MC-FMP-ECAT · Electrocatalytic proton and CO2 reduction: Metal based fused diporphyrins with proton relays for efficient catalysis
Horizon 2020 — Marie Skłodowska-Curie Actions
- Duration
- 2021-03-01 → 2023-02-28
- EU contribution
- €162,806
- Participants
- 1
- Scheme
- MSCA-IF
Lines connect the coordinator with its partners.
Results in brief
Electrocatalytic proton and CO2 reduction: Metal based fused diporphyrins with proton relays for efficient catalysis
- The project “Electrocatalytic proton and CO2 reduction: Metal based fused diporphyrins with proton relays for efficient catalysis” explores the design and development of dinuclear metalloporphyrin catalysts for sustainable hydrogen production and CO2 reduction at laboratory scale. Fused porphyrins are unique structural motifs in which two monoporphyrin units are connected via β–β, meso–meso, β′–β′ triple covalent linkages that allow seamless delocalization and storage of electrons across extended multimetallic ligand scaffolds. The project sought to investigate the impact of covalent linkages on the optical, electronic, (spectro)electrochemical, magnetic and electrocatalytic activities of metal complexes of bis-porphyrins. - The development of catalysts for the sustainable production of hydrogen is one of the most pressing issues of current time. Different catalysts investigated over the years are still plagued with problems related to overpotential, catalytic efficiency and widespread applicability. Therefore, studies on the coordination chemistry, electronic and catalytic properties of the fused porphyrins are expected to open a new avenue for the design of efficient catalytic systems for electrochemical small molecule activation reactions. - Overall objectives of the MSCA IF project are: a) development of effective synthetic protocols for the synthesis of first row transition metal complexes of bimetallic triply fused and monomeric metalloporphyrins; b) tuning the functional groups to study the effect and address solubility problems; c) establishment of electronic structures of the complexes and exploration of the catalytic activity of the metalloporphyrins in electrocatalytic proton and CO2 reduction; d) Quantification of catalytic parameters, analysis of catalytic efficiency for comparison with monomeric complexes and elucidation of the mechanistic pathway for establishing a structure-activity relationship. - The study revealed a positive influence of extensive electron delocalization on the higher activity and lower overpotential of the fused metalloporphyrins in proton reduction than the mononuclear complexes. In addition, the influence of a subtle change in the peripheral substituents on the solubility and catalytic efficiency was also highlighted.
Data: CORDIS, © European Union
Project objective
This project deals with the use of metal-based fused diporphyrins as electrocatalysts for HER/CO2 reduction. The objectives of the proposed work are as follows:i) Synthesis of metal complexes of substituted free base monoporphyrin derivatives bearing hydrophilic groups at the periphery (-SO3H, CH3PhSO3H, phenolic –OH groups). Moreover, attempts will be made to introduce functional groups positioned at the secondary coordination sphere facilitating interaction between metal with protons.ii) Synthesis of fused diporphyrins from respective monoporphyrin derivatives. Elucidation of their geometric and electronic structures through electrochemical, spectroscopic, and X-ray diffraction analyses.iii) Evaluation of the catalytic activity of the metal complexes in HER and CO2 reduction in both aqueous and non-aqueous mediums. A particular emphasis will be laid on the competitive/tandem proton and CO2 reduction, as well as on the interplay of two metal centers for efficient catalysis.iv) Quantification of electrocatalytic efficiency, and elucidation of mechanistic pathway to develop structure-activity correlations.Detailed information’s regarding implementation of objectives have been mentioned in Section 3 of the Part-B containing individual milestones for each sections and expected time period for execution.The proposed research project,if approved,is expected to bring about significant breakthroughs in the field of HER/CO2 reduction reactions. Furthermore, the study will provide new insights into the mechanistic pathway, which in turn will open up new avenues for the development of more efficient and cost-effective catalysts. Besides, the fellowship will provide an exciting opportunity to the researcher to develop new expertise, acquire knowledge, increase professional contacts and lastly a global exposure via mobility between different labs. Together all these skill sets will drastically improve the employability of the researcher in both industry or in academia.
Original text from CORDIS.
Participants
- UNIVERSITY OF STUTTGART · StuttgartCoordinatorGermany
Links
Data: CORDIS, © European Union