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On-surface chemistry holds the potential for ultimate miniaturization of functional devices. Porphyrins are promising building-blocks in exploring advanced nanoarchitecture concepts. More stable molecular materials of practical interest with improved charge transfer properties can be achieved by covalently interconnecting molecular units. On-surface synthesis allows to construct extended covalent nanostructures at interfaces not conventionally available. Here, we address the synthesis and properties of covalent molecular network composed of interconnected constituents derived from halogenated nickel tetraphenylporphyrin on Au(111). We report that the π-extended two-dimensional material exhibits dispersive electronic features. Concomitantly, the functional Ni cores retain the same single-active site character of their single-molecule counterparts. This opens new pathways when exploiting the high robustness of transition metal cores provided by bottom-up constructed covalent nanomeshes.
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http://dx.doi.org/10.1002/anie.202210326 | DOI Listing |
Angew Chem Int Ed Engl
September 2025
International Joint Research Center for Photoresponsive Molecules and Materials, School of Chemical and Material Engineering, Jiangnan University, Lihu Street 1800, Wuxi, 214122, P.R. China.
Electrocatalytic coupling of nitrate reduction (NORR) to ammonia with 5-hydroxymethylfurfural (HMF) oxidation to 2,5-furandicarboxylic acid (FDCA) enables simultaneous wastewater remediation and biomass valorization. However, developing efficient bifunctional electrocatalysts for these multiproton-coupled electron transfer reactions remains challenging as conventional single-active-site catalysts inherently suffer from linear scaling relationships between intermediates and adsorption energies, particularly sluggish proton transfer. To address this, we engineered a triphasic N-doped CuO@CoO@Ni(OH) heterostructure with a gradient built-in electric field (BIEF), which synergistically enhances interfacial charge polarization and accelerates proton transport through dynamic coupling effects in both reactions: sufficient *H supply for NORR and fast Ni(OH)/NiOOH redox cycling during HMF oxidation (HMFOR), thus achieving unprecedented bifunctional performance: at - 0.
View Article and Find Full Text PDFBiochem Biophys Res Commun
August 2025
Department of Biochemistry, School of Chemical and Life Sciences, Jamia Hamdard, New Delhi, 110062, India. Electronic address:
Pyruvate kinase catalyzes the conversion of phosphoenolpyruvate and ADP to pyruvate and ATP in glycolysis and plays a role in regulating cell metabolism. Mammalian pyruvate kinase functions as a tetrameric protein composed of identical subunits, which adopt a dimer-of-dimers configuration. Each monomer features a single active site and consists of three primary domains designated A, B and C, and a small N-terminal domain.
View Article and Find Full Text PDFSmall
August 2025
Key Laboratory of Environmental Optics and Technology, And Environmental Materials and Pollution Control Laboratory, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei, 230031, China.
Single-atom catalysts (SACs) exhibit outstanding catalytic activity, yet their application in real complex environments is constrained by the single active sites and instabilities that are susceptible to inactivation. Extensive efforts have been made to regulate the metal coordination environment, but the catalytic role of nonmetal dopants, especially beyond the first shell, remains underexplored. Herein, S-engineered second-shell Fe single-atom catalysts (FeNSC) are reported, in which S sites not only function as additional nonmetallic active sites separated from Fe but also reinforce the stability of the catalysts.
View Article and Find Full Text PDFNat Commun
July 2025
State Key Laboratory of Mechanics and Control for Aerospace Structures, Key Laboratory for Intelligent Nano Materials and Devices of the Ministry of Education, and Institute for Frontier Science, Nanjing University of Aeronautics and Astronautics, Nanjing, P. R. China.
Conventional passivating ligands bind to perovskite surfaces through only a single active site, which not only creates a resistive barrier due to dense ligand packing but also restricts the enhancement of device stability. Here, we identify an antimony chloride-N,N-dimethyl selenourea complex, Sb(SU)Cl, as a multi-anchoring ligand to significantly enhance perovskite crystallinity, suppress defect formation, and dramatically improve moisture resistance and overall stability. As a result, we achieve a power conversion efficiency of 25.
View Article and Find Full Text PDFJ Colloid Interface Sci
December 2025
State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, School of Chemical Engineering and Technology, Xinjiang University, Urumqi 830017, PR China.
Fe-NC materials have emerged as promising alternatives to platinum-based catalysts for oxygen reduction reaction (ORR). Yet, their performance remains constrained by the intrinsic linear scaling relationship of single-active-site configuration, leading to sluggish kinetics. Herein, a feasible dual-site cascade electrocatalyst was synthesized via a simple one-step pyrolysis, featuring in-situ formed uniformly dispersed ZnS nanoparticles synergistically integrated with FeN-enriched N, S-codoped carbon matrices (denoted as ZnS-Fe-NSC).
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