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Supported single-metal atom catalysts (SACs) are constituted of isolated active metal centers, which are heterogenized on inert supports such as graphene, porous carbon, and metal oxides. Their thermal stability, electronic properties, and catalytic activities can be controlled via interactions between the single-metal atom center and neighboring heteroatoms such as nitrogen, oxygen, and sulfur. Due to the atomic dispersion of the active catalytic centers, the amount of metal required for catalysis can be decreased, thus offering new possibilities to control the selectivity of a given transformation as well as to improve catalyst turnover frequencies and turnover numbers. This review aims to comprehensively summarize the synthesis of Fe-SACs with a focus on anchoring single atoms (SA) on carbon/graphene supports. The characterization of these advanced materials using various spectroscopic techniques and their applications in diverse research areas are described. When applicable, mechanistic investigations conducted to understand the specific behavior of Fe-SACs-based catalysts are highlighted, including the use of theoretical models.
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http://dx.doi.org/10.1021/acs.chemrev.1c00158 | DOI Listing |
ACS Nano
September 2025
Hefei National Research Center for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, China.
Electrocatalytic nitrogen reduction reaction (NRR) to ammonia holds great potential for sustainable ammonia synthesis at ambient conditions, where a single-atom catalyst has recently emerged as a prospective NRR catalyst candidate owing to its advantageous features such as maximal metal-utilization efficiency and low-coordinated single-atom metal sites. Nevertheless, owing to the uncontrolled coordination structures of the single-metal-atom sites in single-atom catalysts and the unregulated gas/ion migration in their surface reaction microenvironments, it still remains a formidable challenge to simultaneously improve the NRR selectivity and activity. In this work, we report a facile and general strategy to prepare a composite catalyst with protic ionic liquids (PIL) modified on conjugated coordination polymers that feature abundant single-atom metal sites with well-defined coordination structures, significantly outperforming its counterpart catalyst without PIL.
View Article and Find Full Text PDFAdv Mater
August 2025
Department of Chemistry, National University of Singapore, Singapore, 117543, Singapore.
Rational design of proximal coordination microenvironments surrounding catalytic sites to achieve optimal reaction kinetics represents a paramount pursuit in single-atom catalysts (SACs), yet continues to pose substantial synthetic challenges. Developing innovative strategies that simultaneously stabilize low-coordinated single-metal species on solid supports, while ensuring atomic precision and high activity, remains imperative. Herein, a de-saturation strategy for SACs is demonstrated (denoted as De-sat SACs) using a top-down approach based on a KOH-mediated Joule thermal shock to obtain under-coordinated and asymmetric SACs for efficient organic synthesis.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2025
State Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, China.
The electrochemical conversion of carbon dioxide (CO) into high-value-added products under mild conditions is crucial for achieving carbon neutrality. Oxalate (CO) is one of the most important industrial raw materials and is widely used as a reducing agent in the fields of medicine, dyeing, and plastics yet faces challenges in efficient C-C bond formation under mild conditions. In this study, we investigate the reduction of CO to CO using single-atom catalysts (SACs) with M-N-C configurations, employing density functional theory (DFT) to assess their catalytic performance under varying reaction conditions.
View Article and Find Full Text PDFNat Commun
August 2025
School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai, China.
In the field of wastewater treatment, the regulation of free radical and non-radical routes has been one of the major challenges. This study investigates the regulation of radical and non-radical oxidation pathways in the peroxymonosulfate (PMS) oxidation system by controlling the calcination temperature of carbon materials and constructing bimetallic single-atom catalysts (NC-FeMn(TA)). Density functional theory calculations and experimental tests indicate that increasing the pyridinic nitrogen content and incorporating single metal atoms in nitrogen-doped carbon materials result in a predominantly non-radical oxidation process.
View Article and Find Full Text PDFACS Appl Mater Interfaces
August 2025
Department of Chemical and Biomolecular Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
The scalable and facile preparation of single-atom catalysts remains a critical challenge. Here, we introduce diluted atomic layer deposition (DALD), a unique approach for synthesizing supported metal catalysts with precisely tunable loadings. Unlike conventional metal deposition by ALD which uses pure metal precursors, DALD employs a diluted precursor mixture, combining organometallic precursors with the corresponding free ligand in controlled ratios.
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