Sensors, the underlying technology that supports the Internet of Things, are undergoing multi-disciplinary integration development to constantly improve the efficiency of human production and life. Simultaneously, the application scenarios in emerging fields such as medical diagnosis, environmental monitoring and industrial safety put forward higher requirements for sensing capabilities. Over the last decade, single-atom catalysts (SACs) have attracted tremendous attention in fields such as environment and energy due to their high atom utilization efficiencies, controllable active sites, tailorable coordination environments and structural/chemical stability. These extraordinary characteristics extend the sensitivity and selectivity of sensors beyond their current limitations. Here, we start with the working principles of SAC-based sensors, and summarize the relationship between sensor performance and intrinsic properties of SACs, followed by an overview of the design strategy development. We then review the recent advances in SAC-based sensors in different fields and highlight the future opportunities and challenges in their exciting applications.
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http://dx.doi.org/10.1039/d2cs00191h | DOI Listing |
J Am Chem Soc
January 2025
CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Well-defined single-atom catalysts (SACs) serve as ideal model systems for directly comparing experimental results with theoretical calculations, offering profound insights into heterogeneous catalytic processes. However, precisely designing and controllably synthesizing SACs remain challenging due to the unpredictable structure evolution of active sites and generation of embedded active sites, which may bring about steric hindrance during chemical reactions. Herein, we present the precious nonpyrolysis synthesis of Re SACs with a well-defined phenanthroline coordination supported by NiO (Re-phen/NiO).
View Article and Find Full Text PDFLangmuir
January 2025
Centre for Energy (M473), The University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia.
The mechanisms of NO reduction by CO over nitrogen-doped graphene (N-graphene)-supported single-atom Ni catalysts in the presence of O, HO, CO, and SO have been studied via density functional theory (DFT) modeling. The catalyst is represented by a single Ni atom bonded to four N atoms on N-graphene. Several alternative reaction pathways, including adsorption of NO on the Ni site, direct reduction of NO by CO, decomposition of NO to NO followed by reduction of NO to N, formation of active oxygen radical O*, and reduction of O* by CO, were hypothesized and the energy barrier corresponding to each of the reaction steps was calculated using DFT.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China.
Single-atom catalysts (SACs) have attracted widespread attention due to their potential to replace platinum-based catalysts in achieving efficient oxygen reduction reaction (ORR), yet the rational optimization of SACs remains challenging due to their elusive reaction mechanisms. Herein, by employing ab initio molecular dynamics simulations and a thermodynamic integration method, we have constructed the potential-dependent free energetics of ORR on a single iron atom catalyst dispersed on nitrogen-doped graphene (Fe-N/C) and further integrated these parameters into a microkinetic model. We demonstrate that the rate-determining step (RDS) of the ORR on SACs is potential-dependent rather than invariant within the operative potential range.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Department of Chemical Engineering, Northeastern University, Boston, Massachusetts, 02115, USA.
Discovering electrocatalysts that can efficiently convert carbon dioxide (CO) to valuable fuels and feedstocks using excess renewable electricity is an emergent carbon-neutral technology. A single metal atom embedded in doped graphene, , single-atom catalyst (SAC), possesses high activity and selectivity for electrochemical CO reduction (COR) to CO, yet further reduction to hydrocarbons is challenging. Here, using density functional theory calculations, we investigate stability and reactivity of a broad SAC chemical space with various metal centers (3d transition metals) and dopants (2p dopants of B, N, O; 3p dopants of P, S) as electrocatalysts for COR to methane and methanol.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Hunan University, Chemistry and Chemical Engineering, Lushan South Road, Yuelu District, 410082, Changsha, CHINA.
Site density and turnover frequency are the two fundamental kinetic descriptors that determine the oxygen reduction activity of iron-nitrogen-carbon (Fe-N-C) catalysts. However, it remains a grand challenge to simultaneously optimize these two parameters in a single Fe-N-C catalyst. Here we show that treating a typical Fe-N-C catalyst with ammonium iodine (NH4I) vapor via a one-step chemical vapor deposition process not only increases the surface area and porosity of the catalyst (and thus enhanced exposure of active sites) via the etching effect of the in-situ released NH3, but also regulates the electronic structure of the Fe-N4 moieties by the iodine dopants incorporated into the carbon matrix.
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