We report the first single-atom catalyst for C─S cross-coupling, featuring atomically dispersed Cu sites on mesoporous carbon nitride. The catalyst enables efficient, selective, and recyclable thioet...

This paper reviews the design and use of structured single-atom catalysts, which integrate porous architectures with the exceptional reactivity of isolated catalytic sites. It explores fabrication st...

The development of single-atom catalysts (SACs) with site-specific and tunable catalytic functionalities remains a highly desirable yet challenging goal in catalysis. In this study, we report a SAC featuring anisotropic coordination cavities synthesized via a one-step polymerization of 2,6-diaminopyridine and cyanuric chloride. These cavities provide a robust framework for anchoring isolated Pd single atoms with exceptional stability. The unique broken symmetry of the catalyst’s local structure enables precise control over reaction pathways, allowing reactivity to be switched between distinct catalytic outcomes. Specifically, under tailored reaction conditions, the catalyst can either halt at the borylation step or proceed seamlessly to Suzuki coupling in a self-cascade process. Mechanistic studies unveil the pivotal role of Pd single atoms in driving key steps, including oxidative addition, base exchange, and reductive elimination. Furthermore, green metrics demonstrate the process’s sustainability, with minimized waste generation and reduced reliance on hazardous reagents in the self-cascade transformation. This work establishes an innovative benchmark in the field of single-atom catalysis: by enabling complex, multistep transformations via strategic activation of multiple functional groups, this catalyst exemplifies the potential of self-cascade processes to revolutionize synthetic chemistry via catalysis engineering.

Enantioselective transformations are crucial in various fields, including chemistry, biology, and materials science. Today, the selective production of enantiopure compounds is achieved through asymme...

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Understanding charge transfer in light-driven processes is crucial for optimizing the efficiency and performance of a photocatalyst, as charge transfer directly influences the separation and migration of photogenerated charge carriers and determines the overall reaction rate and product formation. However, achieving this understanding remains challenging in the context of single-atom photocatalysis. This study addresses this gap and investigates an Ag-based single-atom catalyst (Ag1@CNx) in the photocatalytic oxidation of benzyl alcohol to benzaldehyde. Comprehensive characterization was conducted using a battery of diffractive, textural, spectroscopic, and microscopic methods, confirming the catalyst crystallinity, porosity, elemental composition, and atomic dispersion of silver atoms. This material displayed efficient performance in the selective oxidation of benzyl alcohol to benzaldehyde. Density functional theory calculations were used to rationalize the catalyst structure and elucidate the reaction mechanism, unveiling the role of the photogenerated holes in lowering the reaction energy barriers. Time-resolved transient spectroscopic studies were used to monitor the dynamics of photogenerated charges in the reaction, revealing the lifetimes and behaviors of excited states within the catalyst. Specifically, the introduction of silver atoms led to a significant enhancement in the excited state lifetime, which favors the hole-transfer in the presence of the benzyl alcohol. This indicated that the photoexcited carriers were effectively transferred to the reactant, thereby driving the oxidation process in the presence of oxygen. These mechanistic insights are pivotal in spectroscopically elucidating the reaction mechanism and can be practically applied to design single-atom photocatalysts more rationally, targeting materials that combine both rapid reductive quenching and efficient charge transfer to the metal.

This study compares the environmental and economic impacts of homogeneous, heterogeneous, and single-atom catalysts for ester synthesis, under thermal, photocatalytic, and electrocatalytic conditions, highlighting that heterogeneous, Ni-based single-atom catalysts provide a more sustainable alternative to traditional catalysts. The findings contribute to advancing sustainable manufacturing in fine chemical production.