Periodic Reporting for period 1 - SACforCO2 (Heterogeneous Single-Atom Catalysts for Carbon Dioxide Reduction to Chemicals)
Reporting period: 2022-12-01 to 2025-01-31
The SACforCO2 project has been dedicated to developing innovative single-atom catalysts (SACs) for synthetic chemistry. This research has addressed a fundamental challenge in catalysis: designing stable and efficient active sites at the atomic scale to maximize performance while minimizing precious metal usage. By integrating advanced molecular design, in-depth spectroscopic characterization, and computational modeling, the project has explored the interplay between catalyst structure and reactivity, aiming to establish a new paradigm for sustainable chemical transformations. The focal point has been the synthesis of Pd1@TRIDAP, a new palladium-based SAC supported on a pyridine-triazine framework, which offers a unique platform for tuning catalytic properties through ligand engineering and electronic control. This work aligns with the broader vision of developing catalysts that not only enhance efficiency but also enable a shift toward electrification and modular chemical production, supporting the EU Green Deal's goal of decarbonizing industrial processes.
A key achievement of the project has been the synthesis of Pd1@TRIDAP, which combines precision catalyst design with scalable synthetic strategies. The catalyst was successfully prepared via an organoligand-based polymerization process, ensuring atomic dispersion and site isolation of palladium centers within a well-defined organic matrix. Advanced spectroscopic techniques, including XPS, XAS, and TEM, confirmed the structural integrity and electronic environment of the active sites, while DFT calculations provided insight into their stability and mechanistic role in catalytic processes. The application of Pd1@TRIDAP in C–C coupling and CO2 valorization has demonstrated unprecedented selectivity and recyclability, with experimental findings corroborated by first-principles modeling. In particular, the catalyst has enabled the self-cascade Suzuki coupling reaction, eliminating the need for intermediate purification and setting the stage for more complex tandem catalytic transformations. Furthermore, its implementation in one-pot pharmaceutical synthesis highlights its versatility in constructing bioactive molecules under streamlined reaction conditions. These results have suggested a broader potential for SACs in fine chemical and pharmaceutical manufacturing, in order to bridge the gap between fundamental research and industrial application.
The project's impact extends beyond catalyst design, contributing to the development of integrated catalytic systems that could reshape the landscape of synthetic chemistry. By demonstrating a modular and highly tunable platform, SACforCO2 lays the foundation for future research into adaptive and multifunctional catalysts capable of operating under tunable chemical conditions. The ability to rationally control reaction pathways at the atomic level opens opportunities for expanding the concept of SACs to new classes of reactions, such as asymmetric transformations and selective C–H activation, thereby broadening the scope of green synthetic methodologies. The economic implications of this work are significant, as the technology offers a pathway to reducing the dependence on bulk precious metals while enhancing catalytic efficiency. Discussions with industrial partners indicate strong interest in the potential scale-up and commercialization of these systems, provided that further optimizations and long-term stability assessments are conducted. To accelerate the transition from laboratory-scale discoveries to industrial implementation, efforts are now focused on integrating SACs into continuous-flow reactors, optimizing their performance in real-world operating environments, and refining synthetic protocols to enhance cost-effectiveness.