- ☀️ Utilizing solar light for CO2 reduction reaction (CO2RR) to produce renewable energy is challenging due to high energy barriers and multielectron transfer processes.
- ☀️ Introduction of supramolecular donor-acceptor (D-A) complexes in metal-organic frameworks (MOFs) can enhance the electron transfer kinetics for selective and efficient CO2 reduction to CH4.
- ☀️ MOF-808-PBA-MV, a MOF with a CT (charge transfer) complex of PBA and MV2+ inside its pore, produced CH4 with high selectivity and efficiency under visible light.
- ☀️ MOFs with supramolecular donor-acceptor (D-A) complexes show promise as photocatalysts for CO2 reduction.
- ☀️ MOF-808-PBA-MV is a unique MOF with a charge transfer complex formed by PBA (1-pyrenebutyric acid) and MV2+ (methyl viologen) within its pore.
- ☀️ MOF-808-PBA-MV efficiently harnesses visible light to generate photo-modulated electron-hole pairs for selective CO2 reduction to CH4 in an aqueous medium.
- ☀️ The D-A complex facilitates rapid electron transfer from PBA to MV2+ and then to the catalytic center (Zr-oxo cluster) for CH4 production.
- ☀️ MOF-808-PBA-MV achieved a CH4 production rate of 7.3 mmol g−1 with >99% selectivity, surpassing H2 evolution, using BNAH and TEA as sacrificial agents.
- ☀️ The unique design of MOF-808-PBA-MV enhances the kinetics of electron transfer, leading to highly reduced and selective CO2 reduction products.
- ☀️ In situ DRIFT, EPR, and TA spectroscopy, along with DFT calculations, were used to understand the reaction mechanism.
Researchers have sought innovative solutions to address the global energy crisis and reduce greenhouse gases by utilizing solar light for CO2 reduction. However, the high energy barriers and multielectron transfer processes involved in the photoreduction of CO2 pose significant challenges. To overcome these hurdles, scientists have introduced supramolecular donor-acceptor (D-A) complexes within metal-organic frameworks (MOFs) to enhance the electron transfer kinetics. MOF-808-PBA-MV, a unique MOF, contains a charge transfer complex formed by PBA and MV2+ confined within its pores. This D-A complex acts as a light harvester, generating photo-modulated electron-hole pairs that efficiently reduce CO2 to CH4 in an aqueous medium under visible light. The MOF design facilitates rapid electron transfer from PBA to MV2+ and subsequently to the catalytic center (Zr-oxo cluster), resulting in highly reduced and selective CH4 production. MOF-808-PBA-MV demonstrated exceptional performance, producing CH4 at a rate of 7.3 mmol g−1 with >99% selectivity, effectively suppressing H2 evolution using BNAH and TEA as sacrificial agents. The research was supported by in situ DRIFT, EPR, and TA spectroscopy, along with DFT calculations, to gain insights into the reaction mechanism.
- Sanchita Karmakar, Soumitra Barman, Faruk Ahamed Rahimi, Darsi Rambabu, Sukhendu Nath & Tapas Kumar Maji
- Solar-driven CO2 reduction
- Metal-organic framework (MOF)
- Supramolecular donor-acceptor complex
- Highly selective methane production
- Efficient charge transfer kinetics