Periodic Reporting for period 1 - METHASOL (International cooperation for selective conversion of CO2 into METHAnol under SOLar light)
Berichtszeitraum: 2021-07-01 bis 2022-12-31
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 that 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 will gather 14 partners from EU/Associated MS, 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. Up to now (M18), we have defined the system specifications (WP1), a first set of materials for OER and CO2RR have been synthesised and their photocatalytic activity and stability have been screened (WP2). The most promising materials have been analysed thanks to experimental characterisation and modelling (WP3), leading to guidelines useful for designing enhanced CO2RR and OER materials (WP4). The best systems will then be 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 will be conducted (WP6) to ensure the clean production of methanol compared to other alternatives. The cooperation between European and Chinese research entities will be 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 will propose a new path for decarbonizing Europe.
During this first period of the project we have prepared the technical developments and seamless component integration in the project to build a tandem CO2RR/OER device. It has been done by completing the following tasks:
• Specification of the heterojunction implementation and overall PC device: We have designed the overall PC device, determining additional KPIs and refining all initial constraints.
• Specifications for CO2RR system: We have (1) refined constraints on MOF/Cu materials, (2) studied the consequences of such constraints on project developments, and (3) defined additional KPIs for the CO2RR system.
• Specifications for OER system. We have (1) refined the list of targeted materials for OER and the equipment list needed to produce graphitic Carbon Nitrides (g-CNs) at the appropriate scale. (2) We will study the impacts of the constraints emerging from T1.1 on OER materials and adjust the list of g-CNs envisioned for the OER subsystem in consequence
• Test protocols and end-user considerations. We have defined the key test parameters for performing the photoreduction of CO2, as well as the parameters of the device, i.e. the size of cell, in line with industry’s expectations. Consequently, different protocols have been established by all partners.
For the development of CO2RR photocatalysts, ILV-CNRS and ENS-IMAP synthesized series of composites combining high valence cations MOFs with different Cu based co-catalysts or carbon quantum dots. UPV has tested these composites as photocatalysts for the CO2 reduction in the presence of sacrificial electron donors, in both liquid and gas phase. Amorphous carbon nitride polymer and metal@poly (heptazine imides) (M-PHI) were developed by FZU and MPIKG and a few candidates from this series presented a very interesting photocatalytic OER performance. In parallel of these experiments, DFT simulations were deployed by CNRS-ICGM to systematically study the photocatalytic properties of MOF/Cu composites as well as assess the OER catalytic performance of M-PHI.
Besides the technical developments, the work carried out has been aimed at ensuring a long-lasting cooperation between EU and China via the creation of research cluster or relation network in the field of artificial photosynthesis. Within Methasol, we want to develop this partnership by scientific cooperation activities and exchanges between teachers and also students, to teach and learn in the two environments. In the first months, interregional barriers were analyzed, and mechanisms were identified for overcoming these barriers, which we started to slowly implement. The pandemic situation at the beginning of the project and the so-called Stoff-Report at M18, have been a problem for the development of the long-term international research cooperation. The strategies for the management of the intellectual property have been properly defined in the related deliverable. The first actions have been carried out to create the IIB, which is the first step to develop the exploitation plan of the project.
• Specification of the heterojunction implementation and overall PC device: We have designed the overall PC device, determining additional KPIs and refining all initial constraints.
• Specifications for CO2RR system: We have (1) refined constraints on MOF/Cu materials, (2) studied the consequences of such constraints on project developments, and (3) defined additional KPIs for the CO2RR system.
• Specifications for OER system. We have (1) refined the list of targeted materials for OER and the equipment list needed to produce graphitic Carbon Nitrides (g-CNs) at the appropriate scale. (2) We will study the impacts of the constraints emerging from T1.1 on OER materials and adjust the list of g-CNs envisioned for the OER subsystem in consequence
• Test protocols and end-user considerations. We have defined the key test parameters for performing the photoreduction of CO2, as well as the parameters of the device, i.e. the size of cell, in line with industry’s expectations. Consequently, different protocols have been established by all partners.
For the development of CO2RR photocatalysts, ILV-CNRS and ENS-IMAP synthesized series of composites combining high valence cations MOFs with different Cu based co-catalysts or carbon quantum dots. UPV has tested these composites as photocatalysts for the CO2 reduction in the presence of sacrificial electron donors, in both liquid and gas phase. Amorphous carbon nitride polymer and metal@poly (heptazine imides) (M-PHI) were developed by FZU and MPIKG and a few candidates from this series presented a very interesting photocatalytic OER performance. In parallel of these experiments, DFT simulations were deployed by CNRS-ICGM to systematically study the photocatalytic properties of MOF/Cu composites as well as assess the OER catalytic performance of M-PHI.
Besides the technical developments, the work carried out has been aimed at ensuring a long-lasting cooperation between EU and China via the creation of research cluster or relation network in the field of artificial photosynthesis. Within Methasol, we want to develop this partnership by scientific cooperation activities and exchanges between teachers and also students, to teach and learn in the two environments. In the first months, interregional barriers were analyzed, and mechanisms were identified for overcoming these barriers, which we started to slowly implement. The pandemic situation at the beginning of the project and the so-called Stoff-Report at M18, have been a problem for the development of the long-term international research cooperation. The strategies for the management of the intellectual property have been properly defined in the related deliverable. The first actions have been carried out to create the IIB, which is the first step to develop the exploitation plan of the project.
The microstructural, (photo)electrochemical and CO2 adsorption properties of MOF@Cu composites will be characterized in collaboration with WP3 partners to fully understand their photocatalytic activity for CO2RR and optimize their performance. Selected MOFs with good chemical stability and interesting photoelectronic properties will be transferred to WP4 and WP5 and will be combined with Cu based co-catalysts and carbon nitrides in view of improving the catalytic activity of CO2RR photocatalysts. The photocatalytic activity of this novel series of composites will be evaluated at UPV for the reduction of CO2. The carbon nitrides and M-PHI with a good OER photocatalytic performance will be fully characterized and their photocatalytic mechanism will be explored by coupling experiments and complementary DFT calculations.
Collaborative researches between NKU and EPFL will be conducted in the next one year. In the second period of METHASOL project, some long-term international exchanges, training programs can be further organised between EU and Chinese partners.
To foster the replicability and the transferability of the project’s solutions, an International Industrial Board (IIB) will be constituted in the next six months with a first workshop planned for May/June 2023. This IIB will specify their operating conditions and the technical and economic constraints they face in order to see what solutions can be brought by the consortium. It will also have access to some result of the tests and demonstrations, and they will be invited to scientific workshops and exploitation meetings organized.
Collaborative researches between NKU and EPFL will be conducted in the next one year. In the second period of METHASOL project, some long-term international exchanges, training programs can be further organised between EU and Chinese partners.
To foster the replicability and the transferability of the project’s solutions, an International Industrial Board (IIB) will be constituted in the next six months with a first workshop planned for May/June 2023. This IIB will specify their operating conditions and the technical and economic constraints they face in order to see what solutions can be brought by the consortium. It will also have access to some result of the tests and demonstrations, and they will be invited to scientific workshops and exploitation meetings organized.