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Catalytic oxidation of a number of straight-chain/cyclic aliphatic alcohols was examined in the presence of hydrogen peroxide and Merrifield resin-supported binuclear dioxidovanadium(V) complexes of hydrazone ligands in the absence of any additional solvent. The dioxidovanadium(V) complexes K2[(VO2-sal)2-dmh)]2− (1), K2[(VO2-Csal)2-dmh]2− (2), and K2[(VO2-Bsal)2-dmh]2− (3) were synthesized in the form of their K+-salt by reacting hydrazone based ligands H2(sal)2-dmh (I), H2(Csal)2-dmh (II), and H2(Bsal)2-dmh (III), with the vanadium precursor VO(acac)2, respectively. Imidazole functionalized Merrifield resin was used to heterogenize the dioxidovanadium complexes 1–3. XPS analysis reveals that the vanadium loading in the Merrifield resin is a few percent, and the oxidation state of the vanadium center in the grafted complexes is +5. A maximum substrate conversion of 95% (in the presence of 4), 90% (in the presence of 5), and 92% (in the presence of 6) is observed during the oxidation of ethanol, and acetic acid is the solo product. In general, cyclic alcohols are less reactive than acyclic ones. Whereas, alcohols with a higher number of carbon chains are less reactive than alcohols with fewer carbon atoms. [ABSTRACT FROM AUTHOR]

The development of sustainable synthetic methods for converting alcohols to amines is of great interest due to their widespread use in pharmaceuticals and fine chemicals. In this work, we present an electrochemical approach by using green electrons for the selective oxidation of benzyl alcohol to benzaldehyde using a NiOOH catalyst, followed by its reductive amination to form benzyl-tert-butylamine. The number of Ni monolayer equivalents on the catalyst was found to significantly influence selectivity, with 2 monolayers achieving up to 90% faradaic efficiency (FE) for benzaldehyde in NaOH, while 10 monolayers performed best in a tert-butylamine solution (pH 11), yielding 100% FE for benzaldehyde. Reductive amination of benzaldehyde was optimized on Ag and Pb electrodes, with Ag achieving 39% FE towards the amine product, though hydrogen evolution remained a competing reaction. In situ FTIR spectroscopy confirmed the formation of benzaldehyde and its corresponding imine intermediate during oxidation, while reduction spectra supported the formation of the amine product. These results demonstrate the potential of paired electrolysis for alcohol-to-amine conversion, achieving an overall 35% FE for the synthesis of benzyl-tert-butylamine. This work paves the way for more efficient and sustainable electrochemical routes to amine synthesis. [ABSTRACT FROM AUTHOR]

The generation of aldehydes and sulfoxides through selective oxidation process plays an essential role in different organic synthesis. However, using or toxic solvents under harsh reaction conditions leads to wastes and undesired by-products. With this background, ultrafast one-step fabrication of Ni/Mn doped-ZnO was developed under ultrasonic agitation for the first time. The resulting nanostructure was characterized by XRD, SEM, TEM, and BET analysis. According to data, a single-phase ZnO structure (wurtzite type) with uniform morphology, and acceptable surface area was obtained for the prepared nanocatalyst. Next, the catalytic activity of the nanostructure was investigated in aerobic oxidation of aliphatic and benzylic alcohols and sulfides. Notably, the present work is the first report of using ultrasound-engendered Ni/Mn doped-ZnO for selective aerobic oxidation reactions. It was found that the proposed nanostructure represented a novel chemical function for catalyzed alcohols and sulfides oxidation with excellent yields and selectivity without using any additives. [ABSTRACT FROM AUTHOR]

In this work, a stable bimetallic hydrotalcite-derived NiCu/MgAlO catalyst and O2 as oxidant were used for the toluene oxidation to produce the valuable benzyl alcohol (PhCH2OH) and benzaldehyde (PhCHO) under solvent-free and additive-free conditions. This strategy gave 7.2% toluene conversion with 70.7% selectivity to PhCH2OH & PhCHO. Multiple characterizations showed that highly dispersed metallic Cu and Ni were anchored on the support surface and a chemical bonding interaction occurred between the metallic Ni and the MgAlO. The metal–support interaction contributed to the formation of active Ni0 species and NiCu alloy with abundant oxygen defects, resulting in excellent catalytic activity and acceptable stability. A plausible reaction mechanism for the catalytic oxidation of toluene over NiCu/MgAlO catalyst has been proposed. The attractive feature of the present catalytic oxidation system compared to conventional methods was its ability to achieve high selectivity for the desired target product. The further advantage of NiCu/MgAlO catalyzed toluene oxidation was that the reaction temperature and time could be below 180 °C and 2 h, thereby minimizing energy consumption and reducing effluent wastewater, which has potential application prospects. [ABSTRACT FROM AUTHOR]

Silver and vanadium phosphorus oxide are well known for catalytic activity for benzaldehyde production. Silver also enables the electrochemical oxidation of alcohol. Here, we report the catalytic characterization of Ag/VPO/TiO2 nanostructures for selective benzaldehyde production and oxidation of alcohols. The catalyst composition includes 13.5 wt.% vanadium phosphorus oxide (VPO) and 10 wt.% silver nanoparticles embedded on titanium oxide nanotubes to form nanostructures with flake morphology. In the benzaldehyde production reaction, the mass of VPO was reduced without affecting the conversion efficiency of toluene and styrene of VPO when incorporated with TiO2. Remarkably, the introduction of Ag to the catalyst significantly promoted the conversion of toluene and styrene, which is believed to be due to the ability of Ag to enhance the bond breaking of the H2O2 reagent and the transition compounds. On the other hand, the cyclic voltammetry results revealed that Ag and VPO were both active components for methanol and ethanol oxidation in alkaline medium. The results highlight the ability of Ag to improve the catalytic activity in alcohol oxidation and the benefits of using multi-site catalysts that can be applied for more than one reaction. [ABSTRACT FROM AUTHOR]

The application of MOFs in electrochemical energy fields has attracted great attention in recent years. In this regard, Ni-MOF was synthesized via a solvothermal method using 1,4-benzene dicarboxylic acid (H 2 BDC) as a linker. XRD confirmed the structure of the synthesized Ni-MOF as [Ni 3 (OH) 2 (H 2 O) 4 (C 8 H 4 O 4) 2 ] 2H 2 O. Its porous nature and specific surface area of 82.7 m2 g⁻1 were estimated using BET analysis. Thermal stability was evaluated by TGA, allowing for the calculation of decomposition parameters (E a , ΔH∗, ΔS∗, and ΔG∗). The chemical structure was further validated using FTIR. Ni-MOF powder was blended with carbon black (XC-72) in various ratios to enhance the conductivity and electrocatalytic activity, and the resulting composite was ink-casted onto graphite electrodes. Surface morphology, particle size, and elemental composition were assessed by SEM and EDX, while chemical composition was analyzed through XPS. Notably, the 1:1 Ni-MOF/C composite electrode showed promising catalytic activity for the electrooxidation of methanol, ethanol, ethylene glycol, and glycerol, achieving oxidation current densities of 132, 96, 67, and 57 mA cm⁻2 at +0.8 V (Hg/HgO/OH−), respectively, along with impressive stability. Electrocatalytic performance was further evaluated by calculating electrochemical parameters like diffusion coefficient (D), transfer coefficient (α), catalytic rate constant (K o), Tafel slope, and charge transfer resistance (R ct). The effectiveness of electron transfer processes on Ni-MOF/C relies on the oxidation state of Ni metal ions and the synergistic effect of Ni-MOF and conductive carbon black. EIS results indicated rapid charge transfer processes during alcohol electrooxidation, with the order of efficiency being: methanol > ethanol > ethylene glycol > glycerol. DFT studies investigated the interactions between Ni-MOF crystal facets and alcohol molecules, HOMO−LUMO calculations showed that alcohols possess strong electron donation capabilities, suggesting a favorable affinity for the electrooxidation process. [Display omitted] • Ni-MOF composites with carbon black (XC-72) enhance electrocatalytic activity. • The Ni-MOF: C (1:1) composite exhibited high catalytic activity and durability. • The composite's high performance is due to its porosity and Ni catalytic activity. • DFT revealed that alcohols exhibit strong electron donation abilities. [ABSTRACT FROM AUTHOR]

Utilizing photocatalytic technology for the value-added conversion of biomass derivatives, alongside the production of clean hydrogen energy, represents a viable approach to addressing energy and environmental challenges. However, the design of cost-effective and efficient photocatalysts remains a significant obstacle. In this work, we employed open-framework Prussian blue analogs as co-catalytic centers and combined them with ZnIn2S4 to construct a series of core-shell nanocube photocatalysts with varying metal compositions. This unique structure provides abundant photocatalytic redox-active sites and effectively facilitates the separation and transfer of photoinduced charges. By examining the oxidation of furfuryl alcohol (FOL) to furfural (FAL) with cooperative H2 evolution, the optimal Ni-Co PBA@ZnIn2S4 sample exhibited remarkable catalytic activity, achieving H2 and FAL yields of 739.3 and 705.2 µmol g-1 h-1, respectively, which is approximately four times greater than that achieved with bare ZnIn2S4. This study offers valuable insights into the design of photocatalysts and the selection of co-catalytic metal centers. [ABSTRACT FROM AUTHOR]

Novel porous Fe-doped hcp -PtBi/ fc c-Pt heterostructured nanoplates have been prepared as high-performance multifunctional anode catalysts for C3 alcohol oxidation. [Display omitted] • Porous Fe-doped hcp -PtBi/ fcc -Pt heterostructured nanoplates (h-PtBi/f-Pt@Fe 1.7 PNPs) were achieved. • h -PtBi/ f -Pt@Fe 1.7 PNPs possessed superior C3 alcohol oxidation properties. • h -PtBi/ f -Pt@Fe 1.7 PNPs achieved complete electrooxidation of C3 alcohols. • h-PtBi/f-Pt@Fe 1.7 PNPs delivered higher power density (125.8 mW cm−2) than commercial Pt/C in actual DGFCs. Efficient C C bond cleavage and the complete oxidation of alcohols are key to improving the efficiency of renewable energy utilization. Herein, we successfully prepare porous Fe-doped hexagonal close-packed (hcp)-PtBi/face-centered cubic (fcc)-Pt heterostructured nanoplates with abundant grain/phase interfaces (h -PtBi/ f -Pt@Fe 1.7 PNPs) via a simple solvothermal method. The open porous structure, abundant grain/phase interface and stacking fault defects, and the synergistic effect between intermetallic hcp -PtBi and fcc -Pt make h -PtBi/ f -Pt@Fe 1.7 PNPs an effective electrocatalyst for the glycerol oxidation reaction (GOR) in direct glycerol fuel cells (DGFCs). Notably, the h -PtBi/ f -Pt@Fe 1.7 PNPs exhibit an excellent mass activity of 7.6 A mg Pt −1 for GOR, 4.75-fold higher than that of commercial Pt black in an alkaline medium. Moreover, the h -PtBi/ f -Pt@Fe 1.7 PNPs achieve higher power density (125.8 mW cm−2) than commercial Pt/C (81.8 mW cm−2) in a single DGFC. The h -PtBi/ f -Pt@Fe 1.7 PNPs can also effectively catalyze the electrochemical oxidation of 1-propanol (17.1 A mg Pt −1), 1,2-propanediol (7.2 A mg Pt −1), and 1,3-propanediol (5.2 A mg Pt −1). The in-situ Fourier-transform infrared spectra further reveal that the C C bond of glycerol, 1-propanol, 1,2-propanediol, and 1,3-propanediol was dissociated for the complete oxidation by the h -PtBi/ f -Pt@Fe 1.7 PNPs. This study provides a new class of porous Pt-based heterostructure nanoplates and insight into the intrinsic activity of different C3 alcohols. [ABSTRACT FROM AUTHOR]

The oxidative depolymerization of β-O-4 linkages into value-added aromatic chemicals is of great importance for lignin valorization. However, achieving highly selective and rapid cleavage of β-O-4 linkages under mild conditions remains a challenge. Herein, cobalt–cobalt oxides (Co-CoOx) supported on N-doped carbon (CoMA/C900) combined with a green and recyclable base K7HNb6O19 (KNb6) have shown remarkable activity for the one-step oxidative cleavage of lignin β-O-4 linkages. Under relatively mild conditions (100 °C, 0.2 MPa O2), a lignin β-O-4 alcohol model compound was almost completely converted within 3 h, affording a narrow product distribution of phenol (yield: 99%) and methyl benzoate (yield: 98%). Based on the control experiments, kinetic study, and spectroscopic analysis, a synergistic oxidative cleavage mechanism was proposed: CoMA/C900 activates molecular oxygen to form a superoxide radical, while basic KNb6 promotes deprotonation of secondary alcohol, and they synergistically catalyze the oxidation of β-O-4 alcohol and the rapid cleavage of Cβ–O and Cα–Cβ bonds. During the reaction, the oxidation of β-O-4 alcohol to β-O-4 ketone is the rate-determining step, while the cleavage of PP-one to phenol and methyl benzoate can be completed within 15 min. Moreover, the CoMA/C900–KNb6 catalyst is recyclable at least three times and highly active for the oxidative cleavages of other lignin models and organosolv birch lignin. [ABSTRACT FROM AUTHOR]

The document "Green Chemistry" published by the Royal Society of Chemistry in 2025 features cutting-edge research articles on various topics related to sustainable chemistry. The contents include critical reviews, tutorial reviews, communications, and papers covering a wide range of subjects such as catalytic hydrogenolysis of plastics waste, electrochemical synthesis methods, and green catalytic conversion processes. The journal aims to promote environmentally friendly practices and innovative solutions for a greener future. [Extracted from the article]

In recent years, the catalytic oxidation of cheap and easily available alcohols to value-added carboxylic acids has attracted considerable interest. In this work, a post-synthetic modification strategy was employed to anchor Cu species to coordinate with the -NH2 in UiO-66-NH2(Ce), obtaining the catalyst Cu-UiO-66-NH2(Ce). The catalyst exhibited excellent performance for the direct oxidation of alcohols to carboxylic acids under mild reaction conditions without extra bases. The synthesized materials were characterized by XRD, SEM, XPS, BET, FT-IR, Raman and ICP-OES, the results show that Cu species were successfully anchored onto UiO-66-NH2(Ce) by the coordination with N atoms. Moreover, the coordination between Cu ions and N atoms as well as the unique structure of UiO-66-NH2(Ce) could provide uniformly catalytic active centers on heterogeneous catalyst, which are essential for the high catalytic performance of the catalyst. Furthermore, the recyclability of the catalyst was also investigated, which can be recovered and recycled for 10 times without significant loss of catalytic activity. This work provides an efficient and cost-effective approach to the direct oxidation of alcohols to carboxylic acids. [ABSTRACT FROM AUTHOR]

[Display omitted] • A chemically bonded 0D/2D Au/ZIS-V ohmic junction was prepared. • Synergistic effect of built-in electric field, Au-S bonds and Zn vacancies on dual-function photocatalysis. • Au/ZIS-V is suitable for photocatalytic selective alcohol oxidation coupled with H 2 production and CO 2 reduction. • The thermodynamics and kinetics of photoredox were simultaneously improved. • The utilization factor of photoexcited holes to electrons can reach up to 0.99. Combining photocatalytic reduction with organic synthetic oxidation in the same photocatalytic redox system can effectively utilize photoexcited electrons and holes from solar to chemical energy. Here, we stabilized 0D Au clusters on the substrate surface of Zn vacancies modified 2D ZnIn 2 S 4 (ZIS-V) nanosheets by chemically bonding Au-S interaction, forming surfactant functionalized Au/ZIS-V photocatalyst, which can not only synergistic accelerate the selective oxidation of phenylcarbinol to value-added products coupled with clean energy hydrogen production but also further drive photocatalytic CO 2 -to-CO conversion. An internal electric field of Au/ZIS-V ohmic junction and Zn vacancies synchronously promote the photoexcited charge carrier separation and transfer to optimized active sites for redox reactions. Compared with CO 2 reduction in water and the pristine ZnIn 2 S 4 , the reaction thermodynamics and kinetics of CO 2 reduction over the Au/ZIS-V were simultaneously improved about 11.09 and 45.51 times, respectively. Moreover, the photocatalytic redox mechanisms were also profoundly studied by 13CO 2 isotope tracing tests, in situ electron paramagnetic resonance (in situ EPR), in situ X-ray photoelectron spectroscopy (in situ XPS), in situ diffuse reflection infrared Fourier transform spectroscopy (in situ DRIFTS) and density functional theory (DFT) characterizations, etc. These results demonstrate the advantages of vacancies coupled with metal clusters in the synergetic enhancement of photocatalytic redox performance and have great potential applications in a wide range of environments and energy. [ABSTRACT FROM AUTHOR]

A CuO@ZnFe-LDH composite, prepared from the co-precipitation of Cu2+ with ZnFe-LDH, served as an environmentally friendly photocatalyst. This catalyst was implemented in the selective oxidation of various primary and secondary alcohols to aldehydes or ketones utilizing air as the oxidant, 2,2,6,6-tetramethylpiperidine 1-oxyl radical (TEMPO), and sunlight as the light source. The yields varied from low to excellent. It was notable that the oxidation process also allowed for very selective conversion of benzylic alcohols that had phenolic hydroxyl groups. Moreover, leaching of copper from the catalyst during the reaction was minimal. Also, CuO@ZnFe-LDH could be effectively reused, while maintaining its high catalytic activity. [ABSTRACT FROM AUTHOR]

Using biomass oxidation reactions instead of water oxidation reactions is optimal for accomplishing biomass conversion and effective hydrogen generation. Here, we report that α‐Fe2O3 photoanodes with a NiOOH cocatalyst exhibit excellent performance for photoelectrochemical oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA). The conversion efficiency for HMF reaches 98.5 %, while the selectivity for FDCA is 94.2 %. We revealed that HMF is oxidized through a spontaneous proton‐coupled electron transfer (PCET) process with the high‐valent phase of the Ni‐based catalyst. The dangling oxygen and bridging oxygen of the high‐valent phase species serve as proton‐accepting sites. Furthermore, we pointed out that the deprotonated bond dissociation free energy difference between the catalysts and alcohols is the thermodynamic trigger for the PCET process. This study provides a reasonable explanation for the alcohol oxidation reaction, which is beneficial for designing biomass conversion systems. [ABSTRACT FROM AUTHOR]

PdCu nanorings (NRs) featuring hollow interiors and low coordinated sites are synthesized as efficient electrocatalysts for ethanol and ethylene glycol oxidation reactions. [Display omitted] Two-dimensional (2D) Pd-based nanostructures with a high active surface area and a large number of active sites are commonly used in alcohol oxidation research, whereas the less explored ring structure made of nanosheets with large pores is of interest. In this study, we detail the fabrication of PdCu nanorings (NRs) featuring hollow interiors and low coordinated sites using a straightforward solvothermal approach. Due to increased exposure of active sites and the synergistic effects of bimetallics, the PdCu NRs exhibited superior catalytic performance in both the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR). The mass activities of PdCu NRs for EOR and EGOR were measured at 7.05 A/mg and 8.12 A/mg, respectively, surpassing those of commercial Pd/C. Furthermore, the PdCu NRs demonstrated enhanced catalytic stability, maintaining higher mass activity levels compared to other catalysts during stability testing. This research offers valuable insights for the development of efficient catalysts for alcohol oxidation. [ABSTRACT FROM AUTHOR]

Micelles, a unique structural arrangement, function as nano-dimensional vessels in organic reactions, facilitating numerous catalytic transformations in water. This comprehensive study aims to explore the potential impact of two anionic surfactants (sodium dodecylsulphate or SDS or SC12S and sodium tetradecylsulphate or STS or SC14S) having dissimilar alkyl chain lengths and the hydrophobicity of the aliphatic alcohols (propanol and pentanol) as well on the overall kinetic profile of the oxidation study. The SDS micellar medium significantly encourages the reaction rate compared to STS micellar media. In the case of aliphatic alcohols with varying hydrophobicity, the same kind of rate is observed as with surfactants: (kobs)SDS-Propanol ~ 13-folds > (kobs)SDS-Pentanol ~ 11-folds > (kobs)STS-Propanol ~ 2.4-folds > (kobs)STS-Pentanol ~ 2-folds. The rate of the reaction improves as the aliphatic alcohol and surfactant hydrophobicity reduces. Herein, the effectiveness of micellar catalysis is greatly influenced by the surface charge of the micelle and surfactant-alcohol hydrophobic interaction. The kinetic observations are elucidated with conductometry, fluorometry, UV–Vis spectroscopy, FT-IR, 1H-NMR, DLS, FESEM, TEM, and Zeta potential analysis. The Piszkiewicz's kinetic model has also been applied to enlighten the linear rate acceleration in both micellar media. [ABSTRACT FROM AUTHOR]

The present study introduces polyvinyl cyanuric chloride (PVCC) as an efficient reagent for the selective catalyst/metal-free oxidation of primary and secondary alcohols to the corresponding aldehyde and ketones in the presence of dimethyl sulfoxide (DMSO) as a solvent and oxidant. PVCC was derived from polyvinyl alcohol (PVA) and synthesized simply in the presence of cyanuric chloride (2,4,6-Trichloro-1,3,5-triazine or TCT) in one step. The oxidation was conducted at 50 °C in the absence of any other external oxidant. All 25 entries under study achieved high selectivity, up to 98%, within 30 to 120 min. PVCC could be recovered, re-activated by POCl3/PCl5 and re-used for at least five consecutive runs without any considerable reactivity loss. The oxidation system was inert toward oxidation of aldehydes. A highly selective protocol has been developed for alcohol oxidation to aldehyde using polyvinyl cyanuric chloride and DMSO as a solid reagent and oxidant/solvent respectively. [ABSTRACT FROM AUTHOR]

The first metallasilsesquioxane bearing pyrazolylpyridine ligands, the Cu8-based complex 1, adopts a cage-like structure with two zigzag-type copper tetramers sandwiched by two cyclic Si5 silsesquioxane ligands. The four 3-phenyl-5-(2-pyridyl)pyrazolate ligands in 1 exhibit dual (chelating and bridging) modes of ligation. Compound 1 is very active in the oxidation of alkanes and alcohols. [ABSTRACT FROM AUTHOR]

The liquid-phase selective oxidation of benzyl alcohol is a sustainable route for the synthesis of benzaldehyde. Wherein, the exploration of heterogeneous and cheap metal oxide catalysts instead of noble metal catalysts is of interest in both practical implementation and green chemistry. Herein, vanadium dioxide (VO2) nanosheets were prepared via a one-step hydrothermal reduction of V2O5 by citric acid. The hydrothermal temperature and time played important roles in determining the crystalline structure, morphology, and distribution of V valences of VO2 materials. In the selective oxidation of benzyl alcohol by atmospheric O2, VO2 materials as heterogeneous catalysts showed catalytic activity. Based on XPS and O2-TPD analysis, the catalytically active sites were proposed as V4+ species. At a reaction temperature of 95 °C, the maximum yield of benzaldehyde was up to 91.6% after 6 h, and the VO2-140-5 catalyst can be recycled at least five times without any obvious loss in activity. [ABSTRACT FROM AUTHOR]

The liquid-phase selective oxidation of benzyl alcohol is a sustainable route for the synthesis of benzaldehyde. Wherein, the exploration of heterogeneous and cheap metal oxide catalysts instead of noble metal catalysts is of interest in both practical implementation and green chemistry. Herein, vanadium dioxide (VO2) nanosheets were prepared via a one-step hydrothermal reduction of V2O5 by citric acid. The hydrothermal temperature and time played important roles in determining the crystalline structure, morphology, and distribution of V valences of VO2 materials. In the selective oxidation of benzyl alcohol by atmospheric O2, VO2 materials as heterogeneous catalysts showed catalytic activity. Based on XPS and O2-TPD analysis, the catalytically active sites were proposed as V4+ species. At a reaction temperature of 95 °C, the maximum yield of benzaldehyde was up to 91.6% after 6 h, and the VO2-140-5 catalyst can be recycled at least five times without any obvious loss in activity. [ABSTRACT FROM AUTHOR]

Poly(4‐hydroxybutyrate) (P4HB) is a high‐performance, well‐recyclable, and biodegradable polyhydroxyalkanoate (PHA). However, conventional bioproduction of homopolymeric P4HB involves complex and costly processes with C4 feedstocks, particularly 1,4‐butanediol (BDO), and enzyme‐coenzyme systems in genetically engineered bacteria. An alternative extracellular chemical route utilizing aerial oxidation of BDO offers cost and energy benefits but struggle with conversion efficiency. Inspired by efficient intracellular oxidation of primary alcohols, we propose a ruthenium‐phosphine synergistic catalytic system that mimics enzyme‐coenzyme functionality. This system effectively catalyzed the air‐mediated, solvent‐free oxidation of BDO to produce γ‐butyrolactone (γ‐BL) and oligomeric P4HB, with a space‐time yield (10.37 g [γ‐BL unit] g−1 catalyst h−1) surpassing the values (<5.5) of previous approaches. The oligomer‐containing products were reversibly converted to γ‐BL and then to P4HB (28.9 kDa) via ring‐opening polymerization, exceeding reported values (<16 kDa). This study provides the potential for large‐scale synthesis of high‐value PHAs from diverse non‐grain‐based diols, offering economic and environmental advantages. [ABSTRACT FROM AUTHOR]

Dye‐sensitized photoelectrochemical cells can enable the production of molecules currently accessible through energetically demanding syntheses. Copper(I)‐based dyes represent electronically tunable charge transfer and separation systems. Herein, we report a Cu(I)‐bisdiimine donor‐chromophore‐acceptor dye with an absorbance in the visible part of the solar spectrum composed of a phenothiazine electron donor, and dipyrido[3,2‐a:2′,3′‐c]phenazine electron acceptor. This complex is incorporated onto a zinc oxide nanowire semiconductor surface effectively forming a photoanode that is characterized spectroscopically and electrochemically. We investigate the photo‐oxidation of hydroquinone, and the photosensitization of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl and N‐hydroxyphthalimide for the oxidation of furfuryl alcohol to furfuraldehyde, resulting in near quantitative conversions, with poor selectivity to the alcohol. [ABSTRACT FROM AUTHOR]

An optimised synthesis of the metal‐organic framework (MOF) UiO‐66(Ce) is reported using a modulator‐free route, yielding ~5 g of material with high crystallinity and 22 % ligand defect. Two methods are developed for loading gold nanoparticles onto the MOF. The first uses a double‐solvent method to introduce HAuCl4 onto UiO‐66(Ce), followed by reduction under 5 % H2 in N2, while the second is a novel one‐pot method where HAuCl4 is added to the synthesis mixture, forming Au nanoparticles within the pores of the UiO‐66(Ce) during crystallisation. Analysis using powder X‐ray diffraction (PXRD), nitrogen adsorption isotherms, transmission electron microscopy and small‐angle X‐ray scattering (SAXS) reveals that the two‐step double‐solvent method yields gold crystallites on the external surface of the MOF particles that are visible by PXRD. In contrast, the one‐pot method forms smaller gold crystallites, with a distribution of sizes centred on ~4 nm diameter as seen by SAXS, with evidence from PXRD for the smallest particles being present within the MOF structure. The Au‐loaded UiO‐66(Ce) materials are evaluated for the catalytic oxidation of vanillyl alcohol to vanillin at 60 °C. Our findings indicate that incorporating Au nanoparticles via the one‐pot synthesis method, enhances redox activity, achieving 43 % conversion and 90 % selectivity towards vanillin. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A mechanistically distinctive visible‐light‐promoted metal‐free aerobic oxidation of alkenyl silanes with alcohols was disclosed to efficiently construct α‐alkoxy ketones under mild conditions. The primary, secondary, and tertiary alcohols could be used as reactants. The protocol could be carried out on a gram‐scale. Various derivatizations of products could be conducted. Mechanistic studies indicated the reaction was initiated by single‐electron oxidation of the alkenyl silanes, rather than radical addition to alkenyl silanes. [ABSTRACT FROM AUTHOR]

Industrial production of H2O2 requires lots of energy and causes environmental pollution. Moreover, in subsequent applications, much economic loss could be produced during the transportation process of H2O2 and its dilution process. Therefore, it is highly desirable for in situ application of H2O2. In recent years, catalytic synthesis of H2O2, e. g., direct catalytic synthesis, electrocatalytic synthesis, and photocatalytic synthesis, has attracted more and more attention because the continuous and low‐concentration H2O2 produced by catalytic synthesis can be directly used for the oxidation of organic compounds, effectively avoiding the shortcomings of the current industrial route. Here, we briefly reviewed the latest processes for the catalytic production of H2O2 via various routes. On this basis, we summarized and discussed the in situ application of H2O2 in typical organic conversion reactions, including the ammoximation of ketones, the oxidation of alcohols, the oxidation of C−H bonds, and the oxidation of olefins. Some in situ coupling reactions have shown excellent performance with high conversion and selectivity, and the economic cost has been significantly reduced. Finally, the shortcomings of the in situ utilization of H2O2 in coupling reactions were analyzed, and some strategies for promoting the efficiency of the H2O2 application in organic synthesis were proposed. [ABSTRACT FROM AUTHOR]

Semiconductor‐based photoelectrochemical (PEC) organic transformations usually show radical characteristics, in which the reaction selectivity is often difficult to precisely control due to the nonselectivity of radicals. Accordingly, several simple organic reactions (e.g., oxidations of alcohols, aldehydes, and other small molecules) have been widely studied, while more complicated processes like C─C coupling remain challenging. Herein, a synergistic heterogeneous/homogeneous PEC strategy is developed to achieve a controllable radical‐induced C─C coupling reaction mediated by the copper‐coordination effect at the semiconductor/electrolyte interfaces, which additionally exerts a significant impact on the product regioselectivity. Through experimental studies and theoretical simulations, this study reveals that the copper‐chloride complex effectively regulates the formation of chloride radicals, a typical hydrogen atom transfer agent, on semiconductor surfaces and stabilizes the heterogeneous interfaces by suppressing the radical‐induced surface passivation. Taking the Minisci reaction (the coupling between 2‐phenylquinoline and cyclohexane) as a model, the yield of the target C─C coupling product reaches up to 90% on TiO2 photoanodes with a selectivity of 95% and long‐term stability over 100 h. Moreover, such a strategy exhibits a broad scope and can be used for the functionalization of various heteroaromatic hydrocarbons. [ABSTRACT FROM AUTHOR]

In this study, we investigate the indirect electro‐oxidation of benzyl alcohol (BA) using the copper/TEMPO catalytic system, which combines copper complexes with 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO) in an anaerobic medium. We reexamine the impact of bpy ligand proportions, exploring ratios of 1:1, 2:1, 3:1, and 4:1 on catalytic activity. Cyclic voltammetry and visible spectroscopy reveal distinct electrochemical characteristics and complex formations at different bpy ratios. Simulations uncover intricate energy equilibria involving ion coordination, varying with oxidation state, and bpy proportion. Theoretical and experimental spectra align, supporting the proposed structures. The Brønsted base, triethylamine (TEA), essential in this anaerobic system, shows different voltammetric profiles with each ligand ratio, revealing key interactions with bpy complexes. In the presence of BA, the 1:1 and 2:1 ratios exhibit indirect catalytic activity, with the 2:1 ratio yielding significantly higher current densities. This establishes a new optimal condition where [Cu(bpy)2]2+$[{\rm Cu(bpy)}_{2}]{}^{2+}$ formed in a 2:1 stoichiometry demonstrates superior activity with a lower redox potential, while maintaining labile coordination points for necessary interactions. Theoretical results also indicate weaker TEMPO coordination to [Cu(bpy)2]2+$[{\rm Cu(bpy)}_{2}]{}^{2+}$. [ABSTRACT FROM AUTHOR]

A systematic mechanistic study employing rate constant (kobs) kinetics measurements, linear free‐energy relationship, hydrogen kinetic isotope effect and rate law, as well as the Density Functional Theory (DFT) approach (M06‐2x/6‐311G(d,p)) for the oxidation of diverse substituted benzyl alcohols with trichloroisocyanuric acid (TCCA)/H2O in 50 % MeCN/CH2Cl2 at 25.0 °C is present. The kinetic results showed an autocatalytic behavior and a primary kinetic isotope effect (4.22). The linear free‐energy relationship (σ, ρ=−1.22) indicated a mechanism change for 4‐CF3, 3‐NO2 and 4‐NO2 substituted benzyl alcohols and a fractional rate law (3.25) for benzyl alcohol. The DFT results indicated Cl2, formed in situ from TCCA and HCl. Furthermore, calculations support the kinetic results with high agreement through a transition state that performs a hydride abstraction by autocatalytic Cl2 in the induction zone. In the case of substrates bearing strong electron withdrawing groups, the mechanism changes to hydrogen abstraction from the corresponding benzyl hypochlorite as the main pathway. [ABSTRACT FROM AUTHOR]

Since the report of oxamide ligands, they have been widely used for the efficient construction of various types of C−X (such as C, N, O and S) bonds. To evaluate whether the easily tunable electronic properties and unique coordination modes of oxamide ligands can also shine in the field of oxidation, we initiated a study on oxamide ligand/copper/air oxidation and applied it to the oxidation of alcohols to assess its practicality and potential applications. The practicality of this strategy was further verified through scale‐up reactions on a 100 mmol scale and gram‐scale derivatization of pharmaceutical molecules. [ABSTRACT FROM AUTHOR]

2,2,6,6′‐Tetramethylpiperidine‐N‐oxyl (TEMPO) is a highly efficient oxidation catalyst, valued for its environmentally benign nature, particularly in comparison to transition‐metal catalysts. Despite their merits, TEMPO‐based catalysts are not notably cost‐effective. Immobilization of TEMPO onto supports offers a promising strategy to overcome this limitation. In this work, we present the synthesis and application of immobilized TEMPO catalysts 2–5, prepared via a straightforward condensation reaction, for the aerobic oxidation of alcohols. These catalysts demonstrate remarkable activity for alcohol oxidations under continuous‐flow conditions, employing nitric acid as the co‐catalyst. Notably, catalyst 2 immobilized by COOH silica gel exhibits outstanding performance for the oxidation of benzyl alcohol by oxygen gas, achieving a turnover frequency (TOF) of 15 h−1 and a turnover number (TON) exceeding 300. Catalyst 2 further demonstrates broad substrate scope, effectively oxidizing primary, secondary, and benzylic alcohols. Post‐reaction analysis of spent catalyst 2 reveals that deactivation primarily stems from nitrosation of the N−O bond. Interestingly, the amide moiety remains intact despite the harsh acidic reaction conditions. [ABSTRACT FROM AUTHOR]

Herein, an electrocatalytic coupling system for selective ammonia and glycolic acid production over cathodic single‐atom Co (Co─N─C) and anodic PdNi alloying nanoparticles on the carbonized cellulose (PdNi/CBC), respectively are reported. As a cathodic electrocatalyst for nitrate reduction reaction (NtrRR), the Co─N─C displays remarkably high activity, delivering an NH3 yield rate of 20.5 ± 2.7 mg h−1 mgcat.−1 with a Faradaic efficiency (FE) of 95.5 ± 2.8% at −0.5 V (vs RHE). In situ spectroscopy combined with theoretical calculations unveiled the NtrRR mechanism on Co─N4 site. As an anodic electrocatalyst for ethylene glycol oxidation reaction (EGOR), the PdNi/CBC shows a high FE of 96.6 ± 1.7% for glycolic acid (GA) production at 1.6 V (vs RHE) and robust stability of 168 h. Remarkably, a proof of concept experiment of coupling electrocatalytic NtrRR with EGOR demonstrates that only an applied potential of −0.1 V (vs RHE) is required to reach a current density of 10 mA cm−2 for co‐producing ammonia and glycolic acid. As a result, the coupled NtrRR‐EGOR system can achieve an NH3 yield rate of 6.0 ± 0.6 mg h−1 mgcat.−1 and a GA yield rate of 16.8 ± 1.7 mg h−1 mgcat.−1 at −0.7 V (vs RHE). [ABSTRACT FROM AUTHOR]

Liquid-phase processing of oxygen-containing organic compounds in a chemical microfluidic plasma reactor has been implemented. Excitation of a microdischarge in vapor–gas bubbles in a treated liquid stream by an external electric field makes it possible to intensify redox processes in order to obtain valuable components and intermediate products of organic synthesis without the introduction of complex and unstable oxidizing agents. By controlling the parameters of the microreactor, it is possible to create conditions for the preferential occurrence of a desired chemical reaction: partial or deep liquid-phase oxidation of alcohols, oxidative rearrangement of ketones, and cracking or oxidative degradation of the carbon skeleton. [ABSTRACT FROM AUTHOR]

Multipurpose applications of a newly developed homobimetallic Ru(II) complex, Ru‐NDI[PF6]4, which incorporates 1,10‐phenanthroline and triazole‐pyridine ligands and linked via a (−CH2−)3 spacer to the reputed anion‐π interacting NDI system, are described. Solution‐state studies of the bimetallic complex, including EPR, PL, UV‐vis, and NMR experiments, reveal two sequential one‐electron transfers to the NDI unit, generating NDI⋅− and NDI2− in the presence of F− selectively. This process inhibits the primary electron transfer from Ru(II) to the NDI unit, thereby allowing the 3MLCT‐based emission of the complex to be recovered, resulting in a corresponding ten‐fold increase in luminescence intensity. DFT and TD‐DFT computational studies further elucidate the experimentally observed absorption spectra of the complex. Secondly, CT‐DNA binding studies with the complex are performed using various spectroscopic analyses such as UV‐vis, PL, and CD. Comparative DNA binding studies employing EB and molecular docking reveal that the binding with CT‐DNA occurs through both intercalative and groove binding modalities. Thirdly, the photocatalytic activities of the complex towards C−C, C−N, and C−O bond formation in organic cross‐coupling reactions, including the amidation of α‐keto acids to amines and the oxidation of alcohol to aldehydes, are also demonstrated. [ABSTRACT FROM AUTHOR]

Here, we present the efficient synthesis of benzaldehyde (BnZ) by reacting benzyl alcohol with air and employing CeO2–MnO2 (Ce–Mn) mixed oxide. The addition of MnO2 (Mn) to CeO2(Ce) increased the reducibility, support–support interaction, and oxygen vacancy. The development of oxygen vacancies in the ceria lattice following Mn addition can be used to explain that altering the Mn:Ce ratio refines the oxide's reducibility. The physicochemical characteristics of the synthesized materials were examined using FT-IR, Raman spectroscopy, powder X-ray diffraction (P-XRD), X-ray photoelectron spectroscopy (XPS), and BET surface area analysis. Furthermore, it exhibits superior catalytic activity in the presence of air during the selective oxidation of benzyl alcohol to benzaldehyde in vapor phase reactions, and it keeps its high stability for five successive cycles. [ABSTRACT FROM AUTHOR]

In this study, the catalytic activity of an oxovanadium(IV) unsymmetrical salophen complex immobilized on chloro-functionalized silica-coated CoFe2O4 magnetic nanoparticles CoFe2O4@SiO2@CPTMS@VO(salophen-OH), in which salophen-OH = 4-[(E)-{(2-[(E)-2-hydroxybenzylidene)amino]phenyl}imino)methyl]benzene-1,3-diol was explored in the oxidation of alcohols and hydrocarbons. This heterogeneous nanocatalyst showed high activity and selectivity in oxidizing various primary and secondary alcohols to the equivalent aldehydes and ketones with 30% H2O2 as a green oxidant in polyethylene glycol (PEG) as an eco-friendly solvent at 80 °C. Furthermore, the above catalyst demonstrated significant catalytic efficiency in the alkene epoxidation and alkane hydroxylation using tert-butyl hydroperoxide (tert-BuOOH), and the corresponding products were achieved in good to excellent yields in acetonitrile at ambient temperature. This magnetic nanocatalyst can be easily separated from the reaction mixture utilizing an external magnet and reused up to five times without significant activity loss. Moreover, the recovered catalyst's structure was scrutinized using Fourier transform infrared (FT-IR), vibrating sample magnetometry (VSM), and X-ray diffraction (XRD) techniques, which confirmed that the structure of the catalyst remained unaltered post-recovery. [ABSTRACT FROM AUTHOR]

Amid growing energy demands, innovative solutions are essential to power a variety of devices. Paper‐based microfluidic fuel cells (PμFCs), powered by eco‐friendly alcohols derived from biomass, present a promising option. While lightweight and disposable, they mainly rely on costly noble‐metal catalysts for high efficiency. In this context, the concept of photo paper batteries (pPBs), utilizing affordable sunlight‐activated semiconductors to drive alcohol oxidation on paper, opens the possibility to disposable and affordable energy solutions. Our review highlights recent progress in PμFCs fueled by alcohols like methanol, ethanol, ethylene glycol, and glycerol. We explore semiconductor advancements driving anodic reactions and envision the potential of pPBs. To achieve practical pPBs, refining semiconductors, electrode design, and microfluidic engineering are pivotal. This short review highlights the transformative potential of pPBs and beckons researchers to partake in shaping this new field. [ABSTRACT FROM AUTHOR]

Fabricating a highly active and stable nanocatalyst material displays a great concern when constructing a commercially viable ethylene glycol (EG) fuel cell. Herein, nickel oxide nanostructures were grown onto graphite (NO/T) using coprecipitation and calcination protocol at different temperatures. Techniques for XRD, TEM, SEM, and EDX investigations were used to look into the produced crystal planes, shape, and elemental mapping of synthesized nickel oxide nanoparticles. Different NO/T nanocatalyst electroactivities were examined in order to oxidize EG molecules in basic electrolyte. The surface area values of calcined nanostructures at 200°C and 300°C were much higher than those measured at NO/T‐400 by 7.62 and 3.71 folds to explain their outstanding performance. Some kinetic information for varied NO/T nanocatalysts was derived including the electron transfer coefficient, rate constant, and surface coverage values. Electron transfer rate constants of 0.1946, 0.3734, 0.0113, and 0.0303 s−1 were calculated at NO/T‐200, NO/T‐300, NO/T‐400, and NO/T‐500, respectively. Increased oxidation current densities could be achieved when NO/T nanomaterials were subjected to lowered calcination temperatures. NO/T‐200 and NO/T‐300 nanocatalysts also displayed decreased Eonset for alcohol oxidation process by 20 and 41 mV in relation to that at NO/T‐400. Moreover, chronoamperometric experiments revealed the prevalence of the stable behavior during EG oxidation at these nanostructures, especially for calcined ones at 200°C and 300°C. Much reduced poisoning rates were measured at NO/T‐200 (0.171 s−1) and NO/T‐300 (0.067 s−1) when contrasted to that at NO/T‐500 (0.727 s−1). Increasing the alcohol and supporting electrolyte concentrations was beneficial in improving the charge transfer characteristics of NO/T nanocatalysts as demonstrated by EIS measurements. This study supports the promising activity of NiO nanoparticles onto graphite as anode materials for direct alcohol fuel cells. [ABSTRACT FROM AUTHOR]

This work represents the facile and green synthesis of Molybdenum (Mo)-doped bismuth vanadate (BiVO4). Green synthesis of Mo-doped BiVO4 was done using combustion technique using Mangifera indica (Mango) leaf extract as the fuel for combustion. The material synthesised was pure and characterised using X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, ultraviolet–visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy and photoluminescence (PL). It was found that Mo-doped BiVO4 had monoclinic scheelite phase, with a bandgap of 3.71 eV. Various application was possible from the synthesised material like photodegradation of Malachite Green, a typical organic which showed excellent degradation efficiency of 99% under 120 minutes. The catalyst also gave up to 95% yields in the light-assisted oxidation of aromatic alcohols to corresponding aldehydes. The material also showed excellent antioxidant properties showing 6.7 µg of ascorbic acid equivalence (AAE). It gave an excellent minimum lethal dosage (MLD) of 500 µg against Penicillium and Trichoderma fungal strains and showed maximum of 32 mm zone of inhibition. These applications show the versatility of the material to be used in various fields. [ABSTRACT FROM AUTHOR]

This review analyzes the use of magnetite-based catalysts in various oxidation reactions. It is shown that magnetite-based catalysts are the most promising candidates from the standpoint of easy separation from the reaction zone and reusability. Diverse examples of the use of magnetite-based composites are discussed, including the following reactions: partial oxidation of methane to formaldehyde; the oxidation of cycloalkanes into alcohols and ketones; the oxidation of alkenes and alcohols with the major focus made on benzylic alcohol oxidation; oxidative cracking of alkenes; Fenton-type reactions with H2O2 as a benign oxidant; the removal of dyestuff in water (including wastewater by oxidation); reactions of sulfides and thiols; the oxidation of 5-hydroxymethylfurfural as a platform chemical to 2,5-diformylfuran; the oxidation of D-glucose to D-gluconic acid; and the electrocatalytic oxidation of methanol and ethanol. The most important and best-studied applications of magnetic nanoparticles in the oxidation reactions are believed to be the oxidation of diverse benzylic alcohols and D-glucose, and Fenton-like reactions aiming at the removal of S- and N-compounds from ware and fuels. Magnetic nanocomposites are determined as the materials meeting a range of criteria: (1) they should be magnetic, (2) they contain nanoparticles, and (3) they consist of two (or more) nanocomponents. The core–shell materials with magnetic nanoparticles used as a core or as decorating nanoparticles are discussed in the review. Three main types of magnetic nanocomposites can be distinguished: (1) the systems where the magnetic phase is active in the considered reaction, for instance, Fenton-like oxidation; (2) the systems containing active metal nanoparticles supported onto the magnetic nanoparticles; and (3) materials with magnetic nanoparticles as a core coated with one or two shells (porous or non-porous), with the magnetic nanoparticles being active or not in the title reaction. Magnetic nanoparticles exhibit a number of advantages compared with supported non-magnetic catalysts of oxidation reactions. The advantages include the possibility of separation from the reaction medium (5–10 times) without a significant loss of the activity, their non-toxicity, low cost, and availability, and the easy preparation of these materials. The drawbacks may include the leaching of active components; a decrease in saturation magnetization in comparison with the bulk magnetite; a limited accessibility of active sites due to diffusion through the shells; the complicated composition and structure of the nanomaterials; a decrease in the activity and specific surface area; and a limited number of magnetic compounds with acceptable characteristics. Nevertheless, the advantages of magnetic nanocatalysts stimulate their wide use in liquid-phase oxidation reactions, which will be discussed in the review. Future perspectives on the use of magnetic composites are considered. [ABSTRACT FROM AUTHOR]

Abstract Here, Er/Yb Co-doped CaMoO4 materials (ErxYbyCa1−x−yMoO4 NPs where x = 0, 0.01 and y = 0, 0.05, 0.10, 0.15, 0.20) were prepared by microwave-assisted method and its pure-tetragonal structure were confirmed by X-ray diffraction spectra (XRD), Rietveld-refinement and Raman-vibrational spectra. The transmission-electron microscopy (TEM) study indicates the formation of nearly spherical shaped nanomaterial with average size of ~ 15 nm. Additionally, absorption and emission properties were studied by UV–Visible–NIR and photoluminescence (PL) spectrometer. The UV–Visible–NIR spectra attribute absorption of Er3+ ion in visible region (380–700 nm) and absorption of Yb3+ ion in near-infrared region (700–1400 nm). Moreover, PL up-conversion spectra of the sample recorded under excitation wavelength 980 nm. The PL peaks were observed at 530, 544–552, and 656–670 nm. Prominent PL-intensity was observed for Er0.01Yb0.15Ca0.84MoO4 phosphor. Temperature dependent PL study reveals that present phosphor is robust phosphor for temperature sensor. In addition, Er3+/Yb3+ doped CaMoO4 nanomaterials exhibited excellent activity and selectivity in the aerial oxidation of benzoin over benzyl under oxidant-free reaction conditions. The synergistic effect Er3+/Yb3+ co-doing in CaMoO4 matrix was observed, where only CaMoO4 material found to be inactive towards above oxidation reaction. Moreover, the oxidation of primary benzyl-alcohols was furnished in presence of tertiary butyl hydroperoxideas oxidant.

Zr‐monosubstituted polyoxometalates (Zr‐POMs) of the Keggin (Bu4N)8[{PW11O39Zr(μ‐OH)}2] (Zr‐K), Lindqvist (Bu4N)6[{W5O18Zr(μ‐OH)}2] (Zr‐L), and Wells‐Dawson (Bu4N)11H3[{P2W17O61Zr(μ‐OH)}2] (Zr‐WD) structures are capable of heterolytic activation of the environmentally benign oxidant tert‐butyl hydroperoxide (TBHP) and catalyze epoxidation of alkenes and oxidation of alcohols to carbonyl compounds. Catalytic activity of corresponding Ti‐POMs is much lower. Among Zr‐POMs, Zr‐K revealed higher epoxide yields. All Zr‐POMs do not catalyze unproductive TBHP degradation, and epoxide yields with both aqueous and anhydrous TBHP are generally higher than with aqueous H2O2. Regioselectivity of the Zr‐K‐catalyzed limonene epoxidation with TBHP is different from that with H2O2: the more substituted and nucleophilic double bond is preferably epoxidized, pointing to an electrophilic oxygen transfer mechanism. The oxidation rates are first order in catalyst (Zr‐K) and substrate (cyclooctene or cyclohexanol) and show a saturation behavior with increasing concentration of TBHP. Studies by HR‐ESI‐MS, ATR‐FT‐IR, and 31P NMR spectroscopic techniques implicated the formation of zirconium alkylperoxo species upon interaction of Zr‐POMs with TBHP. HR‐ESI‐MS revealed the existence of monomeric and dimeric alkylperoxo complexes, [{PW11O39Zr}((CH3)3COO)]4− and [{PW11O39Zr((CH3)3COO)}2]8−, with predomination of the former, which is most likely the active species responsible for the selective oxidations. [ABSTRACT FROM AUTHOR]