Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
Homolytic dissociation of ubiquitous water (HO) into radical species is pivotal in driving reactions across chemical, biological, geoscientific, and environmental domains; yet, it faces substantial challenges in cleaving the robust O-H bond and preventing radical recombination. Herein, we demonstrate that greigite with sulfur vacancies (SVs) can ambiently dissociate HO into reactive hydroxyl (•OH) and hydrogen (•H) radicals in a stoichiometric manner. This process is facilitated by the inverse-spinel structure of FeS, where the antiparallel arrangement of high-spin Fe atoms localizes electrons at SVs, enabling barrierless cleavage of the O-H bond to yield •OH and •H. Concurrently, adjacent S atoms with pronounced Lewis basicity effectively stabilize the generated •H, promoting its spatial separation from the •OH confined on SVs. This interesting water homolysis scheme, characterized by synchronous •OH and •H generation, triggers efficient and selective hydrations of styrene and its derivatives to high-value-added aldehydes and energy-rich methane via a radical pathway.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.5c08801 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Ambient-Pressure C-C Coupling of CO Hydrogenation by NiFe/TiO Bimetallic Catalyst.
J Am Chem Soc
September 2025
University of Michigan-Shanghai Jiao Tong University Joint Institute, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Catalytic upgrading of CO to value-added C products offers promising solutions to trim carbon emissions with additional economic benefits. Herein, we report a NiFe bimetallic catalyst showing efficient ambient-pressure C-C coupling performance subject to H pretreatment temperature. An optimal performance was achieved after reducing NiFe/TiO at 350 °C (NiFe-350/TiO), yielding 27.
View Article and Find Full Text PDFDynamics of Metal-Metal Bond Dissociation in Pd-Pd and Ni-Ni Complexes: Reorganization and Redistribution Reactions of the Metalloradicals.
Angew Chem Int Ed Engl
September 2025
Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 276, 69120, Heidelberg, Germany.
Dinuclear M(I)-M(I) complexes (M = Ni, Pd) may serve as stable reservoir forms for highly reactive mononuclear metalloradicals, which are of interest as potential catalytic species. However, their dissociation dynamics as well as the factors governing monomer stabilization remain incompletely understood. This study investigates the influence of steric bulk and residual ligand flexibility within a PNP pincer framework on the homolytic dissociation behavior of unsupported Ni(I)-Ni(I) and Pd(I)-Pd(I) dimers.
View Article and Find Full Text PDFAdvances in the Mechanistic Understanding of Matrix-Assisted Laser Desorption/Ionization In-Source Decay Mass Spectrometry for Peptides and Proteins: Electron Transfer Reaction as the Initiating Step of Fragmentation.
Mass Spectrom Rev
August 2025
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan.
Because matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) induces selective cleavage on the peptide backbone, this technique allows reliable identification of peptides and proteins. In the last 15 years, several new matrices have been developed that more efficiently induce MALDI-ISD, opening new research avenues. Fragmentation of peptides by MALDI-ISD can be divided into two categories: reducing and oxidizing matrices induce selective cleavage of N-Cα and Cα-C bonds, respectively.
View Article and Find Full Text PDFPhotochromic Phenoxyl-Imidazolyl Radical Complex via Homolytic C-O Bond Cleavage.
J Phys Chem Lett
August 2025
Department of Applied Chemistry, College of Life Sciences, Ritsumeikan University, Kusatsu, Shiga 525-8577, Japan.
We report a new photochromic phenoxyl imidazolyl radical complex (PIC) that exhibits reversible homolytic C-O bond cleavage upon UV light irradiation. Ultrafast transient absorption spectroscopy revealed pronounced spectral evolution on nanosecond time scales, reflecting rotational isomerization between two open form isomers. Time-resolved infrared absorption measurements confirmed their biradical character and supported the presence of both isomers in thermodynamic equilibrium.
View Article and Find Full Text PDFHomolytic HO Dissociation into Hydroxyl and Hydrogen Radicals on Sulfur-Deficient Greigite for Efficient Hydration Reactions.
J Am Chem Soc
July 2025
State Key Laboratory of Green Papermaking and Resource Recycling, National Observation and Research Station of Erhai Lake Ecosystem in Yunnan, Yunnan Dali Research Institute, School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.
Homolytic dissociation of ubiquitous water (HO) into radical species is pivotal in driving reactions across chemical, biological, geoscientific, and environmental domains; yet, it faces substantial challenges in cleaving the robust O-H bond and preventing radical recombination. Herein, we demonstrate that greigite with sulfur vacancies (SVs) can ambiently dissociate HO into reactive hydroxyl (•OH) and hydrogen (•H) radicals in a stoichiometric manner. This process is facilitated by the inverse-spinel structure of FeS, where the antiparallel arrangement of high-spin Fe atoms localizes electrons at SVs, enabling barrierless cleavage of the O-H bond to yield •OH and •H.
View Article and Find Full Text PDF