DOE OSTI2024
The capture of CO2 and its simultaneously conversion to useful chemical fuels driven by solar energy represents one of the best solutions to resolve our growing energy and environmental concerns. The most critical challenge to this endeavor is the rational design of a photocatalytic architecture that can effectively couple a given photosensitizer (PS) with an appropriate catalyst, thereby enabling efficient photosensitization of a multi-electron reduction catalysis. This research program aims to address this challenge using an interdisciplinary approach that combines innovative material design and synthesis, fundamental mechanistic studies, and photocatalytic performance evaluation. The strategies include 1) constructing and investigating a novel class of 2D COF hybrid photocatalysts with an effective photoactive organic building block as PS and a precisely incorporated CO2 reduction molecular catalyst (MC); and 2) mechanistic origins of CO2 photoreduction using a set of complementary time-resolved and in situ spectroscopic techniques. The novelty of the proposed hybrid system lies in the unprecedented combination of the unique advantage of porous crystalline COF PS with the precise catalytic function of MC for photocatalytic CO2 reduction. In the periods of the support (09/01/2019-12/31/2022), we have made research progress in four projects: 1) Exploring 2D COFs with incorporated Mn complex for light driven CO2 reduction; 2) The dependence of excited state and charge transfer dynamics on monomer structure of 2D COFs; and 3) Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO2 Photoreduction; and 4) The impact of monomer structure on the photoluminescence properties of COFs. We found that both monomer structure and linker chemistry can effectively impact the excited state dynamics, charge transfer properties, and photoluminescence quantum yields, the important properties that dictate their applications in photocatalysis. In addition, we found that the direction of imine linker determines charge transfer direction and thus controls the types of catalytic reactions (e.g. water oxidation or CO2 reduction reactions). The result from these fundamental studies provides important information for correlating the structure of the COF photocatalysts with their photophysical properties and catalytic functions, paving the way for their novel application in photocatalysis. We expect that our findings will contribute to addressing current shortcomings of semiconductor- and molecular-based photocatalytic systems that suffer from inefficient light harvesting and charge separation and poor adsorption and activation of reactants. In turn, this research will contribute towards the development of novel photocatalytic systems for CO2 reduction to generate renewable chemical fuels and simultaneously address the problem of mitigating climate change due to CO2 accumulation. In addition, the experimental approaches employed in this research can be easily transferred to other energy technologies and are expected to broadly impact fields involving photocatalysis, optoelectronic devices, and solar energy conversion. The proposed research has also been integrated with educational activities and serve as a basis to raise awareness around the critical issues of global energy production and consumption, and to develop the next generation of solar energy scientists.