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Hybrid Materials for Artificial Photosynthesis

Periodic Reporting for period 5 - HyMAP (Hybrid Materials for Artificial Photosynthesis)

Reporting period: 2022-01-01 to 2022-12-31

One of the challenges of this century is the management of the huge CO2 emissions. An alternative to CCS technologies is its transformation into useful products. At present, less than 1% of these emissions are being exploited. So, novels CO2 recycling technologies using sustainable energy sources are needed.
The main goal of HyMAP is the development and integration of a new generation of innovative multifunctional materials and photoreactors that allow exploiting the solar energy to photoreduce the CO2 and converted it into fuels or chemicals.
The implementation of HyMAP project has been carried out in relation of the work packages proposed in the action. The first work package “Design and synthesis of multifunctional hybrid materials”
The synthesis of innovative heterojuntions between inorganic semiconductor oxides and conducting organic polymers was proposed. In this sense, band gap engineering has been exploited to obtain new inorganic semiconductor formulations. Afterwards, metal SPR-NPs have been supported over these modified systems in order to enhance the selectivities towards hydrocarbons (CH4, C2+).
HyMAP team faced the synthesis of new, tailor-made conjugated porous polymers which offered new improved photocatalytic properties not shown on inorganic semiconductors.The preparation of hybrid heterojunctions with Inorganic semiconductors lead to an increase in the solar fuels products and higher selectivities to hydrocarbons. This is due to an increase of the light absorption as well as a better control in the charge dynamos diminish the recombination and leading to a better electron transfer that is translate on higher efficiencies.
In addition, we have developed the rational design and synthesis of new metal organic frameworks (MOFs) with well separated reduction /oxidation active sites as alternative to traditional photocatalysts was explored. At present, the elucidation of the structure of these new MOFs, as well as studies on their implementation as Artificial Photosynthesis catalysts have been described.
As a second strategy, alternative to semiconductor photocatalysts, I proposed the desing and synthesis multi-Functional Metal-Organic Frameworks. These MOFs has been synthetized using selected appropriate functionalized π-conjugated organic molecules (actives under UV and/or visible-light, to increase the light harvest) and two kind of reducible metals that will act as two separate active sites: one for Reduction, and one for oxidation.
A great effort was performed to understand the structural and surface catalytic properties under reaction conditions through the use of innovative In-situ and operando characterization techniques including synchrotron techniques such as HP XPS, XRD… These experiments has been combined with advanced theoretical studies in order to determine the effect of the electronic properties in the mechanism and in reaction activity. This information was help to rationalize the synthesis of improved hybrid catalysts and advance in the CO2 photoreduction process.
In addition, I have design and assembling of a gas phase solar photoreactor that allow good transmission, uniform distribution and maximize the light harvesting in the overall spectra. This photoreactor is constructed using a compound parabolic collector that concentrate direct and diffuses solar radiation increasing the CO2 conversion.
Solar fuels production via artificial photosynthetic processes is a great scientific and engineering challenge due to its complexity. All the approaches described to date open new paths to improve the CO2 photocatalytic reduction, but it is still necessary to develop new catalysts that mimic natural photosynthesis with high enough efficiency so as to consider Artificial Photosynthesis as a viable industrial process. Although there have been considerable advances in the design and synthesis of different multifunctional catalysts based on semiconductors, there are still many fundamental questions to be answered regarding the CO2 valorisation processes. The complexity and lack of knowledge of the role of these new systems in CO2 reduction brings forward the need of performing more theoretical and experimental studies that help to understand the behaviour of the different multifunctional catalysts in the artificial photosynthesis process. In this project, different innovative strategies have been proposed in order to avoid the inherent problems of classical photocatalysts. The results described above represent a step beyond the state of the art in solar fuels production, novel materials synthesis, development of innovative operando characterization tools and the design and built-up of the next generation of solar photoreactors.

This project envisages impacts in different domains, with scientific, environmental, social and economic benefits at a worldwide level.

- Scientific-technological benefits are based in the improvement of the production of solar fuels from CO2 conversion that strongly contribute to the H2020 challenges and those identified by “The Energy Challenge”, related to Low Carbon Technologies with the main objective to develop and bring to market affordable, cost-effective and resource-efficient technology solutions to decarbonize the energy system in a sustainable way, secure energy supply and complete the energy internal market. The most significant advances have been published in international high impact SCI journals. Important efforts will also be devoted to the scientific dissemination of the most appealing results obtained, trying to communicate and interact with the society. In addition, it would be important to remark that patent applications presented when significant advances are achieved with potential industrial scope.

- Environmental and health benefits. HyMAP will have a direct impact on reducing the anthropogenic CO2 in the atmosphere and therefore on the fight against climate change that has a direct impact in the environment and health as is summarized in EU challenges and policies, such as: Climate Action, Environment, Resource Efficiency and Raw Materials challenge and Health 2020.

- Economic and social benefits. The combination of technologies presented in this project may have a huge economic potential. Nowadays, worldwide efforts are being devoted to the development of new materials for emerging applications as proposed here. It would be important to remark that application patents will be presented when significant advances are achieved with potential industrials.

From a social point of view, in addition to the benefits related to environment and health, HyMAP will contribute to the socialization of Science, in general, and of the challenges faced in the project, in particular, through intense outreach and dissemination activities in our web-site or other national or international events such as: European Researcher's Night, ERC week, Week of science…
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