H2020 HyMAP Project: Hybrid Materials for Artificial Photosynthesis

Type Project
Status Filled
Execution 2015 -2022
Assigned Budget 2.506.738,00 €
Scope Europeo
Autonomous community Madrid, Comunidad de
Main source of financing Horizon 2020
Project website https://www.hymap.eu/

Description

The production of solar fuels through artificial photosynthetic processes is a major scientific and engineering challenge due to its complexity. All the approaches described to date open new avenues for improving photocatalytic CO2 reduction, but new catalysts that mimic natural photosynthesis with sufficient efficiency to consider artificial photosynthesis a viable industrial process are still needed. Although considerable progress has been made in the design and synthesis of various semiconductor-based multifunctional catalysts, many fundamental questions remain regarding CO2 valorization processes. The complexity and lack of understanding of the role of these new systems in CO2 reduction necessitates further theoretical and experimental studies to help understand the behavior of different multifunctional catalysts in the artificial photosynthesis process. This project has proposed several innovative strategies to avoid the problems inherent to conventional photocatalysts.

The results described above represent a step beyond the state of the art in solar fuel production, the synthesis of novel materials, the development of innovative characterization tools, and the design and construction of the next generation of solar photoreactors. This project contemplates impacts in different areas, with global scientific, environmental, social, and economic benefits. The scientific and technological benefits are based on the improvement of solar fuel production from CO2 conversion, which strongly contribute to the H2020 challenges and those identified by "The Energy Challenge," related to Low Carbon Technologies. The main objective is to develop and bring to market affordable, cost-effective, and resource-efficient technological solutions to sustainably decarbonize the energy system, guarantee energy supply, and complete the internal energy market. The most significant advances have been published in high-impact international SCI journals. Significant efforts will also be dedicated to the scientific dissemination of the most attractive results obtained, seeking to communicate and interact with society.

Furthermore, it is important to emphasize that patent applications are filed when significant advances with potential industrial reach are achieved.

Benefits for the environment and health. HyMAP will have a direct impact on reducing anthropogenic CO2 in the atmosphere and, therefore, on combating climate change, which has a direct impact on the environment and health, as summarized in EU challenges and policies such as Climate Action, Environment, Resource and Raw Materials Efficiency, and Health 2020.
Economic and social benefits. The combination of technologies presented in this project could have enormous economic potential. Currently, global efforts are being dedicated to the development of new materials for emerging applications, as proposed here. It is important to emphasize that patent applications will be filed when significant advances with industrial potential are achieved. From a social perspective, in addition to the environmental and health-related benefits, HyMAP will contribute to the dissemination of science in general and the challenges faced by the project in particular, through intensive outreach and promotion activities on our website or other national or international events such as the European Researchers' Night, ERC Week, and Science Week.

Description of activities

The HyMAP project was implemented in conjunction with the work packages proposed in the action. The first work package, "Design and synthesis of multifunctional hybrid materials," proposed the synthesis of innovative heterojunctions between inorganic semiconductor oxides and conducting organic polymers. Bandgap engineering was leveraged to obtain new formulations of inorganic semiconductors. Metallic SPR-NPs were subsequently applied to these modified systems to improve selectivities toward hydrocarbons (CH4, C2+).

The HyMAP team focused on the synthesis of novel, tailor-made conjugated porous polymers that offer novel, enhanced photocatalytic properties not exhibited by inorganic semiconductors. The preparation of hybrid heterojunctions with inorganic semiconductors leads to increased solar fuel products and higher hydrocarbon selectivities. This is due to enhanced light absorption, as well as improved control of charge dynamos, which decrease recombination and lead to improved electron transfer, resulting in higher efficiencies. Furthermore, the rational design and synthesis of novel metal-organic frameworks (MOFs) with well-separated redox active sites have been developed as an alternative to traditional photocatalysts.

Currently, the structure elucidation of these new MOFs has been described, as well as studies on their implementation as catalysts for Artificial Photosynthesis. As a second strategy, alternative to semiconductor photocatalysts, I proposed the design and synthesis of multifunctional metal-organic frameworks. These MOFs have been synthesized using appropriate selected conjugated functionalized organic molecules (active under UV and/or visible light, to enhance light harvesting) and two types of reducible metals that will act as two separate active sites: one for reduction and one for oxidation. A great effort was made to understand the structural and surface catalytic properties under reaction conditions by using innovative in-situ and operational characterization techniques, including synchrotron techniques such as HP XPS, XRD...

These experiments have been combined with advanced theoretical studies to determine the effect of electronic properties on the reaction mechanism and activity. This information has helped streamline the synthesis of improved hybrid catalysts and advance the CO2 photoreduction process. In addition, I have designed and assembled a gas-phase solar photoreactor that allows for good transmission, uniform distribution, and maximizes light collection across the overall spectra. This photoreactor is constructed using a compound parabolic collector that concentrates direct solar radiation and diffuses it, increasing CO2 conversion.

Contextual description

One of the challenges of this century is managing the enormous CO2 emissions. An alternative to CCS technologies is their transformation into useful products. Currently, less than 1% of these emissions are exploited. Therefore, new CO2 recycling technologies that utilize sustainable energy sources are needed. The main objective of HyMAP is the development and integration of a new generation of innovative multifunctional materials and photoreactors that can harness solar energy to photoreduce CO2 and convert it into fuels or chemicals.

Objectives

HyMAP aims to develop a new generation of multifunctional hybrid photocatalysts and solar photoreactors that can harness at least 1% of solar energy for CO2 photoreduction using water as the electron donor. This will entail a CO2 conversion of between 12 and 35 tonnes/year ha-1, depending on the product distribution, representing at least a 20-fold improvement over the state of the art. To achieve this goal, I propose an interdisciplinary research program through which several breakthroughs will be achieved at different scales: development of efficient multifunctional organic/inorganic semiconductors and metal-organic framework photocatalysts with separate redox active sites.

The combination of multiple independent redox sites in a single material would maximize charge separation and transport processes, as well as sunlight harvesting; characterization and modeling of the structural and optoelectronic properties of the proposed materials; and evaluation of the materials in artificial photosynthesis devices. At this stage, a solar photoreactor will be developed that allows for good transmission, uniform light distribution, and maximizes energy harvesting across the overall spectrum. HYMAP will provide me with an excellent opportunity to lead a well-established research group.

Throughout my scientific career, I have demonstrated creative thinking, autonomy, and an excellent capacity to conduct cutting-edge research in heterogeneous catalysis, reactor characterization, modeling, and engineering. I have an outstanding research track record, reflected in a good number of scientific publications, extensive professional experience, innovative project design, and a strong international collaboration network. This, together with my leadership and management skills, will ensure the success of the objectives mentioned in this project. HYMAP is a revised version of a proposal that received an A rating (2nd phase) in the last ERC-CoG call.

Results

Mimicking nature, artificial photosynthesis uses sunlight to convert CO2 and water into compounds that produce and release energy. But instead of producing sugars, as occurs with green plants, artificial photosynthesis can produce carbon monoxide (CO), methane (CH4), methanol (CH3OH), and hydrogen (H2), all of which are valuable green fuels.

The European Research Council (ERC)-funded HyMAP (Hybrid Materials for Artificial Photosynthesis) project was established to develop a new generation of hybrid organic-inorganic materials and devices to perform the chemical transformations required for artificial photosynthesis. This would pave the way for developing green alternatives to electrochemical storage electrodes for batteries. The team investigated photo(electro)catalysis at different scales, from nanoscale catalysts to pilot plant reactors, creating new photoactive hybrid materials. "Our results, especially those that increase yield, are at the forefront of knowledge in the field of CO2 conversion, marking a milestone for this research area," says principal investigator Víctor A. de la Peña O'Shea of the New York University IMDEA Energy Institute (opens in a new window). Consequently, the scientific findings are being widely disseminated in high-profile journals. The project's new family of organic semiconductors, Conjugated Porous Polymers (Opens in a new window), has already been patented for solar fuel production. Hybrid materials

The primary goal of HyMAP was to develop multifunctional systems with enhanced capabilities to collect light from the entire solar spectrum.

To achieve this, the team explored hybrid photocatalysts, investigating various materials and approaches. The different strategies adopted were: (i) bandgap engineering of inorganic and (ii) organic semiconductors; (iii) as well as their related heterojunctions; (iv) metal-organic frameworks (MOFs); and (v) upconversion (UC). The first four options can collect ultraviolet along with the visible regions of the light spectrum, while UCs enhance the collection of infrared wavelengths. Critically, inorganic and organic semiconductors enhance charge generation and transfer, increasing photocatalytic performance. "The combination of different materials, each specialized in the separate functions of the photocatalytic reactions—primarily light absorption, charge separation, and catalysis—improved the overall efficiency," explains de la Peña O'Shea.

The reaction mechanisms of these materials were characterized in the laboratory using a variety of advanced in situ techniques, including near ambient pressure, X-ray photoelectron spectroscopy, X-ray diffraction, and synchrotron radiation. Solar reactor As the team’s studies revealed that hybrid organic/inorganic semiconductor heterojunctions made of a conjugated porous polymer had particularly high performance, they designed a gas-phase solar reactor. It consisted of a solar reflector, a compound parabolic collector that redirects all incoming solar radiation back into the reactor, and a tubular annular reactor made of borosilicate glass, which is more resistant to high temperatures.

This prototype reactor was shown to successfully produce solar hydrogen from both water and biomass, as well as other fuels or chemicals, such as CO, CH4, and CH3OH, using CO2 as the reactant. "These excellent results for solar fuel production have already led to a pilot plant, increasing our knowledge and allowing us to fine-tune processes before considering market opportunities," says de la Peña O'Shea. "We need to expand the use of these hybrid materials for other reactions, beyond photo-, to include photo(electro)catalysis, for more sophisticated fuels and chemicals, such as ammonia, ethylene, and dimethyl ether." Scaling up to meet new challenges The HyMAP team has already launched an ERC-funded NanoCPPs proof-of-concept project to develop a proof-of-concept that scales up their nanostructured conjugated porous polymers. "The nanostructure of this polymer offers improved properties, opening the door to better performance," he adds.

A remaining challenge is to truly maximize the electronic properties of these systems so that the proposed environmentally friendly alternatives to current electrochemical storage electrodes for batteries can truly advance and become a reality.

Coordinators

Fundacion IMDEA Energia

Other links

H2020 HyMAP Project: Hybrid Materials for Artificial Photosynthesis

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