122-03-2Relevant articles and documents
A polyoxometalate@covalent triazine framework as a robust electrocatalyst for selective benzyl alcohol oxidation coupled with hydrogen production
Li, Zhen,Zhang, Junhao,Jing, Xiaoting,Dong, Jing,Liu, Huifang,Lv, Hongjin,Chi, Yingnan,Hu, Changwen
, p. 6152 - 6159 (2021)
Electrocatalytic oxidation has been proven as a sustainable and promising alternative to traditional chemical transformation, but its further development is limited by the use of noble-metal electrocatalysts. Herein, a polyoxometalate-based electrode material,H5PMo10V2O40@CTF(denoted asPMo10V2@CTF), has been successfully fabricated through electrostatic assembly of a molecular polyoxometalate catalyst,PMo10V2, with a porous cationic covalent triazine framework (CTF), which, to our knowledge, represents the first combination of polyoxometalate with a cationic CTF. The resultingPMo10V2@CTFexhibits high activity for the selective electrocatalytic oxidation of alcohols to aldehydes, achieving 99% conversion of benzyl alcohol, over 99% selectivity of benzyl aldehyde, and at the same time near unity H2production. Notably, the reported electrocatalytic system presents good atom economy, high energy conversion (96% faradaic efficiency), remarkable catalytic activity and robustness for at least eight recycles. Based on the various experimental and spectroscopic analyses, a possible catalytic mechanism was proposed, revealing that such excellent electrocatalytic performance is attributed to the versatile redox ability ofPMo10V2and the good porosity and adsorption property of the CTF in the constructedPMo10V2@CTFcomposite.
Gold nanoparticles supported on Cs2CO3 as recyclable catalyst system for selective aerobic oxidation of alcohols at room temperature
Karimi, Babak,Kabiri Esfahani, Farhad
, p. 5555 - 5557 (2009)
NaAuCl4/Cs2CO3 was found to be a simple bench top, recyclable and selective catalyst system for the aerobic oxidation of various types of alcohols into their corresponding aldehydes and ketones at room temperature without the need for any further polymeric and/or oxidic support.
Design and development of natural and biocompatible raffinose-Cu2O magnetic nanoparticles as a heterogeneous nanocatalyst for the selective oxidation of alcohols
Eivazzadeh-Keihan, Reza,Esmaeili, Mir Saeed,Ghafuri, Hossein,Maleki, Ali,Varzi, Zahra
, (2020)
Natural polymers are recently playing a vital role as a support for the noble metals. In the present study, raffinose from the classes of oligosaccharide polymer with a high capacity of magnetization was used as active support for the copper metal. The copper immobilized on the raffinose-based magnetic nanoparticles (MNPs) which can be used as a recyclable heterogeneous nanocatalyst for the selective oxidation of primary benzyl alcohols (PBA) to benzaldehyde (BAD) derivatives. The morphology and structure of the recoverable magnetic nanocatalyst were characterized using different microscopic and spectroscopic techniques including FT-IR, GC, VSM, XRD, TEM, TGA, FESEM and EDS analyses. Also, the optimum conditions of co-reactant, reaction time, oxidant, temperature and amount of the nanocatalyst for oxidation reaction were investigated. Moreover, the Fe3O4?raffinose-Cu2O NPs had a significant effect to enhance yield and reduce the reaction time.
Preparation of large-size, superparamagnetic, and highly magnetic Fe3O4@PDA core-shell submicrosphere-supported nano-palladium catalyst and its application to aldehyde preparation through oxidative dehydrogenation of benzyl alcohols
Guo, Haichang,Zheng, Renhua,Jiang, Huajiang,Xu, Zhenyuan,Xia, Aibao
, (2019)
Large-size, superparamagnetic, and highly magnetic Fe3O4@PDA core-shell submicrospheresupported nano-palladium catalysts were prepared in this study. Dopamine was encapsulated on the surface of Fe3O4 particles via self-polymerization and then protonated to positively charge the microspheres. PdCl42- was dispersed on the surface of the microspheres by positive and negative charge attraction and then reduced to nano-palladium. With air as oxidant, the catalyst can successfully catalyze the dehydrogenation of benzyl alcohols to produce the corresponding aldehydes at 120 °C.
Multifunctional radical-doped polyoxometalate-based host-guest material: Photochromism and photocatalytic activity
Liao, Jian-Zhen,Zhang, Hai-Long,Wang, Sa-Sa,Yong, Jian-Ping,Wu, Xiao-Yuan,Yu, Rongmin,Lu, Can-Zhong
, p. 4345 - 4350 (2015)
An effective strategy to synthesize multifunctional materials is the incorporation of functional organic moieties and metal oxide clusters via self-assembly. A rare multifunctional radical-doped zinc-based host-guest crystalline material was synthesized with a fast-responsive reversible ultraviolet visible light photochromism, photocontrolled tunable luminescence, and highly selective photocatalytic oxidation of benzylic alcohols as a result of blending of distinctively different functional components, naphthalenediimide tectons, and polyoxometalates (POMs). It is highly unique to link π-electron-deficient organic tectons and POMs by unusual POMs anion-π interactions, which are not only conducive to keeping the independence of each component but also effectively promoting the charge transfer or exchange among the components to realize the fast-responsive photochromism, photocontrolled tunable luminescence, and photocatalytic activity.
TEMPO-mediated aerobic oxidation of alcohols using copper(II) complex of bis(phenol) di-amine ligand as biomimetic model for Galactose oxidase enzyme
Safaei, Elham,Hajikhanmirzaei, Leila,Karimi, Babak,Wojtczak, Andrzej,Coti?, Patricia,Lee, Yong-Ill
, p. 153 - 162 (2016)
Mononuclear copper complexes of four-dentate N2O2 bis(phenol) diamine ligands (H2LNEX X: C and OB in which C and OB are chloro and tert-butyl-methoxy substituents on phenol groups) have been synthesized and characterized by IR, UV-Vis, single crystal X-ray diffraction, magnetic susceptibility studies and cyclic voltammetry techniques. The CuLNEX complexes show the square pyramid geometry of the coordination sphere with the copper centers surrounded by two nitrogen and oxygen atoms from the coordinating ligand and an axially bound water molecule. The effective magnetic moments of 1.7 and 1.8 BM confirm a monomer complex with copper(II) center. Electrochemical oxidation of these complexes yielded the corresponding Cu(II)-phenoxyl radical species. In addition, CuLNEX complexes, have shown efficient catalytic activities for TEMPO-mediated oxidation of a set of alcohols to the corresponding aldehydes in the presence of molecular oxygen as oxidant at room temperature.
Protonated Pteridine and Flavin Analogues acting as Efficient and Substrate-selective Photocatalysts in the Oxidation of Benzyl Alcohol Derivatives by Oxygen
Fukuzumi, Shunichi,Tanii, Kumiko,Tanaka, Toshio
, p. 816 - 818 (1989)
Protonated aminopterin, lumazine, and riboflavin-tetra-acetate efficiently catalyse the substrate selective photo-oxidation of benzyl alcohol derivatives by oxygen in the presence of perchloric acid in acetonitrile at 298 K.
A copper complex of a noninnocent iminophenol-amidopyridine hybrid ligand: Synthesis, characterization, and aerobic alcohol oxidation
Alaji, Zahra,Safaei, Elham,Chiang, Linus,Clarke, Ryan M.,Mu, Changhua,Storr, Tim
, p. 6066 - 6074 (2014)
Reaction of the noninnocent iminophenol-iminopyridine hybrid ligand HLIPIP, where LIPIP denotes [2-((E)-{(E)-2-[(E)-pyridin-2-ylmethyleneamino]benzylidene}amino)-4,6-di-tert-butylphenolate], with copper acetate afforded a copper complex, LAPIPCuII, in which one of the imine functional groups is oxidized to an amide during metal complexation. The new CuII complex is capable of catalyzing efficient aerobic alcohol oxidation under mild conditions. The crystal structure of LAPIPCuII exhibits a square-planar geometry with the CuII center coordinated by three nitrogen atoms and one oxygen atom. Electrochemical studies were conducted to evaluate the redox-active behavior of the complex, and the results showed a quasireversible reduction and a ligand-based oxidation process. The neutral species of LAPIPCuII is EPR active, which is consistent with a paramagnetic electronic ground state (d9, S = 1/2), whereas the one-electron oxidized complex was X-band EPR silent. One-electron chemical oxidation of LAPIPCuII gave a new species that can be attributed to a CuII-phenoxyl radical complex. Based on EPR measurements in conjunction with density functional theory calculations, [LAPIPCuII]+ is proposed to have a triplet electronic ground state, exhibiting a weak ferromagnetic interaction between the CuII center and the coordinated phenoxyl radical. A new copper complex of a noninnocent iminophenol-pyridine hybrid ligand that is capable of efficient aerobic alcohol oxidation was studied.
Efficient and Reusable Sn(II)-containing Imidazolium-based Ionic Liquid as a Catalyst for the Oxidation of Benzyl Alcohol
Wang, Bingtong,Hu, Yulin,Fang, Dong,Wu, Lin,Xing, Rong
, p. 991 - 999 (2016)
A simple and efficient catalytic system [BBIM]Br–SnCl2 for the oxidation of benzyl alcohol using hydrogen peroxide as the oxidant has been developed. Reaction conditions such as the catalyst dose, the solvents, reaction temperature, reaction time, and the amount of hydrogen peroxide were investigated. The optimum reaction conditions identified were 0.11 g of catalyst, no solvent, 65°C, 15 min, and 2 mmol of hydrogen peroxide. Oxidation of various alcohols was also investigated under the optimized conditions. The catalyst [BBIM]Br–SnCl2 can be easily recovered and reused for six reaction runs without significant loss of catalytic activity, because the Sn species of the catalyst can be coordinated with the imidazole ring of the ionic liquid. The reused catalyst was further characterized by Fourier transform infrared spectroscopy to evaluate its chemical properties. The results proved that the [BBIM]Br–SnCl2 catalyst was stable and reusable for the oxidation reactions. A possible mechanism for the oxidation of benzyl alcohol to benzaldehyde is proposed.
Substrate-selective Photo-oxidation of Benzyl Alcohol Derivatives with Oxygen, catalysed by an NAD+ Model Compound
Fukuzumi, Shunichi,Kuroda, Sadaki,Tanaka, Toshio
, p. 120 - 122 (1987)
An NAD+ model compound, 10-methylacridinium ion (AcrH+), catalyses the substrate-selective photo-oxidation of benzyl alcohol derivatives with oxygen in acetonitrile at 298 K, which is initiated by the electron-transfer reactions from benzyl alcohol derivatives to the singlet excited state of AcrH+.
On the stabilization of gold nanoparticles over silica-based magnetic supports modified with organosilanes
Oliveira, Rafael L.,Zanchet, Daniela,Kiyohara, Pedro K.,Rossi, Liane M.
, p. 4626 - 4631 (2011)
The immobilization of gold nanoparticles (Au NPs) on silica is made possible by the functionalization of the silica surfaces with organosilanes. Au NPs could only be stabilized and firmly attached to silica-support surfaces that were previously modified with amino groups. Au NPs could not be stabilized on bare silica surfaces and most of the NPs were then found in the solution. The metal-support interactions before and after the Au NP formation, observed by X-ray absorption fine structure spectroscopy (XAFS), indicate a stronger interaction of gold(III) ions with amino-modified silica surfaces than with the silanol groups in bare silica. An amino-modified, silica-based, magnetic support was used to prepare an active Au NP catalyst for the chemoselective oxidation of alcohols, a reaction of great interest for the fine chemical industry.
Creation of a high-valent manganese species on hydrotalcite and its application to the catalytic aerobic oxidation of alcohols
Nagashima, Kohji,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
, p. 2142 - 2144 (2010)
A high-valent Mn oxide species is successfully synthesized on the surface of hydrotalcite (Mn/HT-Ox), and is found to act as an efficient heterogeneous catalyst for the oxidation of alcohols using molecular oxygen as an oxidant.
Maximizing the Number of Interfacial Sites in Single-Atom Catalysts for the Highly Selective, Solvent-Free Oxidation of Primary Alcohols
Li, Tianbo,Liu, Fei,Tang, Yan,Li, Lin,Miao, Shu,Su, Yang,Zhang, Junying,Huang, Jiahui,Sun, Hui,Haruta, Masatake,Wang, Aiqin,Qiao, Botao,Li, Jun,Zhang, Tao
, p. 7795 - 7799 (2018)
The solvent-free selective oxidation of alcohols to aldehydes with molecular oxygen is highly attractive yet challenging. Interfacial sites between a metal and an oxide support are crucial in determining the activity and selectivity of such heterogeneous catalysts. Herein, we demonstrate that the use of supported single-atom catalysts (SACs) leads to high activity and selectivity in this reaction. The significantly increased number of interfacial sites, resulting from the presence of individually dispersed metal atoms on the support, renders SACs one or two orders of magnitude more active than the corresponding nanoparticle (NP) catalysts. Lattice oxygen atoms activated at interfacial sites were found to be more selective than O2 activated on metal NPs in oxidizing the alcohol substrate. This work demonstrates for the first time that the number of interfacial sites is maximized in SACs, providing a new avenue for improving catalytic performance by developing appropriate SACs for alcohol oxidation and other reactions occurring at metal–support interfacial sites.
The selective catalytic oxidation of terminal alcohols: A novel four-component system with MTO as catalyst
Herrmann, Wolfgang A.,Zoller, Jochen P.,Fischer, Richard W.
, p. 404 - 407 (1999)
A four-component system (H2O2, MTO, HBr, TEMPO) in acetic acid catalyzes the selective oxidation of terminal alcohols to the corresponding aldehydes with excellent selectivity and yield. The system allows the oxidation of alcohols with hydrogen peroxide as oxidants either selectively to aldehydes or to the corresponding acids, depending on the reaction parameters. The new technique is especially applicable to the oxidation of carbohydrates.
Zinc substituted Keggin-type polyoxometalate on Dowex: a green heterogeneous catalyst for oxidation of alcohols in water
Aghayi, Mehdi,Yadollahi, Bahram,Farsani, Mostafa Riahi
, p. 2895 - 2900 (2020)
In this work, homogeneous and heterogeneous oxidation of alcohols by H2O2 in the presence of [(n-C4H9)4?N]5[PW11ZnO39].3H2O and [PW11ZnO39]5? supported on Dowex 22 as catalysts have been investigated. Using water as a green solvent, different alcohols were converted into the corresponding aldehydes and ketones in high to excellent yields. Dowex 22 supported polyoxometalate, PW11Zn@Dowex, was also catalyzed highly robust and selective oxidation of unsaturated alcohols. Leaching and recycling experiments on supported catalyst revealed the excellent stability and reusability of this catalytic system.
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Arai,M.
, p. 252 - 255 (1965)
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Borgwardt,Schwenk
, p. 1185,1187 (1934)
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Electrochemical Aerobic Oxidative Cleavage of (sp3)C-C(sp3)/H Bonds in Alkylarenes
Liu, Shuai,Liu, Zhong-Quan,Shen, Tong,Shen, Xu,Wang, Nengyong,Wu, Jintao,Yang, Le,Zhao, Jianyou
, p. 3286 - 3295 (2022/03/14)
An electrochemistry-promoted oxidative cleavage of (sp3)C-C(sp3)/H bonds in alkylarenes was developed. Various aryl alkanes can be smoothly converted into ketones/aldehydes under aerobic conditions using a user-friendly undivided cell setup. The features of air as oxidant, scalability, and mild conditions make them attractive in synthetic organic chemistry.
Selective Electrochemical Oxygenation of Alkylarenes to Carbonyls
Li, Xue,Bai, Fang,Liu, Chaogan,Ma, Xiaowei,Gu, Chengzhi,Dai, Bin
supporting information, p. 7445 - 7449 (2021/10/02)
An efficient electrochemical method for benzylic C(sp3)-H bond oxidation has been developed. A variety of methylarenes, methylheteroarenes, and benzylic (hetero)methylenes could be converted into the desired aryl aldehydes and aryl ketones in moderate to excellent yields in an undivided cell, using O2 as the oxygen source and lutidinium perchlorate as an electrolyte. On the basis of cyclic voltammetry studies, 18O labeling experiments, and radical trapping experiments, a possible single-electron transfer mechanism has been proposed for the electrooxidation reaction.
PhIO-Mediated oxidative dethioacetalization/dethioketalization under water-free conditions
Du, Yunfei,Ouyang, Yaxin,Wang, Xi,Wang, Xiaofan,Yu, Zhenyang,Zhao, Bingyue,Zhao, Kang
, p. 48 - 65 (2021/06/16)
Treatment of thioacetals and thioketals with iodosobenzene in anhydrous DCM conveniently afforded the corresponding carbonyl compounds in high yields under water-free conditions. The mechanistic studies indicate that this dethioacetalization/dethioketalization process does not need water and the oxygen of the carbonyl products comes from the hypervalent iodine reagent.