For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of metal active centers. Comparatively, the preparation of single-atom catalysts is much easier with more straightforward and effective accesses for the arrangement and control of metal active centers. The presence of coordination atoms or neighboring functional atoms on the supports' surface ensures the stability of metal single-atoms and their interactions with individual metal atoms substantially regulate the performance of metal active centers. Therefore, the collaborative interaction between metal and the surrounding coordination environment enhances the initiation of reaction substrates and the formation and transformation of crucial intermediate compounds, which imparts single-atom catalysts with significant catalytic efficacy, rendering them a valuable framework for investigating the correlation between structure and activity, as well as the reaction mechanism of catalysts in organic reactions. Herein, comprehensive overviews of the coordination interaction for both homogeneous metal complexes and single-atom catalysts in organic reactions are provided. Additionally, reflective conjectures about the advancement of single-atom catalysts in organic synthesis are also proposed to present as a reference for later development.
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http://dx.doi.org/10.1002/adma.202402747 | DOI Listing |
ACS Catal
January 2025
Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg, 1, 8093 Zurich, Switzerland.
Buchwald-Hartwig (BH) aminations are crucial for synthesizing arylamine motifs in numerous bioactive molecules and fine chemicals. While homogeneous palladium complexes can be effective catalysts, their high costs and environmental impact motivate the search for alternative approaches. Heterogeneous palladium single-atom catalysts (SAC) offer promising recoverable alternatives in C-C cross-couplings.
View Article and Find Full Text PDFSmall
January 2025
Department of Chemistry, Materials and Chemical Engineering "Giulio Natta", Politecnico di Milano, Piazza Leonardo da Vinci 32, Milano, 20133, Italy.
Single-atom catalysts (SACs) are gathering significant attention in chemistry due to their unique properties, offering uniform active site distribution and enhanced selectivity. However, their precise structure often remains unclear, with multiple models proposed in the literature. Understanding the coordination environment of the active site at the atomic level is crucial for explaining catalytic activity.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
Diatomic catalysts featuring a tunable structure and synergetic effects hold great promise for various reactions. However, their precise construction with specific configurations and diverse metal combinations is still challenging. Here, a selective etching and metal ion adsorption strategy is proposed to accurately assign a second metal atom (M) geminal to the single atom site (M-N) for constructing diatomic sites (e.
View Article and Find Full Text PDFACS Nano
January 2025
Key Laboratory of Photoelectronic Conversion and Utilization of Solar Energy, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 260101, China.
Engineering the local coordination environment of single metal atoms is an effective strategy to improve their catalytic activity, selectivity, and stability. In this study, we develop an asymmetric Pd-Ag diatomic site on the surface of g-CN for the selective electrocatalytic semihydrogenation of alkynes. The single Pd atom catalyst, which has a locally symmetric Pd coordination, was inactive for the semihydrogenation of phenylacetylene in a 1 M KOH and 1,4-dioxane solution at an applied potential of -1.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul 08826, Republic of Korea.
Iridium single atom catalysts are promising oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane water electrolysis (PEMWE), as they can reduce the reliance on costly Ir in the OER catalysts. However, their practical application is hindered by their limited stability during PEMWE operation. Herein, we report on the activation of Ir-doped CoMnO in acidic electrolyte that leads to enhanced activity and stability in acidic OER for long-term PEMWE operation.
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