Commercial vanadium oxide catalysts exhibit high efficiency for the selective catalytic reduction (SCR) of NO with NH, especially in the presence of NO (i.e., occurrence of fast NH-SCR). The high-activity sites and their working principle for the fast NH-SCR reaction, however, remain elusive. Here, by combining spectroscopy, isotopic labeling experiments, and density functional theory (DFT) calculations, we demonstrate that polymeric vanadyl species act as the main active sites in the fast SCR reaction because the coupling effect of the polymeric structure alters the elementary reaction step and effectively avoids the high energy barrier of the rate-determining step over monomeric vanadyl species. This study unveils the high-activity dinuclear mechanism of the NO-involved SCR reaction over vanadia-based catalysts and provides a fundamental basis for developing high-efficiency and low VO-loading SCR catalysts.
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http://dx.doi.org/10.1021/acs.est.3c05070 | DOI Listing |
Dalton Trans
January 2025
Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica, Facultad de Química, and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Consejo Superior de Investigaciones Científicas (CSIC) and Universidad de Sevilla, 41092 Sevilla, Spain.
Redox-active ligands provide alternative reaction pathways by facilitating redox events. Among these, tridentate bis(piridylimino)isoindole (BPI) fragments offer great potential, though their redox-active behaviour remains largely underdeveloped. We describe herein a family of BPI germanium(II) complexes and the study of their redox properties.
View Article and Find Full Text PDFDalton Trans
January 2025
Department of Chemistry, Panskura Banamali College, Panskura RS, WB 721152, India.
The coordination compounds featuring a {CuO} core, typically bridged by hydroxo or alkoxo groups, are particularly intriguing due to their notable magnetic properties and catalytic activity. In this study, we explored the synthesis and characterization of four new Schiff base ligands and their subsequent complexation with Cu salts, which resulted in the formation of three tetranuclear complexes: [Cu(L)]·2HO (1), [Cu(L)(HL)](Cl)(NO)·5HO (2), and [Cu(L)] (3), as well as one dinuclear complex: [Cu(L)] (4). These tetranuclear complexes all feature a {CuO} core, but with differing coordination environments around the Cu centers.
View Article and Find Full Text PDFNucleic Acids Res
January 2025
School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland.
Copper compounds with artificial metallo-nuclease (AMN) activity are mechanistically unique compared to established metallodrugs. Here, we describe the development of a new dinuclear copper AMN, Cu2-BPL-C6 (BPL-C6 = bis-1,10-phenanthroline-carbon-6), prepared using click chemistry that demonstrates site-specific DNA recognition with low micromolar cleavage activity. The BPL-C6 ligand was designed to force two redox-active copper centres-central for enhancing AMN activity-to bind DNA, via two phenanthroline ligands separated by an aliphatic linker.
View Article and Find Full Text PDFInorg Chem
January 2025
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education; Yunnan Provincial Center for Research and Development of Natural Products; School of Pharmacy, Yunnan University, Kunming 650500, P. R. China.
A series of dinuclear Ir(III) complexes have been constructed for enhanced photodynamic and photothermal therapy (PDT and PTT) for cisplatin-resistant non-small-cell lung cancer. They enter cells via caveolar endocytosis, target mitochondria but not nuclear, generate both singlet oxygen and superoxide anion, and release heat when exposed to infrared (IR) irradiation, thus inducing reactive oxygen species (ROS)-associated cell disruption and thermal ablation. The IR-generated ROS can further activate caspases, triggering apoptosis.
View Article and Find Full Text PDFChemistry
January 2025
Department of Chemistry, National Tsing Hua University, 101, Sec 2, Kuang-Fu Rd., Hsinchu, 30013, Taiwan.
This study focuses on enhancing the water oxidation reaction (WOR) efficacy of dinuclear cobalt complex catalysts from both kinetic (turnover frequency, TOF) and thermodynamic (overpotential, η) perspectives. For this purpose, we synthesized six dinuclear cobalt complexes 1-6 comprising non-innocent ligands with different electronically active substituents (-OMe (1), -Me (2), -H (3), -F (4), -Cl (5), and -CN (6)). The electronic effects on the electrochemical WOR under neutral, acidic, and alkaline conditions were investigated experimentally and computationally.
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