Visible-light Responsive Cu-MOF-NH 2 for Highly Efficient Aerobic Photocatalytic Oxidation of Benzyl Alcohol

The current study focuses on the photocatalytic oxidation of benzyl alcohol in acetonitrile under air bubbling conditions comparing titania-based materials, Cu-MOF, and Cu-MOF-NH2 as semiconductor photocatalysts. The catalysts were characterized by XRD, N2 adsorption-desorption, FT-IR, Raman spectroscopy, and TEM. The photocatalytic benzyl alcohol conversion reached ~ 100% after exposing the four prepared catalysts to a 125W mercury lamp for up to 240 min. Benzaldehyde is formed with a moderate selectivity (after a reaction time of 60 min. ca. 30% over the titania-based catalysts 37%, 45% over Cu-MOF, and Cu-MOF-NH2, respectively). The formation of electron-hole pairs at the surface of the semiconductor nanoparticles followed by oxidation reaction was the suggested mechanism. A first-order kinetic model was observed for the photocatalytic oxidation of the investigated alcohols, and the rate constants were calculated. According to preliminary research, decorating MOF linker by amine (MOF-NH2) could improve visible-light harvesting, charge separation, and electron transport of the resulting catalyst, resulting in increased photocatalytic activity. The current work offers some direction for the development of MOF-based photocatalysts for organic synthesis.

Palladium-doped hierarchical ZSM-5 for catalytic selective oxidation of allylic and benzylic alcohols

Hierarchical zeolites have the potential to provide a breakthrough in transport limitation, which hinders pristine microporous zeolites and thus may broaden their range of applications. We have explored the use of Pd-doped hierarchical ZSM-5 zeolites for aerobic selective oxidation (selox) of cinnamyl alcohol and benzyl alcohol to their corresponding aldehydes. Hierarchical ZSM-5 with differing acidity (H-form and Na-form) were employed and compared with two microporous ZSM-5 equivalents. Characterization of the four catalysts by X-ray diffraction, nitrogen porosimetry, NH 3 temperature-programmed desorption, CO chemisorption, high-resolution scanning transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy allowed investigation of their porosity, acidity, as well as Pd active sites. The incorporation of complementary mesoporosity, within the hierarchical zeolites, enhances both active site dispersion and PdO active site generation. Likewise, alcohol conversion was also improved with the presence of secondary mesoporosity, while strong Brønsted acidity, present solely within the H-form systems, negatively impacted overall selectivity through undesirable self-etherification. Therefore, tuning support porosity and acidity alongside active site dispersion is paramount for optimal aldehyde production.

Synthesis, Crystal Structure of Tetra-Nuclear Macrocyclic Zn(II) Complex and Its Application as Catalyst for Oxidation of Benzyl Alcohol

A new six coordinated tetra-nuclear macrocyclic Zn(II) complex, ZnL4(Phen)2 (1) (HL= 3-bromo-2-hydroxybenzaldehyde-pyridine-2-carbohydrazone, Phen = 1,10-phenanthroline) has been synthesized by the self-assembly of 3-bromo-2-hydroxybenzaldehyde-pyridine-2-carbohydrazone, Zn(CH3COO)2•2H2O, NaOH and 1,10-phenanthroline in water/ethanol (v:v = 1:3) solution. Complex 1 was characterized by elemental analysis, infra red (IR), and single-crystal X-ray diffraction (XRD) analysis. The results show that Zn1 and Zn1b ions are six-coordinated with a distorted octahedral geometric configuration by four O atoms of two different L ligands and two N atoms of two different L ligands, Zn1a and Zn1c ions are also six-coordinated with a distorted octahedral geometric configuration by two N atoms of two different L ligands, two N atoms of Phen ligands and two O atoms of two different L ligands. Complex (1) forms 3D network structure by the - interaction. The selective oxidation reactions of benzyl alcohols catalyzed by complex (1) was investigated. The highest benzyl alcohol conversion and benzaldehyde selectivity were obtained at 100 °C for 4 h under 5 bar of O2. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Catalytic Effects of the New Schiff Base Metal Complexes on the Conversion of Benzyl Alcohol to Benzaldehyde and Benzoic Acid

In this study, two new salicylidene hydroxyl ligands (HL1 and HL2) and their metal complexes (Cu2+, Mn2+, Fe3+, Ru3+, Cr3+, and VO2+) were synthesized and characterized by the spectroscopic and analytical methods. The molecular structure of the ligand HL1 was determined by a single-crystal X-ray diffraction study. Catalytic effects of the Schiff base metal complexes on benzyl alcohol were investigated in the H2O2 medium. In this oxidation reaction, the percent conversion of benzyl alcohol to benzaldehyde and benzoic acid was determined as %benzaldehyde and %benzoic acid by the gas chromatography (GC) method. Finally, the synthesized metal complexes found the highest catalytic effect that Co and Mn metal complexes 97-98% benzyl alcohol conversion. And maximum %benzoic acid formation is seen in MnL1 (39%) and VOL1 (58%) metal complexes.

Reversible ketone hydrogenation and dehydrogenation for aqueous organic redox flow batteries

Aqueous redox flow batteries with organic active materials offer an environmentally benign, tunable, and safe route to large-scale energy storage. Development has been limited to a small palette of organics that are aqueous soluble and tend to display the necessary redox reversibility within the water stability window. We show how molecular engineering of fluorenone enables the alcohol electro-oxidation needed for reversible ketone hydrogenation and dehydrogenation at room temperature without the use of a catalyst. Flow batteries based on these fluorenone derivative anolytes operate efficiently and exhibit stable long-term cycling at ambient and mildly increased temperatures in a nondemanding environment. These results expand the palette to include reversible ketone to alcohol conversion but also suggest the potential for identifying other atypical organic redox couple candidates.

Ru0·Run+/Al2O3 as a Versatile Catalyst in the Isomerization of Allyl Alcohol

This study focuses on examining the isomerization of allyl alcohol using ruthenium (Ru) supported on alumina as a heterogeneous catalyst. The synthesized Ru/Al solids were characterized by various characterization techniques. The content of Ru was estimated by the energy dispersive x-ray technique. The x-ray diffraction (XRD) confirmed the presence of phases in the support and active species in the catalysts. The surface area of the support after Ru impregnation and the pore volume were determined by nitrogen physisorption. The analysis of programmed temperature (TPR and TPO) shows different redox sites which is confirmed by XPS. The catalytic results suggest a dependence on the amount of available metallic Ru, as well as the importance of the continuous regeneration of the metal using H2 to achieve a good conversion of the allyl alcohol. For comparison purposes, the commercial Ru on alumina 5% (CAS 908142) was used. The results show up to 68% alcohol conversion and 27% yield of the isomerization product using Ru(1,5.4h)/Al catalyst in comparison with 86% conversion and 39% yield of the isomerization product using CAS 908142. In contrast, our catalysts always presented higher TOF values (149–160) in comparison with CAS 908142 (101).

Tuning the Reaction Selectivity over MgAl Spinel-Supported Pt Catalyst in Furfuryl Alcohol Conversion to Pentanediols

Catalytic conversion of biomass-derived feedstock to high-value chemicals is of remarkable significance for alleviating dependence on fossil energy resources. MgAl spinel-supported Pt catalysts were prepared and used in furfuryl alcohol conversion. The approaches to tune the reaction selectivity toward pentanediols (PeDs) were investigated and the catalytic performance was correlated to the catalysts’ physicochemical properties based on comprehensive characterizations. It was found that 1–8 wt% Pt was highly dispersed on the MgAl2O4 support as nanoparticles with small sizes of 1–3 nm. The reaction selectivity did not show dependence on the size of Pt nanoparticles. Introducing LiOH onto the support effectively steered the reaction products toward the PeDs at the expense of tetrahydrofurfuryl alcohol (THFA) selectivity. Meanwhile, the major product in PeDs was shifted from 1,5-PeD to 1,2-PeD. The reasons for the PeDs selectivity enhancement were attributed to the generation of a large number of medium-strong base sites on the Li-modified Pt catalyst. The reaction temperature is another effective factor to tune the reaction selectivity. At 230 °C, PeDs selectivity was enhanced to 77.4% with a 1,2-PeD to 1,5-PeD ratio of 3.7 over 4Pt/10Li/MgAl2O4. The Pt/Li/MgAl2O4 catalyst was robust to be reused five times without deactivation.