Reactive High-Valent Iron Intermediates in Enhancing Treatment of Water by Ferrate

2021 ◽  
Author(s):  
Virender K. Sharma ◽  
Mingbao Feng ◽  
Dionysios D. Dionysiou ◽  
Hong-Cai Zhou ◽  
Chetan Jinadatha ◽  
...  
Keyword(s):  
High Valent

Kinetic Control of Interpenetration in Fe-Biphenyl-4,4′-dicarboxylate MOFs by Coordination and Oxidation Modulation

2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  
Keyword(s):  
Self Assembly ◽  
Surface Areas ◽  
Metal Precursors ◽  
Additional Coordination ◽  
Fine Control ◽  
Multiple Alternative ◽  
Metal Organic ◽  
Dft Simulations ◽  
High Valent ◽  
And Control

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4'-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2'-bipyridine-5,5'-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br><br>

Mechanistic insight into the reaction pathway of peroxomonosulfate-initiated decomplexation of EDTA-NiII under alkaline conditions: Formation of high-valent Ni intermediate

2021 ◽  
pp. 120375
Author(s):  
Sheng Liang ◽  
Xiaoting Hu ◽  
Haolin Xu ◽  
Zhenchao Lei ◽  
Chaohai Wei ◽  
...  
Keyword(s):  
Reaction Pathway ◽  
Mechanistic Insight ◽  
Alkaline Conditions ◽  
High Valent ◽  
Insight Into

High-valent Zirconium-doping modified Co3O4 weave-like nanoarray boosts oxygen evolution reaction

2021 ◽  
pp. 161172
Author(s):  
Guijin Yang ◽  
Botao Zhu ◽  
Yujun Fu ◽  
Jing Zhao ◽  
Yanna Lin ◽  
...  
Keyword(s):  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Zirconium Doping ◽  
High Valent

Redefining the Mechanistic Scenario of Carbon–Sulfur Nucleophilic Coupling via High‐Valent Cp*Co(IV) Species

2021 ◽  
Author(s):  
Sara López-Resano ◽  
Sara Martínez de Salinas ◽  
Felipe A. Garcés-Pineda ◽  
Andrea Moneo-Corcuera ◽  
José Ramón Galán-Mascarós ◽  
...  
Keyword(s):  
High Valent

Activation of peroxymonosulfate by single-atom Fe-g-C3N4 catalysts for high efficiency degradation of tetracycline via nonradical pathways: Role of high-valent iron-oxo species and Fe–Nx sites

2021 ◽  
pp. 130803
Author(s):  
Xiaoming Peng ◽  
Jianqun Wu ◽  
Zilong Zhao ◽  
Xing Wang ◽  
Hongling Dai ◽  
...  
Keyword(s):  
High Efficiency ◽  
Single Atom ◽  
High Valent

Nonradical activation of peroxymonosulfate by hematite for oxidation of organic compounds: A novel mechanism involving high-valent iron species

2021 ◽  
pp. 130743
Author(s):  
Hyeonseok Kang ◽  
Donghyun Lee ◽  
Ki-Myeong Lee ◽  
Hak-Hyeon Kim ◽  
Hongshin Lee ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Iron Species ◽  
Oxidation Of Organic Compounds ◽  
High Valent

Mechanistic insights into the allylic oxidation of aliphatic compounds by tetraamido iron(v) species: A C–H vs. O–H bond activation

2020 ◽  
Vol 44 (44) ◽  
pp. 19103-19112
Author(s):  
Monika ◽  
Azaj Ansari
Keyword(s):  
Comparative Study ◽  
Bond Activation ◽  
Iron Complex ◽  
Catalytic Reactions ◽  
Allylic Oxidation ◽  
Deep Insight ◽  
Aliphatic Compounds ◽  
High Valent ◽  
Insight Into

This work is based on a deep insight into a comparative study of C–H vs. O–H bond activation of allylic compound by the high valent iron complex. Our theoretical findings can help to design catalysts with better efficiency for catalytic reactions.

Reaction of 2-nitrophenols with high-valent trimethylphosphine complexes of cobalt

2003 ◽  
Vol 342 ◽  
pp. 179-184 ◽  
Author(s):  
Hans-Friedrich Klein ◽  
Xiaoyan Li ◽  
Ulrich Flörke ◽  
Hans-Jürgen Haupt
Keyword(s):  
High Valent
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