Molecular Metalloenzyme Mimics for the Electroreduction of CO2

PhD Start date: September 2021

The catalytic conversion of carbon dioxide into fuels and chemical feedstocks is one of the grand challenges for a global green economy, particularly when it can be driven by renewable electrical energy. Recent progress in electrocatalytically converting CO2 has resulted in the production of C1 molecules such as CO, methane and formate. The production of multi-carbon products is also essential, particularly ethylene, ethanol and carboxylic acids, which are important feedstocks for the chemical industry. However, the costs of producing multi-carbon molecules via direct CO2 conversion are not economically viable, due to the low activity and selectivity of present-day catalysts. Furthermore, there is a lack of information about the requirements of CO2 reduction and subsequent C−C bond formation, and more mechanistic understanding about this topic is essential.

Project Outline:
This PhD project explores a new bio-inspired approach to develop synthetic catalysts, using metalloenzymes as paradigms. Key enzymes for biological CO2 fixation are carbon monoxide dehydrogenase for reversible CO2 reduction, and acetyl coenzyme-A synthase for carbonylation, which both feature bimetallic sub-sites containing a redox-active nickel centre.

Two aims are outlined:
(i) Synthesis of highly reducing, bio-inspired transition metal compounds for CO2 activation.
In the first system, molecular compounds of earth-abundant transition metals will be synthesised, featuring a sulfur-rich ligand environment, as is commonly found in metalloenzymes. The reactivity patterns of these mono- and bimetallic complexes with CO2 and CO will then be established.
(ii) Development of well-defined electrocatalysts for C−C bond forming reactions of CO2 and CO.
In the second system, the potential of these new complexes as electrocatalysts for CO2 conversion will be realised. These new electrocatalysts will be benchmarked against the best performing literature examples, and structure/activity relationships established to feed back into the synthesis of improved catalysts. Finally, catalysts will be immobilised onto carbon electrodes to reduce solvent restrictions and facilitate recyclability.

These systems provide a new approach to the catalytic reduction of CO2 to multi-carbon products, namely, utilising bimetallic complexes inspired by the active sites of metalloenzymes.

Academic entry requirements:
UK Bachelor Degree with at least 2:1 in a relevant subject or overseas equivalent. University of Leicester English language requirements apply (where applicable).

This EPSRC studentship would suit an ambitious and highly motivated researcher with interests in organometallic chemistry and catalysis. A strong background in air-sensitive synthetic chemistry is highly desirable, but adequate training will be provided. Relevant previous research experience in academic laboratories essential.

How to apply:
Please submit your online application: https://srs.le.ac.uk/sipr/sits.urd/run/siw_ipp_lgn.login?process=siw_ipp_app&code1=RCHF00FN&code2=0093

Include with your application:
CV
Degree Certificates and Transcripts
Details of any study currently being undertaken
Enter the supervisor name and project title in the Proposal Section (no proposal required)
Enter contact details of two academic referees in the boxes provided or upload reference letters if already obtained.
Evidence of English language.
In the funding section include: Ref EPSRC-Kilpatrick

When you have submitted your application we will send you a personal statement form to complete separately.

Eligibility: UK/EU/ International