Steady-state and time-resolved emission spectroscopy techniques were employed to study the excited-state proton transfer (ESPT) to water and D(2)O from QCy7, a recently synthesized near-infrared (NIR)-emissive dye with a fluorescence band maximum at 700 nm. We found that the ESPT rate constant, k(PT), of QCy7 excited from its protonated form, ROH, is ~1.5 × 10(12) s(-1). This is the highest ever reported value in the literature thus far, and it is comparable to the reciprocal of the longest solvation dynamics time component in water, τ(S) = 0.8 ps. We found a kinetic isotope effect (KIE) on the ESPT rate of ~1.7. This value is lower than that of weaker photoacids, which usually have KIE value of ~3, but comparable to the KIE on proton diffusion in water of ~1.45, for which the average time of proton transfer between adjacent water molecules is similar to that of QCy7.
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Langmuir
January 2025
Beijing Key Laboratory of Energy Conversion and Storage Materials, College of Chemistry, Beijing Normal University, Beijing 100875, China.
Nontraditional luminogens (NTLs) without large π-conjugated aromatic structures have attracted a great deal of attention in recent years. Developing NTLs with red-shifted and enhanced emissions remains a great challenge. In this work, we developed a NTL composed of three components, i.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Departament de Ciència de Materials i Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, c/Martí i Franquès 1-11, Barcelona 08028, Spain.
The oxygen reduction reaction (ORR) stands as a pivotal process in electrochemistry, finding applications in various energy conversion technologies such as fuel cells, metal-air batteries, and chlor-alkali electrolyzers. Hereby, a comprehensive density functional theory (DFT) investigation is presented into the proposed conventional and unconventional ORR mechanisms using single-atom catalysts (SACs) supported on nitrogen-doped graphene (NG) as model systems. Several reaction intermediates have been identified that appear to be more stable than the ones postulated in the conventional mechanism, which follows the *OOH, *O, and *OH intermediates.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Nanjing University of Aeronautics and Astronautics, College of Materials Science and Technology, No. 169 Sheng Tai West Road, Jiangning District, Nanjing, Jiangsu, China, 211106, Nanjing, CHINA.
The neutral oxygen catalysis is an electrochemical reaction of the utmost importance in energy generation, storage application, and chemical synthesis. However, the restricted availability of protons poses a challenge to achieving kinetically favorable oxygen catalytic reactions. Here, we alter the interfacial water orientation by adjusting the Brønsted acidity at the catalyst surface, to break the proton transfer limitation of neutral oxygen electrocatalysis.
View Article and Find Full Text PDFSmall Methods
January 2025
State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, Guiyang, Guizhou, 550025, China.
Photocatalytic transfer hydrogenation of biomass-derived aldehydes to alcohols often results in unwanted coupling co-products. Herein, an ultraselective hydrogen transfer system enabled by in situ oxidative C─C bond cleavage over a Janus single-atom palladium on titanium dioxide (0.5Pd/TiO) photocatalyst is presented.
View Article and Find Full Text PDFChemistry
January 2025
Indian Institute of Technology Delhi, Department of Chemistry, Hauz Khas, 110016, New Delhi, INDIA.
A mononuclear CoIII complex (1) of a bisamide-bisalkoxide donor ligand was synthesized and thoroughly characterized. The reaction of 1 with 0.5 equiv.
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