Activity For Oxidation Of Alcohols Research Articles

Chemically Bonded α‐Fe2O3/Bi4MO8Cl Dot‐on‐Plate Z‐Scheme Junction with Strong Internal Electric Field for Selective Photo‐oxidation of Aromatic Alcohols

AbstractInferior contact interface and low charge transfer efficiency seriously restrict the performance of heterojunctions. Herein, chemically bonded α‐Fe2O3/Bi4MO8Cl (M=Nb, Ta) dot‐on‐plate Z‐scheme junctions with strong internal electric field are crafted by an in situ growth route. Experimental and theoretical results demonstrate that the internal electric field provides a powerful driving force for vectorial migration of photocharges between Bi4MO8Cl and α‐Fe2O3, and the interfacial Fe−O bond not only serves as an atomic‐level charge flow highway but also lowers the charge transfer energy barrier, thereby accelerating Z‐scheme charge transfer and realizing effective spatial charge separation. Impressively, α‐Fe2O3/Bi4MO8Cl manifests a significantly improved photocatalytic activity for selective oxidation of aromatic alcohols into aldehydes (Con. ≥92 %, Sel. ≥96 %), with a performance improvement of one to two orders of magnitude. This work presents atomic‐level insight into interfacial charge flow steering.

Crystalline porous ionic salts assembled from polyoxometalates and cationic capsule for the selective photocatalytic aerobic oxidation of aromatic alcohols to aldehydes

Crystalline porous ionic salts (CPISs) represent a new type of porous materials constructed by electrostatic interaction, however, synthesis of CPISs bearing pre-designed functionality while exhibiting permanent porosity is still challenging. Herein we report the facile synthesis of a series of CPISs 1-3 built from photocatalytic-active polyoxometalate (POM) clusters and cationic Zr-based capsules, which showed open porous frameworks with BET surface area up to 33 m2/g and high activity and selectivity for photo-driven aerobic oxidation of alcohols to aldehydes. Compared with the pristine POM cluster {W10}, 1 can promote the reaction in much higher efficiency due to the concerted catalysis of preinstalled {W10} and Zr-based capsule together with open channels. This work highlights the advantage of CPISs as porous heterogeneous catalysts in organic transformation, and may shed light on the rational design of more delicate CPISs-derived functional materials.

Passivating the pH-Responsive Sites to Configure a Widely pH-Stable Emulsifier for High-Efficiency Benzyl Alcohol Oxidation.

Widely pH-stable emulsions configured by solid emulsifiers with high chemical stabilities and anti-corrosion properties under strong acid or alkaline conditions are highly sought after for practical and wide application of Pickering interfacial catalysis. Herein, a unique strategy was reported for synthesis of a widely pH-stable and novel emulsifier by passivating the pH-responsive sites on graphene oxide nanoribbon (GONR) surface using ionic liquid (IL). The suitable wettability of GONR-IL was derived from the positive binding energy between IL and water, which ensured the stability of the emulsion in a wide pH range. Benefiting from the passivated surface chemistry of GONR, the emulsion microreactor stabilized by GONR-IL exhibited a remarkable stability over a wide range of pH values. A GONR-IL-supported Pd catalyst stabilized at the toluene-water interface achieved an excellent emulsion catalytic activity for benzyl alcohol oxidation (conversion of 92 %), which was exceedingly higher than that of Pd/GONR (<1 %), Pd/CNTs-IL (51 %), or Pd/GO-IL (8 %).

Bimetallic Oxide Catalyst for the Dehydrogenative Oxidation Reaction of Alcohols: Practical Application in the Synthesis of Value-Added Chemicals

This work demonstrates the preparation of zinc cobalt oxide materials (ZCO-1, ZCO-2, and ZCO-3) via thermal annealing of novel zinc cobalt acetate hydroxide precursors prepared in three different Co/Zn molar ratios (2:1, 1:1, and 1:2). Among these, the ZCO-1 sample displayed superior catalytic activity for the dehydrogenative oxidation of alcohols to carboxylic acids, exhibiting wide substrate applicability and high yield output with concomitant evolution of hydrogen gas (latent fuel) under oxidant-free conditions. The high catalytic activity of ZCO-1 can be accredited to synergistic effects arising from a balanced molar ratio of Co/Zn (2:1), which led to the formation of pure spinel-structured zinc cobalt oxide and a sufficiently high surface area capable of furnishing copious active sites, resulting in faster reaction kinetics and higher productivity. Moreover, the practical utility of the current protocol was displayed via ZCO-1-catalyzed gram-scale synthesis of value-added chemicals like nicotinic acid, terephthalic acid, and succinic acid.

Insight into Au/ZnO catalyzed aerobic benzyl alcohol oxidation by modulation–excitation attenuated total reflection IR spectroscopy

The chemisorbed or dissociated oxygen species is associated with the catalytic activity in alcohol oxidation catalyzed by Au/ZnO catalysts.

A smart hydrogel carrier for silver nanoparticles: an improved recyclable catalyst with temperature-tuneable catalytic activity for alcohol and olefin oxidation

Radical polymerization reactions were employed to synthesize thermo-responsive poly(N-isopropylacrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid) hydrogels at room temperature.

Synthesis of active, robust and cationic Au25 cluster catalysts on double metal hydroxide by long-term oxidative aging of Au25(SR)18.

Synthesis of an atomically precise Au25 cluster catalyst was attempted by long-term, low-temperature aging of Au25(BaET)18 (BaET-H = 2-(Boc-amino)ethanethiol) on various double metal hydroxide (DMH) supports. X-ray absorption fine structure analysis revealed that bare Au25 clusters with high loading (1 wt%) were successfully generated on the DMH containing Co and Ce (Co3Ce) by oxidative aging in air at 150 °C for >12 h. X-ray absorption near-edge structure and X-ray photoelectron spectroscopies showed that the Au25 clusters on Co3Ce were positively charged. The Au25/Co3Ce catalyst thus synthesized exhibited superior catalytic performance in the aerobic oxidation of benzyl alcohol under ambient conditions (TOF = 1097 h-1 with >97% selectivity to benzoic acid) and high durability owing to a strong anchoring effect. Based on kinetic experiments, we propose that abstraction of hydride from α-carbon of benzyl alkoxide by Au25 is the rate-determining step of benzyl alcohol oxidation by Au25/Co3Ce.

Metal-Directed Self-Assembly of {Ti8L2} Cluster-Based Coordination Polymers with Enhanced Photocatalytic Alcohol Oxidation Activity.

Cooperative assembly of the neutral cluster {Ti8O5(OEt)18L2} (L = pyrazine-2,3-dicarboxylic acid) with different metal units of Mn(NO3)2, CuCl2, Zn(OEt)2, Cd(NO3)2, Ce(NO3)3, Lu(NO3)3, and Lu(NO3)2(OEt), or the [Cu2I2] cluster, generates a family of titanium-oxygen cluster (TOC)-based coordination polymers. These one-dimensional (1D) linear structures contain the same {Ti8L2} cluster but with variable bridging metal units. The regulation of the heterometal not only affects the chain geometries of the {MTi8} but also affects the way the 1D chains are stacked in the crystal lattice. Investigation of the catalytic activities toward alcohol oxidation demonstrated the synergetic effect of combining the metal site and the photosensitive {Ti8L2} cluster in the tailored structure. Under light illumination, the {MTi8} with dual catalytic sites shows greatly enhanced catalytic activity in the selective oxidation of alcohols to aldehydes. Because the compositions and structures of {MTi8} are highly tunable, this work spotlights the potential of utilizing such metal-bridged multidimensional Ti-oxo materials for cooperative photoredox catalysis for organic transformation.

Nano-Sized NiO Immobilized on Au/CNT for Benzyl Alcohol Oxidation: Influences of Hybrid Structure and Interface.

Tiny gold nanoparticles were successfully anchored on carbon nanotubes (CNT) with NiO decoration by a two-step synthesis. Characterizations suggested that Ni species in an oxidative state preferred to be highly dispersed on CNT. During the synthesis, in situ reduction by NaBH4 and thermal treatment in oxidation atmosphere were consequently carried out, causing the formation of Au-Ni-Ox interfaces and bimetal hybrid structure depending on the Ni/Au atomic ratios. With an appropriate Ni/Au atomic ratio of 8:1, Ni atoms migrated into the sub-layers of Au particles and induced the lattice contraction of Au particles, whilst a higher Ni/Au atomic ratio led to the accumulation of NiO fractions surrounding Au particles. Both contributed to the well-defined Au-Ni-Ox interface and accelerated reaction rates. Nickel species acted as structure promoters with essential Au-Ni-Ox hybrid structure as well as the active oxygen supplier, accounting for the enhanced activity for benzyl alcohol oxidation. However, the over-layer of unsaturated gold sites easily occured under a high Ni/Au ratio, resulting in a lower reaction rate. With an Au/Ni atomic ratio of 8:1, the specific rate of AuNi8/CNT reached 185 μmol/g/s at only 50 °C in O2 at ordinary pressure.

A TEMPO-Functionalized Ordered Mesoporous Polymer as a Highly Active and Reusable Organocatalyst.

The properties of high stability, periodic porosity, and tunable nature of ordered mesoporous polymers make these materials ideal catalytic nanoreactors. However, their application in organocatalysis has been rarely explored. We report herein for the first time the incorporation of a versatile organocatalyst, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), into the pores of an FDU-type mesoporous polymer via a pore surface engineering strategy. The resulting FDU-15-TEMPO possesses a highly ordered mesoporous organic framework and enhanced stability, and shows excellent catalytic activity in the selective oxidation of alcohols and aerobic oxidative synthesis of 2-substituted benzoxazoles, benzimidazoles and benzothiazoles. Moreover, the catalyst can be easily recovered and reused for up to 7 consecutive cycles.

Dual-Site Cooperation for High Benzyl Alcohol Oxidation Activity of MnO2 in Biphasic MnOx–CeO2 Catalyst Using Aerial O2 in the Vapor Phase

Selective oxidation of benzyl alcohol to benzaldehyde in the vapor phase has drawn growing interest recently. In this work, MnOx–CeO2 mixed oxide compositions have been prepared by a coprecipitation method and tested for their oxidation activities of benzyl alcohol to benzaldehyde in the vapor phase. Detailed structural analyses have indicated that MnOx–CeO2 catalysts contain two phases, namely, α-MnO2 and fluorite CeO2 phases. The benzyl alcohol oxidation activity of pure MnO2 is more than 7 times higher compared to that of CeO2, indicating a much higher intrinsic oxidation ability of the MnO2 phase. Further, enhancement of the benzyl alcohol oxidation rate over MnO2 in 10%MnOx–CeO2 catalyst by 13 times is observed in relation to pure MnO2. The role of CeO2 in the MnOx–CeO2 catalyst has also been investigated, which indicates that the oxidation activity is almost independent of CeO2. However, stronger adsorption of benzyl alcohol over the MnOx–CeO2 catalysts compared to that of MnO2 points to the role of CeO2 in adsorption. Thus, both the CeO2 and the MnO2 components have different roles in the catalytic process—adsorption of benzyl alcohol on the CeO2 surface and its oxidation on MnO2 at the interface. The cooperation between the two sites toward oxidation could happen due to jumping of adsorbed benzyl alcohol from the surface of the CeO2 phase to the closest Mn4+ site in the MnO2 phase at the contact surface with MnO2 by thermal motion.

Immobilization of hexamolybdate onto carbon-coated Fe3O4 nanoparticle: A novel catalyst with high activity for oxidation of alcohols

A novel core-shell structural magnetic nanocatalyst involving carbon coatings on magnetic Fe3O4 nanoparticle (Fe3O4@C) for immobilizing polyoxometalate hexamolybdate (HM), were prepared by a facile chemical approach. The catalyst was identified by various techniques such as FE-SEM, EDX, VSM, XRD, TG, TEM, and FT-IR spectroscopy. This nanocatalyst were applied in the oxidation of alcohols using tert-butyl hydroperoxide, an oxidant in acetonitrile. The oxidation product was obtained at a high yield. The new nanocatalyst showed good recoverability without any significant loss of activity within successive runs.

Pd nanoparticles supported on pyrazolone-functionalized hollow mesoporous silica as an excellent heterogeneous nanocatalyst for the selective oxidation of benzyl alcohol

Hollow mesoporous silica nanoparticles (HMSNs), by exploiting both their organo-functionalized surface and porous shell were chosen as the ideal support for the immobilization of palladium nanoparticles (Pd-NPs). The HMSNs were created by acidic removal of Fe3O4 nanoparticles from silica-coated Fe3O4 core-shell. The catalyst was prepared following surface modification of HMSNs by (3-chloropropyl)-triethoxysilane (CPTES), functionalization by pyrazolone-based ligand, and stabilization of Pd-NPs on HMSNs. The resulting catalyst was fully characterized by different analytical techniques. This new heterogeneous catalyst showed high catalytic activity and excellent selectivity in the selective oxidation of benzyl alcohols in ethanol at ambient temperature. Easy separation by centrifuge and reusability for five successive cycles without significant loss of catalytic activity were some advantages of this catalyst.

Synthesis of Fe3O4@GO Nanocomposites Modified with La2O3 Nanoparticles as an Efficient Catalyst for Selective Oxidation of Aromatic Alcohols to Aldehydes

Graphene oxide (GO)-based nanocomposites decorated with metal oxide nanoparticles are promising catalysis fields owing to their multi-component interactions. In this research, a green approach for selective oxidation of benzyl alcohols to benzaldehydes was presented using novel Fe3O4@GO-La2O3 nanocomposite for the first time. The proposed nanocomposite exhibits excellent selectivity and catalytic activity for benzyl alcohol oxidation. Apart from that, this protocol can be scaled up. Absence of toxic solvent, simple product isolation, magnetic catalyst separation, and high recoverability are remarkable advantages of this approach.

A new catalytic approach for aerobic oxidation of primary alcohols based on a Copper(I)-thiophene carbaldimines

• Novel in situ copper(I) iodide schiff base catalysts. • High activity for the aerobic oxidation of benzylic, allylic and aliphatic alcohols. • Quantitative yields for benzaldehyde in 3 h with a catalyst loading of 2.5 mol%. • Diol oxidation to the corresponding lactol. We report here novel Cu(I) thiophene carbaldimine catalysts for the selective aerobic oxidation of primary alcohols to their corresponding aldehydes and various diols to lactones or lactols. In the presence of the in situ generated Cu(I) species, a persistent radical (2,2,6,6-tetramethylpiperdine-N-oxyl (TEMPO)) and N-methylimidazole (NMI) as an auxiliary ligand, the reaction proceeds under aerobic conditions and at ambient temperature. Especially the catalytic system of 1-(thiophen-2-yl)-N-(4-(trifluoromethoxy)phenyl)methanimine (ligand L2 ) with copper(I)-iodide showed high reactivity for all kind of alcohols (benzylic, allylic and aliphatic). In the case of benzyl alcohol even 2.5 mol% of copper loading gave quantitative yield. Beside high activity under aerobic conditions, the catalysts ability to oxidize 1,5-pentadiol to the corresponding lactol (86% in 4 h) and N-phenyldiethanolamine to the corresponding morpholine derivate lactol (86% in 24 h) is particularly noteworthy.

SBA-15 Supported 1-Methyl-2-azaadamanane N-Oxyl (1-Me-AZADO) as Recyclable Catalyst for Oxidation of Alcohol.

Herein, we designed and synthesized an SBA-15 supported 1-methyl-2-azaadamanane N-oxyl (1-Me-AZADO) and investigated its catalytic performance for selective oxidation of alcohols under Anelli's conditions. The first example of immobilization of 1-Me-AZADO was very important to advance the oxgenation effectively because this supported N-oxyl has excellent catalytic activity for oxidation of alcohols to carbonyl compounds, and more importantly, it can be conveniently recovered and reused at least 6 times without significant effect on its catalytic efficiency.

Novel oxovanadium and dioxomolybdenum complexes of tridentate ONO-donor Schiff base ligand: Synthesis, characterization, crystal structures, Hirshfeld surface analysis, DFT computational studies and catalytic activity for the selective oxidation of benzylic alcohols

Two new oxovanadium and dioxomolybdenum Schiff base complexes, [VvO(L)(OCH3)(CH3OH)] and [MoVIO2(L)(CH2CH3OH)], were synthesized by treating an ONO-donor type Schiff base ligand (H2L) derived by condensation of 5-nitrosalicylaldehyde and nicotinic hydrazide with oxo and dioxo acetylacetonate salts of vanadium and molybdenum, [VO(acac)2 and MoO2(acac)2], respectively. The synthesized ligand and complexes were characterized by various spectroscopic techniques like FT-IR, multinuclear (1H, 13C) NMR, elemental analysis and the most authentic single crystal X-ray diffraction analysis. In both complexes the geometry around the central metal ions was distorted octahedral as revealed by the data collected from diffraction studies. Theoretical calculation of the synthesized compounds were carried out by DFT as well as TD-DFT using B3LYP method by employing the Def2-TZVP basis set. The findings of theoretical data indicated that the calculated results are in accordance with the experimental findings. Moreover, the catalytic efficiencies of both complexes were investigated by oxidizing the benzylic alcohols in the presence of urea hydrogen peroxide (UHP) in acetonitrile.

Recognition of Water-Induced Effects toward Enhanced Interaction between Catalyst and Reactant in Alcohol Oxidation.

Pickering emulsion stabilized by solid nanoparticles provides a diverse solvent microenvironment and enables to promote the phase transfer of reaction substrates/products in catalytic reactions, but the intrinsic role of solvent is still not clear. Herein, using benzyl alcohol (BA) as a model reactant, we demonstrate the nature of the water-promoted activity for alcohol oxidation over the Pd/MgAl-LDO catalyst. Depending on the water in the solvent, we observe different reactivities regarding the proportion of the water in the system. Kinetic isotope effects confirm the participation and positive effects of water for oxidation of BA. The water promotion effects are recognized and identified by the water vapor pulse adsorption coupled with temperature program desorption. Moreover, the adsorption behavior of BA or benzaldehyde at the interface of water and Pd/MgAl-LDO is also investigated by quasi-in-situ Raman spectroscopy. In addition, the mechanism of water-promoted alcohol oxidation is rationally proposed based on the Langmuir-Hinshelwood mechanism. The general applicability of the water promotion effects is further demonstrated over different supports and substrates, which well achieves excellent catalytic activity and selectivity in Pickering emulsion compared to that in the pure toluene system.

Ternary synergistic catalyst system of Pt–Cu–Mo2C with high activity and durability for alcohol oxidation

Efficient catalyst system of high activity and durability is urgently required to convert alcohols directly on the anode in the direct alcohol fuel cells technique. Herein, an efficient ternary catalyst system of Pt–Cu–Mo2C catalyst is compositionally optimized and mechanically probed for the oxidation of methanol and ethanol fuels. Outstanding catalytic capabilities including high catalytic activity, stability, fast kinetics and high anti-poisoning ability are found due to the strong electronic effect, ligand effect and multi-oxophilic component synergism. Cu and Mo2C play different roles in the oxophilic functionalities formation as well as the anti-poisoning effect, and the combined advantages of Mo2C and Cu in the catalyst system make this ternary system more efficient for alcohols fuel oxidation compared with the traditional binary catalysts. Specifically, the peak current density of Pt–Cu–Mo2C is 80.31 mA cm−2 for methanol oxidation with a nearly 3.5-fold enhancement compared to the state-of-the-art commercial Pt/C catalyst (23.61 mA cm−2); the highest CO-tolerance ability is demonstrated by the lowest CO-oxidation peak at 0.451 V(117 mV less than Pt/C), and as high as 74.55 and 86.81% of the initial current density are maintained, respectively, after a 1000-cycle accelerated stability test towards methanol and ethanol oxidation for fuel cell reaction.

Platinum quantum dots enhance electrocatalytic activity of bamboo-like nitrogen doped carbon nanotubes embedding Co-MnO nanoparticles for methanol/ethanol oxidation

Interaction of multi-active components can effectively maximize the overall catalytic ability of alcohol fuel cells. Herein, the self-assembled nitrogen doped carbon nanotubes (NCNTs) containing Co-MnO composite (Co-MnO/NCNTs) are successfully synthesized using dihydrodiamine as carbon and nitrogen source through one-step synthesis. In order to further improve the catalytic activity of Co-MnO/NCNTs for alcohol oxidation, small amounts of platinum quantum dots are uniformly loaded on Co-MnO/NCNTs formation of quaternary hybrid (named Pt/Co-MnO/NCNTs) during microwave reduction stage. Notably, the prepared Pt/Co-MnO/NCNTs hybrids possess the excellent methanol and ethanol oxidation mass current density of 1775.4 and 1112.8 mA mg−1 in alkaline condition, which are 3.6 and 2.25 times higher than that of Pt/C catalysts, respectively. The current density of ethanol catalytic oxidation is lower than that of methanol, which may be due to the partial oxidation of acetyl (the intermediate product of ethanol) on the Pt (1 1 1) crystal surface. More importantly, CO oxidation experiments reveal that strong electronic synergistic effect between MnO and Pt quantum dot can greatly improve the CO anti-poisoning ability. Another significant advantage of Pt/Co-MnO/NCNTs is that low platinum loading leads to low cost effective, which demonstrates that the modification non-noble metal catalysts with a few noble metals quantum dots is a promising choice to mass produce high performance catalyst with remarkably boosting electrocatalytic activity for alcohol oxidation.