THE METHASOL PROJECT

 

METHASOL is a European project with 14 partners that received 4.0 M€ from the EU’s Horizon 2020 research and innovation programme out of a total budget of 5.2 M€.

OBJECTIVES

The main objective of the METHASOL project is to produce methanol through a sustainable and cost-effective process based on the selective visible light driven gas phase CO2 reduction

Create a long-lasting cooperation framework between EU and China

As China and Europe gather key expertise to make solar fuels a reality, the METHASOL project is based on five existing strong EU-China cooperation: ICL and DICP (e.g. on transient optical spectroscopies to measure charge carrier kinetics), MPIKG and FZU (e.g. Joint International Laboratory which was followed by a DFG- NSC Program for four years), MPIKG and WHUT, UPV and FZU (incl. five joint papers and exchange of materials), EPFL and NKU. Together, all partners will strengthen inter-continent collaboration during the project and ensure the durability of the collaboration between EU and China on the topic of photocatalytic production of renewable fuels.

Validate the durable operation in gas phase of a photocatalytic device for methanol and oxygen production

METHASOL partners will design photocatalytic reactors that enable the optimal photocatalytic CO2 reduction reaction (CO2RR) to methanol at standard conditions of pressure and temperature. Two designs will be investigated: a single chamber reactor in gas phase, and a two-compartment reactor with gas phase for CO2RR to methanol and liquid phase for the Oxygen Evolution Reaction (OER).

Synthetise materials for light harvesting, charge separation and catalytic reduction of CO2 to methanol in gase phase

METHASOL partners will exploit Metal Organic Frameworks (MOFs) as photocatalysts, together with an appropriate Cu-based co-catalysts for tuning the selectivity of the CO2RR reaction towards methanol (one of the main challenges of METHASOL). For optimal charge separation, the structure of MOFs will be optimised using inter alia computational predictions. To enhance CO2RR light harvesting, partners will use carbon quantum dots (CQDs) that have shown their durable performances (creation of CQDs-MOFs@Cu complexes). For greater performance, the band gap will be tuned to the adequate values.

Enhance water oxidation thanks to high performance light-harvesting, charge separation and catalytic materials

METHASOL partners will develop an optimised gas phase OER system built out of the carbon nitride family (CN), playing the role of both light harvester and photocatalyst with a tunable band gap. Its optimisation will be realised thanks to advanced quantum calculations, operando transient optical analyses of charge transfer, charge carrier lifetimes and catalysis kinetics that will allow to build reliable structure-activity relationships. The optimal catalysts will be selected considering properties such as water binding and surface area. Finally, partners will consider addition of an OER co-catalyst for optimising further OER evolution rates.

Combine in a Z-scheme heterojunction the photocatalytic reduction of CO2 and oxidation of H2O

The METHASOL project will develop a complete photocatalytic system with optimised Z-scheme heterojunction by assembling CO2RR and OER photocatalysts, optimised thanks to a unique computational tool developed during the project, combining advanced quantum and force-field based simulations. To mitigate risks and achieve the best performance possible, two strategies will be used (in line with the two designs mentioned above), 1/ an heterojunction without mediator and 2/ an heterojunction with mediator, a thin metal layer that will foster electron conductivity while avoiding degradation of yield due to poisonous reactions.

Ensure the sustainability of the system developed

METHASOL partners will ensure the sustainability of their system by 1/ taking into account environmental aspects through life cycle assessment (LCA), 2/ assessing the social and societal impacts, in particular the European and Chinese independence gains in fuel production, jobs creation, social acceptance of the CO2 streams coming from urban systems and of the new technology, and 3/ analysing the economic relevance of the solution compared to current production processes in both European and Chinese contexts.

Ensure exploitation of project results

The pathway for the project to reach industrialisation will be paved by an exploitation and a business plan. To foster the progress of the technology to higher TRLs, MI will support partners in the creation of an International Industrial Board (IIB) with global actors of the chemical and fuel industry with interests in solar methanol production. A common roadmap will be created to take the technologies to TRL9 less than 7 years after the end of the project.

Concepts

The general concept of the project is to combine through a Z-scheme photocatalytic cell a MOF-based CO2RR system and a g-CN OER system. This concept is supported by three problematics, leading to an operational photocatalytic cell:
• Why gas phase photocatalysis?
• What systems for CO2RR and OER systems?
• How can we do their assembly?
The following scheme gathers the main concepts investigated in the METHASOL activities. METHASOL investigates two main families of novel materials, with different purposes:
• Materials for CO2 reduction reaction (CO2RR), allowing to transform CO2 into methanol (CH3OH). These new materials will associate in a complex:
• Carbon Quantum Dots (CQDs), a family of materials enhancing the light harvesting on this side of the reaction for a better efficiency
• Metal-Organic Frameworks (MOFs), a family of materials which properties when associated with Cupper (Cu) will allow to selectively convert CO2 into methanol
• Materials for Oxygen Evolution Reaction to convert water (H2O) into oxygen (O2). This step allows in the end to obtain the H+ ions necessary to transform CO2 in methanol, it will be carried out by a family of materials called graphitic Carbon Nitrides (g-CN), recently highlighted for such properties
The core activities of the project will be to find the best non-toxic non-critical raw materials in each category that would allow the optimal operation of CO2 reduction reaction and Oxygen Evolution Reaction on each side and the good combination of both into a single photocatalyst, which would strongly increase the efficiency of the overall reaction. Finding the right green chemistry processes for all the steps of materials synthesis and combinations is also at the heart of the research done in METHASOL.

ACTIVITIES

WORK PACKAGES

WP1: Specification, led by UPV

Duration: July 2021 – November 2021

The aim of this WP is to prepare the technical developments and seamless component integration in the project. This will include the study of the required constraints to build a tandem CO2RR/OER device, the realisation of a more advanced sketch of overall system, an update on the state of the art, and the description of technical specifications (operating conditions and test protocols).

 

WP2: Synthesis and performances screening of first set of materials for CO2RR and OER, led by CNRS

Duration: October 2021 – February 2022

This WP aims to design, synthetise and characterise robust photoactive MOFs based composites and g-CN materials, evaluate separately their catalytic properties for CO2RR and OER respectively, and finally assess their chemical and thermal stability under operating conditions. The outcome of this WP is the down-selection the best performing CO2RR and OER photocatalysts to be further analysed in WP3 prior to their optimisation in WP4.

WP3: In-depth mechanistic studies towards materials with improved performances, led by ICL

Duration: March 2022 – June 2024

The aim of this WP is to analyse the physico-chemical characteristics (electronic, optical, spectroscopic) of the best performing WP2 materials, revealing the key catalyst descriptors which are the origin of their OER and CO2RR performances, and optimising this level of performances by formulating concrete design guidelines towards advanced materials for WP4 (establishment of reliable structure-activity relationships). The advanced materials delivered by WP4 will be equally characterised in order to deepen the understanding, train and further refine the computational predictions.

WP4: Preparation of an advanced set of materials for CO2RR and OER and performances screening, led by ENS

Duration: December 2022 – March 2024

This WP aims to synthetise a second set of advanced materials based on the findings and trends of WP2 and as supported and guided by WP3. Their photo-electronic and catalytic activities and stability under operation for CO2RR and OER (primary characterisation) will be investigated in order to select candidates with the best performances. The best materials will be transferred to WP5 for integration in Z-scheme reactors and reviewed in WP3.

WP5: Study of the integration in a Z-scheme heterojunction and tests, led by WHUT

Duration: February 2022 – November 2024

The aim of this WP is to integrate in a small-scale prototype all components for CO2RR and OER through a Z-scheme heterojunction, and then assess its performances through stress tests. Two cycles of advanced characterisation and tests are expected: one for materials transferred from WP2 and another with refined materials from WP4. Two types of heterostructured photocatalysts (with/without mediator) will be considered.

WP6: International societal, market and environmental analysis, led by UM

Duration: December 2022 – December 2024

This WP aims to develop and implement a common framework for international societal, market and environmental analysis. The societal, environmental and economic impacts of the solution on the total carbon cycle will be determined, and its relevance in the context of global warming will be assessed, as well as its market horizons on mid-long term.

WP7: Long-term international research cooperation and implementation, led by MPIKG

Duration: All along the project

The aim of this WP is to ensure the long-lasting collaboration between EU and China/USA on the topic of solar renewable fuels produced by photocatalytic way. To that purpose, partners will create and implement a research and industrial cluster on photocatalysis between EU and China in order to determine the roadmap to TRL9 for the solution.

WP8: Communication, dissemination and networking activities, led by EQY

Duration: All along the project

This WP aims at ensuring that the project results have the highest impact by highlighting its advances and structure.

WP9: Project management, led by UPV

Duration: All along the project

The aims of this WP are to ensure the seamless coordination and management of the project making optimal use of the project resources, to provide the best chance to the partners to jointly achieve the project’s objectives.

EXPECTED IMPACTS

From its early stages, the METHASOL project is expecting to positively impact the capactiy of our societies to produce renewable (solar) fuels in a cost-effective and rely on all vectors of renewable energy beyond the sole electricity

Progress the scientific understanding and the technology state-of-the-art through the exchange of knowledge with China and/or USA

Strengthen the European and Chinese partners’ technology base

Accelerate the outperforming development of renewable fuels compared to the
best fossil fuel alterna

Contribute towards building a sustainable renewable energy system

Foster the decarbonisation of the European economy

Entail economic activity and create job opportunities

Increase the European energy security by enabling fuel production from solar resource