Dinitrogen Activation Using Heterobimetallic Complexes Supported by an Extended Cryptand Ligand

Lead Research Organisation: King's College London
Department Name: Chemistry

Abstract

Fertilisers. Detergents. Nylons. All of these products are derived from ammonia, which is produced on a megaton scale every year by the Haber-Bosch process. This is one of the world's most important industrial processes: it is the only commercially viable method for transforming nitrogen from the atmosphere into ammonia. However, the environmental impact of the Haber-Bosch process is huge: between 1-2% of the global energy demand, and 1.4% of global CO2 emissions, are a direct result of this process. Despite over a century of research, no commercially viable alternatives have been developed to mitigate this damage.

One of the reasons that the Haber-Bosch process consumes so much energy is the need to break the very strong triple bond between two nitrogen atoms, followed by the reaction with hydrogen to generate ammonia. This project aims to develop an entirely new method for synthesising ammonia by using a single molecule as a catalyst to break that triple bond and form ammonia, all in one step. The key feature of the single molecule is that it will incorporate two different transition metal atoms. One metal will be responsible for binding and activating nitrogen, whilst the other metal atom will carry out the hydrogenation to form ammonia.

Using two different metal atoms means that each metal can be the best one for the job it needs to do, whereas more traditional metal-based catalysts have to compromise on one (or both) parts of this reaction. By selecting the best metals for the job, the energy demand of the reaction will be substantially reduced. This will translate into lower CO2 emissions and lower energy consumption on a global scale.

Publications

10 25 50
 
Description We have made significant advances in understanding the chemical properties of bimetallic cryptand systems. We can now reliably make bimetallic molecules using multiple different cryptand architectures without needing to use anions that have the potential to be explosive. We can also do this chemistry in solvents other than water, none of which was possible before this grant.

One other achievement was correcting an old error in the literature, namely the synthesis of a ferrocene-based cryptand had been claimed but without much supporting evidence. We spent a significant amount of time trying to make this molecule but discovered that the final step in the synthesis did not work as claimed.
Exploitation Route The project is ongoing in my lab and will be picked up by a new PhD student starting in October 2023. This will enable us to write up some of the key findings for an initial publication.
Sectors Chemicals

 
Description Departmental studentship
Amount £100,000 (GBP)
Organisation King's College London 
Sector Academic/University
Country United Kingdom
Start 09/2023 
End 09/2027
 
Description Royal Society of Chemistry Outreach fund
Amount £4,400 (GBP)
Organisation Royal Society of Chemistry 
Sector Charity/Non Profit
Country United Kingdom
Start 03/2022 
End 12/2022