Periodic Reporting for period 3 - METHASOL (International cooperation for selective conversion of CO2 into METHAnol under SOLar light)
Periodo di rendicontazione: 2024-01-01 al 2024-12-31
Methanol is an appealing energy vector, with attractive volumetric and gravimetric energy values, storable in liquid phase at ambient conditions of pressure and temperature, and it can be used as fuel directly or converted into chemicals or gasoline. However, its production lacks a sustainable route. Thus, the METHASOL project aims to produce methanol through a sustainable and cost-effective process based on the selective sun light driven gas phase CO2 reduction, with a solar to methanol energy conversion efficiency of 5%. During 42 months, METHASOL gathered 14 partners from EU/Associated member states, China and the USA, including some of the world’s most recognized researchers on artificial photosynthesis, to achieve a ground-breaking combination of a photocatalytic CO2 reduction reaction (CO2RR) system based on Metal-Organic Framework (MOF) and a graphitic Carbon Nitride (g-CN) for photocatalytic oxygen evolution reaction (OER), through a Z-scheme heterojunction. At the end of the project, we were able to define the system specifications (WP1), synthesis and optimize several sets of materials for OER and CO2RR and to screen their photocatalytic activity and stability (WP 2 and 4). The most promising materials were analyzed by experimental characterization and modelling (WP3), leading to guidelines useful for designing enhanced CO2RR and OER materials (WP4). The best systems have been integrated through a Z-scheme heterojunction, either with or without a mediator, and tested in tailored reactors operating in the gas phase under different conditions (WP5). A complete sustainability analysis has been conducted (WP6) to ensure the clean production of methanol compared to other alternatives. The cooperation between European and Chinese research entities has been consolidated to last beyond the project lifetime through the creation of a common exploitation plan (WP7). Through its ambitious activities on photocatalyst developments for solar to methanol conversion, METHASOL has proposed a new path for decarbonizing Europe.
In WP4 different series of composites have been synthesized for the photocatalytic reduction of CO2. MOF@Cu composites are based on different chemically stable Ti and Zr MOFs combined with CuOx and Cu0 nanoparticles (NPs) and nanoclusters (NCs). To optimize their visible light harvesting properties, MOF@Cu composites were combined with carbon quantum dots (CQDs) as photosensitizers. Also hydrophobic Zr MOFs have been employed to increase the CO2 adsorption capacity in presence of water. As shown by multiple advanced characterization tools (PXRD, N2 adsorption/desorption, ICP-OES, TGA, FT-IR, TEM, HAADF-STEM, XPS, electrochemical characterization), these composites presented a high crystallinity and porosity, good charge transfer kinetics.
In WP 3 the photophysical properties, the microstructural, (photo)electrochemical and CO2 adsorption properties of selected CO2RR and ORR materials developed in this project have been explored to identify key catalyst descriptors linked to their performances and provide design guidelines to improve and optimize material efficiency.
In WP5, the best Z-scheme heterojunctions without mediator (CuO@MIL-125(Ti)-NH2/Co@K-PHI, Cu2O@MIL-125(Ti)-NH2/Co@K-PHI, CuO@ UiO-66(Zr)-(CF3)2 /Co@K-PHI and Cu2O@ UiO-66(Zr)-(CF3)2 /Co@K-PHI; (5 wt.%)MOF@(95 wt.%)S-PHI using MIL-140B(Zr) and MIP-177(Ti)LT; several Cu species (e.g. Cu(II), CuO, Cu2O) grafted in MIP-177(Ti)-LT and their composites with Co-PHI) have been finally evaluated for the photocatalytic CO2 reduction to CH3OH under solar and visible light irradiation. The photocatalytic experiments have been optimized in terms of illumination conditions, CO2/H2O or H2 mol ratio, voltage and pressure. A novel photocatalytic reactor has been developed that is comprised of an asymmetric membrane that separates between the two half reactions. It uses copper NPs supported on MIL-125(Ti)-NH2 for CO2RR and Co-KPHI for OER, while decoupling between the transport of protons and the transport of electrons. Following illumination, several products were identified, in particular ethanol, methanol, C2H4 and other compounds, yet to be determined (suspected as formic acid/formaldehyde). In parallel, it was shown that in the absence of CO2, these products are not obtained, thus pointing out to the possibility of formation of fuels from CO2 by utilizing solar light.
Participation in several meetings and workshops related to Carbon Capture, Utilisation and Storage (CCUS) & Alternative Fuels., public perception and business models has been an excellent opportunity to network with industry experts, project representatives, investors and policy makers, facilitating collaboration, knowledge sharing and future partnerships. Participation in events such as conferences and workshops has enabled the development of relations with projects with similar research themes.
To foster the replicability and the transferability of the project’s solutions, two events on the International Industrial Board have been organized during the project, one in June 2023 with a progressed roadmap, and the other meeting at the end of the project in December 2024.
In WP 3 the photophysical properties, the microstructural, (photo)electrochemical and CO2 adsorption properties of selected CO2RR and ORR materials developed in this project have been explored to identify key catalyst descriptors linked to their performances and provide design guidelines to improve and optimize material efficiency.
In WP5, the best Z-scheme heterojunctions without mediator (CuO@MIL-125(Ti)-NH2/Co@K-PHI, Cu2O@MIL-125(Ti)-NH2/Co@K-PHI, CuO@ UiO-66(Zr)-(CF3)2 /Co@K-PHI and Cu2O@ UiO-66(Zr)-(CF3)2 /Co@K-PHI; (5 wt.%)MOF@(95 wt.%)S-PHI using MIL-140B(Zr) and MIP-177(Ti)LT; several Cu species (e.g. Cu(II), CuO, Cu2O) grafted in MIP-177(Ti)-LT and their composites with Co-PHI) have been finally evaluated for the photocatalytic CO2 reduction to CH3OH under solar and visible light irradiation. The photocatalytic experiments have been optimized in terms of illumination conditions, CO2/H2O or H2 mol ratio, voltage and pressure. A novel photocatalytic reactor has been developed that is comprised of an asymmetric membrane that separates between the two half reactions. It uses copper NPs supported on MIL-125(Ti)-NH2 for CO2RR and Co-KPHI for OER, while decoupling between the transport of protons and the transport of electrons. Following illumination, several products were identified, in particular ethanol, methanol, C2H4 and other compounds, yet to be determined (suspected as formic acid/formaldehyde). In parallel, it was shown that in the absence of CO2, these products are not obtained, thus pointing out to the possibility of formation of fuels from CO2 by utilizing solar light.
Participation in several meetings and workshops related to Carbon Capture, Utilisation and Storage (CCUS) & Alternative Fuels., public perception and business models has been an excellent opportunity to network with industry experts, project representatives, investors and policy makers, facilitating collaboration, knowledge sharing and future partnerships. Participation in events such as conferences and workshops has enabled the development of relations with projects with similar research themes.
To foster the replicability and the transferability of the project’s solutions, two events on the International Industrial Board have been organized during the project, one in June 2023 with a progressed roadmap, and the other meeting at the end of the project in December 2024.
A cradle-to-gate ex-ante life cycle assessment was conducted to assess the environmental feasibility of photocatalytic CO2 reduction using H2O for producing 1 kg of CH3OH. The results revealed that catalyst preparation and electricity consumption for the reduction are the hotspots of the process, exhibiting higher environmental impacts. Lower environmental burdens are obtained upon recycling the catalyst ten times and using a more sustainable method for its synthesis. The public acceptance survey highlights widespread support for the project, with recognition of its environmental benefits and contributions to energy sustainability, though concerns about costs and resource use were noted. The energy security analysis aligns with European and Chinese energy policies aimed at reducing fossil fuel dependency and enhancing renewable energy adoption. METHASOL demonstrates a scalable solution to energy resilience and decarbonization, combining public support with meaningful contributions to global energy security goal.
The primary goals of fostering cross-cultural dialogue and strengthening research collaboration between China and the EU revolve around enhancing scientific exchange, building long-term partnerships, and addressing global challenges through joint innovation in the field of artificial photosynthesis. To achieve these goals, we organized a consortium meeting alongside a summer school in Fuzhou University, creating a platform for partners from both regions to engage in productive discussions, exchange their latest research insights, and explore potential future collaborations beyond the scope of current projects.
Although METHASOL project has a low technology readiness level and is still far from a developed technology, the coordinator has participated in several CINEA meetings to continue looking for future collaborations, knowledge sharing and partnerships.
The primary goals of fostering cross-cultural dialogue and strengthening research collaboration between China and the EU revolve around enhancing scientific exchange, building long-term partnerships, and addressing global challenges through joint innovation in the field of artificial photosynthesis. To achieve these goals, we organized a consortium meeting alongside a summer school in Fuzhou University, creating a platform for partners from both regions to engage in productive discussions, exchange their latest research insights, and explore potential future collaborations beyond the scope of current projects.
Although METHASOL project has a low technology readiness level and is still far from a developed technology, the coordinator has participated in several CINEA meetings to continue looking for future collaborations, knowledge sharing and partnerships.