Reductive synthesis of C1 products from CO2 via functionalised tubular nanomaterials

Project background (identification of the problem and its importance and relevance to sustainability)
As one will be aware, increasing global temperatures and climate change are at the forefront of global and governmental policies to slow the production of pollutant gases. The focused culprit in many new schemes to tackle climate change is CO2, this causes the so called "Greenhouse" gas affect, trapping heat within our atmosphere, increasing global temperatures. Moreover, the greenhouse gas affect is not the only side effect of increased CO2 production, with increased levels of CO2 within the atmosphere this can affect the pH of sea water; this can have drastic effects on delicate ecosystems such as coral reefs. For many years CO2 has been emitted in large quantities with no regulation or care for our planet, but only within the last decade(s) has money been inputted into technologies and research to stop CO2 production, to entrap and store CO2 and to convert CO2 into useful products. By increasing research output for CO2 sequestration, this increases the speed at which we can tackle the climate crisis. Therefore, by implementing new and emerging, this will allow for preservation of precious materials and reduced CO2 production.
Proposed solution and methodology
Tackling CO2 concentration within the atmosphere is of upmost importance, hereby the proposed solution is electrocatalytic conversion of CO2 using functionalised carbon nanotube structures with ionic liquids and metal nanoparticles. The excellent conductivity of carbon nanotubes is well documented as well as ionic conductivity of ionic liquids alike, as such a composite material of the two coupled with metal nanoparticles for specific conversion of CO2 to useful products will allow for a broad overview of the system and its viability. Ionic liquids will be chosen based on the interaction strengths with CO2. I propose that increasing the aromatic groups within the ionic liquid will dramatically increase the absorption or uptake of CO2; all the while not utilising fluorine containing ionic liquids, although these have shown excellent CO2 uptake properties, production of hydrofluoric acid to functionalise these materials is highly polluting and must be avoided to not produce extremely harmful materials that could potentially be released into the environment. Also, by increasing aromatic groups within the ionic liquid, this also allows for further pi-pi stacking between the ionic liquid and carbon nanotube, which could allow for surface fictionalised nanotubes as well as internally trapped ionic liquids; potentially providing two pathways CO2 could follow. Therefore, it is proposed that by utilising magnetron sputtering a known metal loading can be achieved and with further analysis (TEM) leading to the locating of these metal cluster sites and if the desired material is formed. Lastly, all ionic liquids will be prepared using Schlenk techniques to ensure a purified material, with no unwanted compounds within the ionic liquid to ensure no side reactions occur within electrochemical cell. Furthermore, present technologies utilise precious metals, that are quickly being depleted through overuse or scarcity on out planet, I plan to use a naturally abundant metal (copper), this has shown to effectively activate CO2 and has been shown to produce desirable products such as methanol over less desirable compounds. By utilising this system in electrocatalysis, this has the unique opportunity to use "green electrons", this is the production of electricity through sustainable non-polluting methods (wind farms, hydroelectric dams etc.) and with the increased presence of these forms of energy production on the national grid providing a more sustainable process.

This CDT will deliver impact aligned to the following agendas:

People
A2P will provide over 60 PhD graduates with the skill sets required to deliver innovative sustainable products and processes into the UK chemicals manufacturing industry. A2P will inspire and develop leaders who will:
- understand the needs of industrial end-users;
- embed sustainability across a range of sectors; and
- catalyse the transition to a more productive and resilient UK economy.

Economy
A2P will promote a step change towards a circular economy that embraces resilience and efficiency in terms of atoms and energy. The benefits of adopting more sustainable design principles and smarter production are clear. For example, the global production of active pharmaceutical ingredients (APIs) has been estimated at 65,000-100,000 tonnes per annum. The scale of associated waste is > 10 million tonnes per annum with a disposal cost of more than £15 billion. Consequently, even a modest efficiency increase by applying new, more sustainable chemical processes would deliver substantial economic savings and environmental wins. A2P will seek and deliver systematic gains across all sectors of the chemicals manufacturing industry. Our goals of providing cross-scale training in chemical sciences with economic and life- cycle awareness will drive uptake of sustainable best practice in UK industry, leading to improved economic competitiveness.

Knowledge
This CDT will deliver significant new knowledge in the development of more sustainable processes and products. It will integrate the philosophy of sustainability with catalysis, synthetic methodology, process engineering, and scale-up. Critical concepts such as energy/resource efficiency, life cycle analysis, recycling, and sustainability metrics will become seamlessly joined to what is considered a 'normal' approach to new molecular products. This knowledge and experience will be shared through publications, conferences and other engagement activities. A2P partners will provide efficient routes to market ensuring the efficient translation and transferal of new technologies is realised, ensuring impact is achieved.

Society
The chemistry-using industries manufacture a rich portfolio of products that are critical in maintaining a high quality of life in the UK. A2P will provide highly trained people and new knowledge to develop smarter, better products, whilst increasing the efficiency and sustainability of chemicals manufacture.
To amplify the impacts of our CDT, effective public engagement and technology transfer will become crucially important. As a general comment, 'sustainability' styled research is often regarded in a positive light by society, however, the science that underpins its effective implementation is often poorly appreciated. The University of Nottingham has developed an effective communication portfolio (with dedicated outreach staff) to tackle this issue. In addition to more traditional routes of scientific communication and dissemination, A2P will develop a portfolio of engagement and outreach activities including blogs, webpages, public outreach events, and contribution of material to our award-winning YouTube channel, www.periodicvideos.com.

A2P will build on our successful Sustainable Chemicals and Processes Industry Forum (SCIF), which will provide entry to networks with a wide range of chemical science end-users (spanning multinationals through to speciality SMEs), policy makers and regulators. We will share new scientific developments and best practice with leaders in these areas, to help realise the full impact of our CDT. Annual showcase events will provide a forum where knowledge may be disseminated to partners, we will broaden these events to include participants from thematically linked CDTs from across the UK, we will build on our track record of delivering hi-impact inter-CDT events with complementary centres hosted by the Universities of Bath and Bristol.