institutes. Ultimately we believe that many will go on to be future research leaders, driving innovation and changing research culture, and thereby making a lasting contribution to the UK economy.