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Description
Overcoming of barriers in the CO2 photoconversion into valuable chemicals requires formation of a new family of materials, possessing high stability, visible light response, long lifetime of photogenerated carriers, good charge mobility, high CO2 adsorption capacity, selectivity and low toxicity, however, none of individual known materials has at the same time all mentioned above features.
To meet all these requirements laid out about, the main objective of the HotHybrids project is to develop a thoroughly groundbreaking class of hybrid materials composed of new double perovskite nanocrystals (DPNs), encapsulated by MOFs. This hybrid system combines unique properties of: (i) DPNs (composition, size and morphology dependent band structure) and (ii) MOFs (high stability in aqueous environment, tremendous surface area and porosity, high capacity of CO2 adsorption, catalytic activity and structure enabling charge mobility). This challenge of the HotHybrids project will be achieved by efficient coupling (chemical or physicochemical linking) of these components into cutting-edge hybrid system allowing for effective charge carriers transport and not blocking activity of any hybrid’s unit.
Summary of project results
The scope of the project was to synthesize new materials able to overcome commonly encountered characteristics in the investigation of the CO2 capture and photoconversion such as a low efficiency under visible light, fast recombination of generated e-/h+, instability and/or toxicity. Based on this state of the art the project focused/investigated the synthesis of new single perovskite NCs materials and their further use in the CO2 capture and its photoconversion into valuable hydrocarbons. Overcoming of barriers of clean energy generation requires developing of new materials, which could be used in eco-friendly processes such as photocatalysis. Photocatalysis could support energy transformation process via utilization of solar energy for carbon dioxide (CO2) phototransformation into valuable hydrocarbons or hydrogen (H2) generation (clean energy carrier and step in CO2 photoconversion).
During HotHybrids realization a set of novel materials have been developed, including CsPbBr3@UiO-66, CsPbBr3@UiO-66-NH2, CsPbI3@ZIF-67, CsPbI3@UiO-66; Cs2AgBiBr6@ZIF-68. During project realization more than 40 types of novel hybrid materials have been synthesized and checked in hydrogen production and CO2 photoconversion. It was found that materials obtained by combining of CsPbX3 with (Ce)-UiO-66, CuGaS2 with NH2-MIL-125(Ti), SrTiO3 with MIL-125-NH2 and TiO2-X with CsBi2X9 (where X = Cl, Br or I) are active in photocatalytic hydrogen generation, while MIL-125-NH2 modified by copper shows activity in carbon dioxide photoconversion into formic acid. Obtained materials have been characterized to correlate their surface properties with photocatalytic activity.
The project delivered 14 protocols describing the synthesis of the perovskites with all the necessary details. Moreover, ction spectra analysis and photoconversion of isotope-labeled 13CO2 allowed to understand the excitation mechanism of the most active obtained hybrid materials. These discoveries constitute the next step in the development of technologies enabling the development of clean technologies for generating chemical fuels or raw materials for chemical syntheses (hydrogen and hydrocarbons).