Hetero-Metallic Metal-Organic Frameworks for Photoreduction of CO2 to C2+ Hydrocarbons
Lead Research Organisation:
University of Manchester
Department Name: Chemistry
Abstract
In this project, we will be focusing on the efficient visible-light-driven photoreduction of CO2 to produce high-value-added C2+
products rather than intensively reported C1 ones, which will hopefully eliminate the impact of the massive global CO2 emission and
produce valuable hydrocarbons. Transition metals, such as Cu, Fe, Ni, and Co, will be incorporated into the structure of Ti(IV)-MOFs
(Metal-organic Frameworks). We will evaluate the catalytic performance of the prepared catalysts to target C2+ hydrocarbon
products. Full characterization, including X-ray absorption near edge structure (XANES), inelastic neutron scattering (INS), pair
distribution function (PDF), and electro-optics spectroscopies will be applied to analyze the spatial distribution and electron transfer
process of the catalysts. The optimized catalysts will be scaled up and performance evaluated in large-scale reactions.
products rather than intensively reported C1 ones, which will hopefully eliminate the impact of the massive global CO2 emission and
produce valuable hydrocarbons. Transition metals, such as Cu, Fe, Ni, and Co, will be incorporated into the structure of Ti(IV)-MOFs
(Metal-organic Frameworks). We will evaluate the catalytic performance of the prepared catalysts to target C2+ hydrocarbon
products. Full characterization, including X-ray absorption near edge structure (XANES), inelastic neutron scattering (INS), pair
distribution function (PDF), and electro-optics spectroscopies will be applied to analyze the spatial distribution and electron transfer
process of the catalysts. The optimized catalysts will be scaled up and performance evaluated in large-scale reactions.
Organisations
| Description | To mitigate climate change and reduce atmospheric CO2 concentrations, the CO2 reduction reaction (CO2RR) presents an attractive strategy for converting CO2 into valuable commodity chemicals. However, state-of-the-art catalysts still suffer significantly from poor selectivity toward targeted products, complicating product separation. Metal-organic frameworks (MOFs) have emerged as promising porous catalysts capable of integrating CO2 capture with photo-conversion. Their exceptional structural and compositional tunability allows precise optimization of optical and electrochemical properties, thereby enabling tailored photocatalytic performance. Additionally, the well-defined binding and active sites within MOFs offer a valuable opportunity to achieve overall CO2 photoreduction, a process often hindered by challenging oxidation half-reactions. In our ongoing fellowship project, we have focused on redox-active Ce(IV)-based MOFs utilizing the linker 2-aminoterephthalate (Ce-UiO-66-NH2). Ce-UiO-66-NH2 is particularly intriguing due to the availability of empty 4f orbitals in Ce(IV), which readily accept electrons from 2-aminoterephthalate due to the orbital overlapping. This interaction significantly enhances charge separation, promoting efficient CO2 reduction. Consequently, our studies have demonstrated that Ce-UiO-66-NH2 facilitates highly efficient overall CO2 photoreduction (ca. 92 µmol/g/h), selectively converting CO2 into CO with 100% selectivity while simultaneously oxidizing water to O2. Remarkably, given its superior catalytic efficiency, excellent selectivity, and the absence of sacrificial agents or co-catalysts, Ce-UiO-66-NH2 outperforms top-tier photocatalysts, establishing itself as a new benchmark for photocatalytic CO production. Furthermore, comprehensive characterizations-including isotope-labeling experiments, in situ FTIR, in situ XANES, and in situ synchrotron PXRD analyses-have revealed a novel reaction mechanism involving dynamic CO2 binding on Ce metal sites facilitated by efficient ligand-to-metal charge transfer (LMCT). This mechanism provides unprecedented atomic-level insights into the overall CO2 photoreduction process, advancing fundamental understanding in the field and potentially guiding the development of even more active photocatalytic systems. |
| Exploitation Route | We are currently in discussion with external stakeholders, funders and industry to take our results forward via scale up experiments. Key publications and IP protection are in preparation. |
| Sectors | Chemicals Energy |