scholarly journals Biomimetic Cu/Nitroxyl Catalyst Systems for Selective Alcohol Oxidation

Catalysts ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 395 ◽  
Author(s):  
Lindie Marais ◽  
Andrew John Swarts
Keyword(s):  
Active Sites ◽  
Alcohol Oxidation ◽  
Galactose Oxidase ◽  
Co Catalyst ◽  
Co Catalysts ◽  
Mechanistic Pathway ◽  
Oxidation Of Alcohols ◽  
Catalyst Systems ◽  
Carbonyl Products

The oxidation of alcohols to the corresponding carbonyl products is an important organic transformation and the products are used in a variety of applications. The development of catalytic methods for selective alcohol oxidation have garnered significant attention in an attempt to find a more sustainable method without any limitations. Copper, in combination with 2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO) and supported by organic ligands, have emerged as the most effective catalysts for selective alcohol oxidation and these catalyst systems are frequently compared to galactose oxidase (GOase). The efficiency of GOase has led to extensive research to mimic the active sites of these enzymes, leading to a variety of Cu/TEMPO· catalyst systems being reported over the years. The mechanistic pathway by which Cu/TEMPO· catalyst systems operate has been investigated by several research groups, which led to partially contradicting mechanistic description. Due to the disadvantages and limitations of employing TEMPO· as co-catalyst, alternative nitroxyl radicals or in situ formed radicals, as co-catalysts, have been successfully evaluated in alcohol oxidation. Herein we discuss the development and mechanistic elucidation of Cu/TEMPO· catalyst systems as biomimetic alcohol oxidation catalysts.

Photocatalytic reforming of glycerol for H2 evolution on Pt/TiO2: fundamental understanding the effect of co-catalyst Pt and the Pt deposition route

2015 ◽  
Vol 3 (5) ◽  
pp. 2271-2282 ◽  
Author(s):  
Xiaoliang Jiang ◽  
Xianliang Fu ◽  
Li Zhang ◽  
Sugang Meng ◽  
Shifu Chen
Keyword(s):  
Active Sites ◽  
H2 Evolution ◽  
Co Catalyst ◽  
Fundamental Understanding

The effects of deposited Pt and its deposition route on the photocatalytic reforming of glycerol for H2 evolution over Pt/TiO2 were investigated. Intimately loaded Pt(0) particles are the key active sites for the reaction, the formation of which was favored by an in situ photo-deposition route.

Ag–CoO nanocomposites for gas-phase oxidation of alcohols to aldehydes and ketones: intensified O2 activation at Ag–CoO interfacial sites

2020 ◽  
Vol 10 (24) ◽  
pp. 8445-8457
Author(s):  
Kun Liu ◽  
Yichen Zhao ◽  
Jiale Wang ◽  
Qingsong Xue ◽  
Guofeng Zhao
Keyword(s):  
Gas Phase ◽  
Active Sites ◽  
Active Oxygen Species ◽  
Alcohol Oxidation ◽  
Oxygen Species ◽  
Oxidation Of Alcohols ◽  
Phase Oxidation ◽  
Aldehydes And Ketones ◽  
Catalytic Active Sites ◽  
Gas Phase Oxidation

The fabrication of qualified catalysts is a key issue to implement gas-phase aerobic alcohol oxidation, but necessarily requires understanding the structures of catalytic active sites and the supply of active oxygen species.

scholarly journals Preparation of High-Purity Ammonium Tetrakis(pentafluorophenyl)borate for the Activation of Olefin Polymerization Catalysts

Molecules ◽  
2021 ◽  
Vol 26 (9) ◽  
pp. 2827
Author(s):  
Hyun-Ju Lee ◽  
Jun-Won Baek ◽  
Yeong-Hyun Seo ◽  
Hong-Cheol Lee ◽  
Sun-Mi Jeong ◽  
...  
Keyword(s):  
Type Species ◽  
Olefin Polymerization ◽  
Bulk Polymerization ◽  
Aliphatic Hydrocarbon ◽  
Polymerization Catalysts ◽  
Co Catalyst ◽  
Co Catalysts ◽  
Hydrocarbon Solvents ◽  
In Situ Activation

Homogeneous olefin polymerization catalysts are activated in situ with a co-catalyst ([PhN(Me)2-H]+[B(C6F5)4]− or [Ph3C]+[B(C6F5)4]−) in bulk polymerization media. These co-catalysts are insoluble in hydrocarbon solvents, requiring excess co-catalyst (>3 eq). Feeding the activated species as a solution in an aliphatic hydrocarbon solvent may be advantageous over the in situ activation method. In this study, highly pure and soluble ammonium tetrakis(pentafluorophenyl)borates ([Me(C18H37)2N-H]+[B(C6F5)4]− and [(C18H37)2NH2]+[B(C6F5)4]−) containing neither water nor Cl− salt impurities were prepared easily via the acid–base reaction of [PhN(Me)2-H]+[B(C6F5)4]− and the corresponding amine. Using the prepared ammonium salts, the activation reactions of commercial-process-relevant metallocene (rac-[ethylenebis(tetrahydroindenyl)]Zr(Me)2 (1-ZrMe2), [Ph2C(Cp)(3,6-tBu2Flu)]Hf(Me)2 (3-HfMe2), [Ph2C(Cp)(2,7-tBu2Flu)]Hf(Me)2 (4-HfMe2)) and half-metallocene complexes ([(h5-Me4C5)Si(Me)2(k-NtBu)]Ti(Me)2 (5-TiMe2), [(h5-Me4C5)(C9H9(k-N))]Ti(Me)2 (6-TiMe2), and [(h5-Me3C7H1S)(C10H11(k-N))]Ti(Me)2 (7-TiMe2)) were monitored in C6D12 with 1H NMR spectroscopy. Stable [L-M(Me)(NMe(C18H37)2)]+[B(C6F5)4]− species were cleanly generated from 1-ZrMe2, 3-HfMe2, and 4-HfMe2, while the species types generated from 5-TiMe2, 6-TiMe2, and 7-TiMe2 were unstable for subsequent transformation to other species (presumably, [L-Ti(CH2N(C18H37)2)]+[B(C6F5)4]−-type species). [L-TiCl(N(H)(C18H37)2)]+[B(C6F5)4]−-type species were also prepared from 5-TiCl(Me) and 6-TiCl(Me), which were newly prepared in this study. The prepared [L-M(Me)(NMe(C18H37)2)]+[B(C6F5)4]−-, [L-Ti(CH2N(C18H37)2)]+[B(C6F5)4]−-, and [L-TiCl(N(H)(C18H37)2)]+[B(C6F5)4]−-type species, which are soluble and stable in aliphatic hydrocarbon solvents, were highly active in ethylene/1-octene copolymerization performed in aliphatic hydrocarbon solvents.

Boosting activity of molecular oxygen by pyridinium-based photocatalysts for metal-free alcohol oxidation

2021 ◽  
Vol 23 (3) ◽  
pp. 1337-1343
Author(s):  
Shuai Ma ◽  
Jing-Wang Cui ◽  
Cai-Hui Rao ◽  
Meng-Ze Jia ◽  
Yun-Rui Chen ◽  
...  
Keyword(s):  
Energy Transfer ◽  
Molecular Oxygen ◽  
Noble Metal ◽  
Photocatalytic Oxidation ◽  
Alcohol Oxidation ◽  
Free Alcohol ◽  
Metal Free ◽  
Co Catalysts ◽  
Mild Conditions ◽  
Oxidation Of Alcohols

Pyridinium molecules are developed as electron- and energy-transfer mediators to boost the activity of air oxygen and thus achieve highly efficient photocatalytic oxidation of alcohols without any noble metal and additional co-catalysts/additives under mild conditions.

scholarly journals 2D MXenes as Co-catalysts in Photocatalysis: Synthetic Methods

2019 ◽  
Vol 11 (1) ◽  
Author(s):  
Yuliang Sun ◽  
Xing Meng ◽  
Yohan Dall’Agnese ◽  
Chunxiang Dall’Agnese ◽  
Shengnan Duan ◽  
...  
Keyword(s):  
Self Assembly ◽  
Large Family ◽  
Synthetic Methods ◽  
Future Research ◽  
Synthesis Methods ◽  
Mechanical Mixing ◽  
Co Catalyst ◽  
Co Catalysts ◽  
Photogenerated Charge Separation

Abstract Since their seminal discovery in 2011, two-dimensional (2D) transition metal carbides/nitrides known as MXenes, that constitute a large family of 2D materials, have been targeted toward various applications due to their outstanding electronic properties. MXenes functioning as co-catalyst in combination with certain photocatalysts have been applied in photocatalytic systems to enhance photogenerated charge separation, suppress rapid charge recombination, and convert solar energy into chemical energy or use it in the degradation of organic compounds. The photocatalytic performance greatly depends on the composition and morphology of the photocatalyst, which, in turn, are determined by the method of preparation used. Here, we review the four different synthesis methods (mechanical mixing, self-assembly, in situ decoration, and oxidation) reported for MXenes in view of their application as co-catalyst in photocatalysis. In addition, the working mechanism for MXenes application in photocatalysis is discussed and an outlook for future research is also provided.

scholarly journals Electrokinetic and in situ spectroscopic investigations of CO electrochemical reduction on copper

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Jing Li ◽  
Xiaoxia Chang ◽  
Haochen Zhang ◽  
Arnav S. Malkani ◽  
Mu-jeng Cheng ◽  
...  
Keyword(s):  
Mass Transport ◽  
Active Sites ◽  
Gas Diffusion ◽  
Reduction Reaction ◽  
Adsorbed Hydrogen ◽  
Diffusion Type ◽  
Proton Coupled Electron Transfer ◽  
Alkaline Electrolytes ◽  
Reaction Orders

AbstractRigorous electrokinetic results are key to understanding the reaction mechanisms in the electrochemical CO reduction reaction (CORR), however, most reported results are compromised by the CO mass transport limitation. In this work, we determined mass transport-free CORR kinetics by employing a gas-diffusion type electrode and identified dependence of catalyst surface speciation on the electrolyte pH using in-situ surface enhanced vibrational spectroscopies. Based on the measured Tafel slopes and reaction orders, we demonstrate that the formation rates of C2+ products are most likely limited by the dimerization of CO adsorbate. CH4 production is limited by the CO hydrogenation step via a proton coupled electron transfer and a chemical hydrogenation step of CO by adsorbed hydrogen atom in weakly (7 < pH < 11) and strongly (pH > 11) alkaline electrolytes, respectively. Further, CH4 and C2+ products are likely formed on distinct types of active sites.

scholarly journals The Effect of Iron Impurities on Transition Metal Catalysts for the Oxygen Evolution Reaction in Alkaline Environment: Activity Mediators or Active Sites?

2020 ◽  
Author(s):  
Ioannis Spanos ◽  
Justus Masa ◽  
Aleksandar Zeradjanin ◽  
Robert Schlögl
Keyword(s):  
Transition Metal ◽  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Active Sites ◽  
Water Electrolysis ◽  
Metal Catalysts ◽  
Transition Metal Catalysts ◽  
Alkaline Water Electrolysis ◽  
Co Catalysts ◽  
Model Transition

AbstractThere is an ongoing debate on elucidating the actual role of Fe impurities in alkaline water electrolysis, acting either as reactivity mediators or as co-catalysts through synergistic interaction with the main catalyst material. This perspective summarizes the most prominent oxygen evolution reaction (OER) mechanisms mostly for Ni-based oxides as model transition metal catalysts and highlights the effect of Fe incorporation on the catalyst surface in the form of impurities originating from the electrolyte or co-precipitated in the catalyst lattice, in modulating the OER reaction kinetics, mechanism and stability. Graphic Abstract

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