Catalyst For Oxidation Of Alcohols Research Articles

4‐OH‐TEMPO radical grafted onto a novel polyaromatic ether sulfone containing carboxyl side chains as solid catalyst for alcohol oxidation

Abstract2,2,6,6‐Tetramethylpiperidinium‐nitroxide (TEMPO) is a mild and efficient catalyst, which is important in the industrial production of selective oxidation of alcohols to the corresponding aldehyde or ketone compounds. However, it is a challenge to recover the expensive TEMPO catalyst in homogeneous catalytic systems. In this study, a novel polymer‐supported catalyst was prepared using 4‐hydroxy‐2,2,6,6‐tetramethylpiperidin‐1‐oxy (4‐OH‐TEMPO) and polyaromatic ether sulfone (PAES). The successful grafting of 4‐OH‐TEMPO in PAES‐C was demonstrated by 1H nuclear magnetic resonance (1H NMR) and Fourier transform infrared (FT‐IR), load capacity can be calculated by elemental analysis (EA). BET and scanning electron microscopy (SEM) to depict the structure‐performance relationship. Herein, SEM images revealed the existence of porous structure. This structure can effectively adsorb NO molecules to form a PAES‐TEMPO/NOx catalytic system to selectively oxidize benzyl alcohol. The experimental results indicated the high activity, the subsequent benzyl alcohol oxidation cycle can reach more than 93% conversion without showing a large loss of selectivity. More importantly, the as‐prepared catalyst exhibited the attractive recyclability (recovery rate is 98%). After 10 consecutive runs, no significant loss of conversion and selectivity was observed (the conversion rate of benzyl alcohol was more than 93% and the selectivity was more than 95%). This study might provide some recommendation on the development of highly efficient catalysts for alcohol oxidation.

Improved Catalytic Performance toward Selective Oxidation of Benzyl Alcohols Originated from New Open-Framework Copper Molybdovanadate with a Unique V/Mo Ratio.

A new organic-inorganic hybrid open-framework molybdovanadate with mixed-valences of vanadium (V4+ /V5+ =4/3) and molybdenum (Mo5+ /Mo6+ =8/2) cations has been synthesized. The complex possesses the unique V/Mo ratio (7/10), fascinating 8-C topological network and 1D 4-MR channels (7.793 Å×6.699 Å). Importantly, its catalytic activities for the selective oxidation of benzyl alcohol to benzaldehyde (oxidant: H2 O2 , 30 wt %) have been well evaluated. The results indicated that it exhibited improved catalytic activities (conv.: 96.8 %) compared with the catalyst (Cpyr)5 PV2 Mo5 W5 O40 [conv.: 88.51 %, Cpyr=(C16 H32 C5 H4 N)+ )], high recyclability and structural stability. Moreover, the conversions and selectivities (conv.: 82.4-92.5 %; sele.: 91.5-95.7 %) of the substrates containing electron donating groups (-OH, -CH3 , -OCH3 and -Cl) were significantly higher than those of the substrate containing electron withdrawing group (-NO2 ) (conv. 67.4 %; sele.: 80.8 %). This is due to the fact that the -NO2 with a large Hammett substituent constant is not conducive to the generation of transition state products. The studies revealed the complex could act as a highly efficient heterogeneous catalyst in selective oxidation of benzyl alcohols.

Photocatalytic activity of CuBi2O4/WO3 p-n heterojunction photocatalysts in benzyl alcohol oxidation to benzaldehyde

CuBi2O4/WO3 (CBO/WO3) p-n heterojunction composite was synthesized by mechanical stirring and sonication for the selective oxidation of benzyl alcohol to benzaldehyde under visible light. Multiple characterization methods, including XRD, XPS, SEM, TEM, UV–vis DRS, BET, EIS and ESR, were used to investigate the origin of the excellent photocatalytic activity. The results of XRD, XPS, SEM, and TEM revealed that CBO/WO3 catalyst was successfully synthesized. Benzaldehyde selectivity of over 99 % and benzyl alcohol conversion of 54.8 % were obtained under an optimized condition using 50 mg of 40-CBO/WO3 (40 stood for the mass percentage of CBO in CBO and WO3.). DFT results showed that ∆Eads values of benzyl alcohol were − 0.51, − 0.66 and − 0.88 eV on CBO, WO3 and CBO/WO3. The oxidation of benzyl alcohol occurred more easily on the surface of CBO/WO3. Meanwhile, the stability of 40-CBO/WO3 was investigated. After 5 repeated experiments, a high conversion was still maintained, indicating its potential in practical application. A possible mechanism of benzyl alcohol to benzaldehyde was proposed through the capturing experiment of active species. This work successfully designed an efficient p-n heterojunction composite catalyst for selective oxidation of benzyl alcohol. Replacing traditional thermal synthesis with selective photocatalysis can promote more environmentally friendly processes.

Development of sustainable green catalysts for oxidation of alcohols via decorated palladium nanoparticles on magnetic carbon nanotube/MOF

Using a straightforward method, this study fabricated an eco-friendly low-cost magnetic nanocomposite consisting of magnetic carbon nanotube/MOF as a stabilizer. Pd nanoparticles (Pd NPs) were then decorated on the designed magnetic carbon nanotube/MOF microspheres, and the resulting magnetic carbon nanotube/MOF/Pd NPs nanocomposite were employed as heterogeneous catalysts in Aerobic oxidation of primary and secondary alcohols. The attractiveness of this work is in the selective oxidation of several types of active and inactive alcohol substrates. The most important feature of this catalyst is its successful recovery and simple separation repeatedly without reducing its activity and selectivity. The active surface area of this Nanocatalyst is very large due to its structural properties, and as a result, it provides more available catalytic sites, which increases its activity. The identification techniques used to investigate the structural properties of this Nanocatalyst confirm its successful synthesis and appropriate palladium loading into the catalyst sites. The oxidation of alcohols was determined by Gas Chromatography (GC). The 100% selectivity, excellent turnover number (TON), high yield, almost complete and fast conversion of alcohol to the desired aldehydes and ketones without more oxidation, and easy and no-trouble isolation of product and catalyst are outstanding features of this catalytic system. The use of picolinaldehyde lead to the high loading of Pd NPs, reducing the catalyst content needed for the reaction. Regarding the high catalyst loading, using a small amount of catalyst is recommended for proceeding with the reaction efficiently.

Polyhedral Coordination Determined Co‐O Activity for Electrochemical Oxidation of Biomass Alcohols

AbstractEarth‐abundant transition metal oxides are promising electrocatalysts for oxidation of biomass alcohols. Here, CoO and Co3O4 are selected as representative cobalt oxide catalysts and grown on carbon fiber paper (CFP) electrodes to reveal the interplay between electronic structure and catalytic activity of catalysts for oxidation of glycerol, diols, and monohydric alcohols. In situ electrochemical tests elucidate that the CoO/CFP electrode has lower interfacial impedance, higher charge transfer, faster oxidation rate, and thereby the higher catalytic activity for alcohol oxidation than the Co3O4/CFP electrode. Especially for glycerol oxidation, the CoO/CFP electrode only requires 1.32 V to reach 10 mA cm−2, the potential is 120 mV lower than that for the Co3O4/CFP electrode. The CoO/CFP electrode can also produce value‐added products such as formate, acetate, and glycolate with high selectivity and efficiency at low energy consumptions from oxidation of biomass alcohols. Theoretical calculations further confirm the dominant role of octahedrally coordinated Co‐O sites in adsorption, activation, and oxidation of C3‐C1 alcohols. This work sheds light on the design of highly efficient transition metal oxide catalysts for oxidation of alcohols by populating octahedral sites in the crystal structure.

Copper Nanoparticles Supported on ZIF-8: Comparison of Cu(II) Reduction Processes and Application as Benzyl Alcohol Oxidation Catalysts.

We report the synthesis of a stable heterogeneous catalyst based on copper metal nanoparticles with oxidized surface supported on ZIF-8 for the oxidation of benzyl alcohol under mild temperature and using air as a sustainable oxygen source as well as for the implementation of the tandem "one-pot" catalytic system allowing the sustainable synthesis of benzylidene malononitrile. The influence of the reduction process applied to form the nanoparticle upon the catalyst texture and its performances was extensively examined. After ZIF-8 impregnation with a copper chloride precursor, the reduction of cupric ions into Cu0 nanoparticles was carried out according to two procedures: (i) by soaking the solid into a solution of NaBH4 and (ii) by submitting it to a flow of gaseous H2 at 340 °C. The in-depth physicochemical characterization and comparison of the resulting two types of Cu/ZIF-8 materials reveal significant differences: the reduction with NaBH4 led to the formation of 16 nm sized Cu0 nanoparticles (NP) mainly localized on the external surface of the ZIF-8 crystals together with ZnO nanocrystallites, while the reduction under H2 flow resulted in Cu0 nanoparticles with a mean size of 22 nm embedded within the bulk of ZIF-8 crystals. More, when NaBH4 was used to reduce cupric ions, ZnO particles were highlighted by high-resolution microcospy imaging. Formation of ZnO impurities was confirmed by the photoluminescence analysis of ZIF-8 after NaBH4 treatment. In contrast, ZnO was not detected on ZIF-8 treated with H2. Both types of Cu0 NPs supported on ZIF-8 were found to be active as catalysts toward the aerobic oxidation of benzyl alcohol under moderate temperature (T < 80 °C) and using air as a sustainable O2 source. Benzaldehyde yield of 66% and selectivity superior to 90% were obtained with the Cu/ZIF-8 catalyst prepared under H2 flow after 24 h under these conditions. The same material could be recycled 5 times without loss of activity, unlike the catalysts synthesized with NaBH4, as a result of the leaching of the surface copper NPs over the consecutive catalytic cycles. Finally, the most stable catalyst was successfully implemented in a tandem "one-pot" catalytic system associating benzyl alcohol oxidation and Knoevenagel condensation to synthesize benzylidene malononitrile.

Synthesis and characterization of N4-donor Schiff base copper(II) immobilized on superparamagnetic Fe3O4@SiO2 and its use as a recyclable catalyst for oxidation of alkenes, alcohols, and determination of antibacterial activity

N4-donor Schiff base copper(II) nanoparticles were easily prepared through surface modification of silica-coated magnetite nanoparticles (Fe3O4@SiO2) with pyrrole 2-carbaldehyde Schiff base and a subsequent reaction with Cu(CH3COO)2.H2O in ethanolic solution. This nanocatalyst was characterized using thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and magnetization. Efficient oxidation of alkenes and alcohols was carried out over the Schiff base copper(II) nanoparticles. Catalytic tests showed that the catalyst was particularly effective for the oxidation of α-methyl styrene, norbornene, benzyl alcohol, and benzohydrol. The results showed that acetophenone, 2-norbornanone, benzoic acid, and benzophenone with selectivity values of 88, 100, 100, and 100, respectively, were obtained. The heterogeneous catalyst of N4-donor Schiff base copper(II) offers advantages such as ease of product separation, catalyst recycling, and ease of preparation. Antibacterial tests against two gram-positive and two gram-negative bacterial species found that the bacteria stopped growing in the catalyst medium.

Core–Shell Catalysts for Conventional Oxidation of Alcohols: A Brief Review

This review highlights recent research on the application of core–shell structured materials as catalysts in the oxidation of alcohols to value-added products, such as benzaldehyde, acetophenone, benzophenone, cinnamaldehyde, and vanillin, among others. While the application of various unconventional energy inputs (such as microwave and ultrasound irradiation) was reported, this paper focuses on conventional heating. The oxidation of homocyclic aromatic, heterocyclic aromatic, aliphatic, and alicyclic alcohols catalyzed by core–shell composite catalysts is addressed. This work also highlights some unique advantages of core–shell nanomaterial catalysis, namely the flexibility of combining individual functions for specific purposes as well as the effect of various parameters on the catalytic performance of these materials.

Aerobic oxidation of benzylic alcohols catalysed by new (aryl‐BIAN)copper(I) complexes: Their synthesis and structural characterization

A new neutral dimeric Ar‐BIAN Cu(I) complex (where Ar‐BIAN = bis(aryl‐imino)acenaphthene) of formulation [CuBr(4‐iPrC6H4‐BIAN)]2 (2) was obtained by reacting CuBr and ligand 4‐iPrC6H4‐BIAN (L2) in refluxing acetonitrile under an argon atmosphere. When the ligand used was 2,4,6‐Me3C6H2‐BIAN (L1), we obtained 1 in which the expected dimer (1a) is present, but we could also observe, in solution, the presence of the bis‐chelate dimer [Cu(2,4,6‐Me3C6H2‐BIAN)2][CuBr2] (1b) bearing CuBr2− as counter‐ion; attempts to separate them failed. When the ligand used was 2‐iPrC6H4‐BIAN (L3), we obtained 3 in which the expected dimer (3a) is in equilibrium, in solution, with its bis‐chelate isomer [Cu(2‐iPrC6H4‐BIAN)2][CuBr2] (3b). The solid‐state molecular structures of compounds 2 and 3b were determined by single crystal X‐ray diffraction. The electrochemical behaviour of complexes: 1 (1a, and 1b), 2, and 3 (3a and 3b) and the known compound [Cu(2‐iPrC6H4‐BIAN)2][BF4] (7) were investigated by cyclic voltammetry. The new complexes 1 (1a, 1b), 2, and 3 (3a, 3b) were tested as catalysts for the aerobic oxidation of benzylic alcohols into aldehydes; they all catalyse the reaction, with good results; the catalytic studies were extended to the similar known complexes [CuBr(2,6‐iPr2C6H3‐BIAN)]2 (4), [CuI(2,6‐iPr2C6H3‐BIAN)]2 (5), [CuCl(2,6‐iPr2C6H3‐BIAN)]2 (6) and (7), in order to study the effect of different bridging halides or counter ions in the catalytic activity. We found that compound 4 exhibited a high catalytic activity comparable to the best results published so far. The oxidation products, benzaldehydes, were detected and further confirmed by NMR spectroscopy, and the conversion rate was determined after GC‐FID analysis.

One-pot synthesis of 3D surface-wrinkled PdAu nanospheres for robust alcohols electrocatalysis

Three dimensional (3D) noble-metal nanomaterials with special surface structures have been regarded as high-performance catalysts for alcohol oxidation on account of their superior thermal stability, electrical conductivity and large specific surface area. Although extensive efforts have been devoted to the preparation of 3D Pd-based catalysts with superior activity and stability, designing a simple, effective and eco-friendly method remains a challenge. Herein, we developed a facile one-step coreduction strategy to synthesize a series of 3D surface-wrinkled PdAu nanospheres (NSs) with tunable Pd/Au atomic ratios and found a universal method to prepare surface-wrinkled PdM (M = Au, Pt, Cu and Pb) NSs. Benefiting from the function of the surfactant cetyltrimethylammonium chloride (CTAC), the synthesized PdAu NSs with different composition possess abundant surface wrinkles, which is beneficial for exposing more electroactive centers. Attributed to the unique geometric morphology and optimized atomic ratio, the PdAu-2 NSs exhibited an optimal mass activity (MA) of 8103 mA mg−1 and 5113 mA mg−1 for the ethylene glycol oxidation reaction (EGOR) and ethanol oxidation reaction (EOR), which was 6.1 and 4.1 times that of commercial Pd/C, respectively. Moreover, the PdAu-2 NSs exhibited superb stability after long-term current–time (i-t) and cyclic voltammetry (CV) tests of the EGOR and EOR. This work not only provides new avenues to engineer PdAu NSs with enhanced electrocatalytic performance but also offers guidance for extending to more 3D PdM (M = other metals) NSs with novel morphology applied to fuel cell fields.

Metal-Support Interaction in Gold Zeolitic Octahedral Metal Oxide and the Catalytic Activity for Low-Temperature Alcohol Oxidation.

Au nanoparticles are efficient catalysts for selective oxidations. The interaction between Au nanoparticles and supports is critical for achieving high catalytic activity. Herein, Au nanoparticles are supported on a zeolitic octahedral metal oxide based on Mo and V. The charge of Au is controlled by the surface oxygen vacancies of the supports, and the redox property of the zeolitic vanadomolybdate is highly dependent on Au loading. The Au-supported zeolitic vanadomolybdate is used as a heterogeneous catalyst for alcohol oxidation under mild conditions with molecular oxygen as an oxidant. The supported Au catalyst can be recovered and reused without the loss of activity.

Mononuclear Cu-complex embedded ordered nano-porous silica based hybrid catalyst for oxidation of benzyl alcohol

A novel mixed ligand copper (׀׀) complex having 2,9-dimethyl-1,10-phenanthroline and nitrate has been successfully synthesized and characterized by single crystal XRD. Following synthesis, this complex was anchored on acid functionalized nano-porous materials such as MCM-41-SO3H and SBA-15-SO3H, and these hybrid materials were characterized using a variety of techniques such as FT-IR, PXRD, BET, SEM, TG, and so on. These modified mesoporous materials (MCM-41-SO3HCu and SBA-15-SO3HCu) were subjected to solvent-free selective benzyl alcohol oxidation with TBHP (Tert-Butyl Hydroperoxide) as an oxidant. Various reaction parameters were investigated to optimize the reaction conditions. MCM-41-SO3HCu was discovered to be an excellent catalyst in terms of benzyl alcohol conversion and benzaldehyde selectivity.

Ti doped CeO2 nanosheets supported Pd catalyst for alcohol oxidation: Catalysis of interfacial sites

AbstractThe oxidation of alcohols is a significant chemical reaction, and the efficient oxidation of alcohols over heterogeneous catalysts using oxygen as oxidant has attracted much attention in recent years. Among them, Pd/CeO2 exhibits excellent alcohol oxidation performance. However, the structure-activity relationship between the catalyst's structure and its catalytic performance for alcohol oxidation is still not clearly understood. This study involved the preparation of CeO2 nanosheets with different concentrations of surface oxygen vacancies (Ov) and their subsequent loading with Pd to explore their catalytic performance for alcohol oxidation. The findings obtained through XPS, Raman, and XAS indicated a positive correlation between the surface Ov concentration of CeO2 as well as the ratio of Pd2+ fraction. The alcohol oxidation results and structure-performance relationship studies showed that there was a good linear relationship between the Pd2+ ratio as well as the surface Ce3+ concentration and the TOF of benzyl alcohol oxidation reaction, respectively. And the interfacial site (Pd–O–Ce) formed by Pd and CeO2 was the main catalytic site for this type of alcohol oxidation catalysts. This study contributes to the understanding of the catalytic role of interfacial sites in metal and oxide support for the development of better alcohol oxidation catalysts.

Nanoflower core-shell Cu@Pd catalysts for glycol oxidation reaction with an enhanced performance

Direct alcohol fuel cells' performance is significantly affected by the phase and composition of the catalyst, thereby the development of high-performance alcohol oxidation catalysts is essential. In this study, PVA preparation was used for the first time to create PdCu core-shell nanoflowers with a high electrochemically active surface area and a potent synergistic effect. Notably, the presence of PVA causes Pd and Cu nanoparticles with different reduction rates to form a core-shell structure, and the Pd nanoparticles continue to migrate regularly under the action of PVA, forming a flower-like morphology with a high degree of branching. Cu@Pd22.3 catalyst exhibited 13 times higher catalytic performance (4353.04 mA mgPd−1) than Pd/C (334.09 mA mgPd−1) in ethylene glycol oxidation reaction. The Cu@Pd22.3 catalyst also exhibits higher stability than commercial Pd/C in stability tests lasting up to 20,000 s. This core-shell combination and highly branched structural design result in more active sites for fast ion adsorption/desorption,offering an original method to improving the activity and endurance of polyol oxidation.

Iron-palladium supported graphene as an efficient bimetallic catalyst for the selective oxidation of benzyl alcohol to benzaldehyde

The catalytic oxidation of benzyl alcohol (OBA) is one of the significant methods to produce benzaldehyde, an essential reagent in the chemical and pharmaceutical industries. However, developing an active and efficient catalyst for OBA is a tremendous challenge in commercialization. This research describes a simple, eco-friendly method for producing Fe, Pd, and Fe: Pd bimetallic nanoparticles fabricated by sol immobilization over graphene to conduct OBA. The resulting composite nano-alloys were then characterized using X-ray diffraction (XRD), Fourier transforms infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM). The oxidation state and elemental composition of as-fabricated nanoparticles were analyzed using XPS. The point of zero charges (pHPZC) was analyzed and the PZC value indicated that the proposed adsorbent material tends to have a positive charge. The OBA reaction efficiency (87%) of bimetallic nanocatalysts stabilized in graphene support was increased through surface modification of the ratio of both metals. The experimental error was based on three parallel tests and the carbon balance (99.6%) was analyzed during the experiments A proposed reaction mechanism of OBA validated the β-hydride step's elimination by molecular oxygen converting the metal hydride into a water molecule, forming a peroxide intermediate to form water and oxygen molecules. The Fe on the nanocatalyst’s surface is preferentially responsible for the adsorption of the substrate molecule, resulting in the formation of metal-alkoxide. Since it lacks electrons, Fe is more likely to be oxidized, allowing it to perform better than monometallic catalysts in terms of catalytic activity. The present study has great potential to be applied on an industrial scale and studied for industrialists, researchers, and academicians.

Facile synthesis of CoSi alloy catalysts with rich vacancies for base- and solvent-free aerobic oxidation of aromatic alcohols

The rational design and green synthesis of low-cost, robust, and efficient catalysts for the selective oxidation of various alcohols are highly challenging. Herein, we report a fast and solvent-free arc-melting (AM) method to controllably synthesize a semimetallic CoSi alloy catalyst (denoted as AM-CoSi) that is efficient in the base- and solvent-free oxidation of six types of aromatic alcohols. X-ray absorption fine structure analysis, electron paramagnetic resonance spectroscopy, and aberration-corrected high angle annular dark field scanning transmission electron microscopy confirmed the successful synthesis of AM-CoSi with abundant Si vacancies (Siv). The as-prepared CoSi alloy catalysts exhibit an order of magnitude greater activity in the oxidation of a model reactant, benzyl alcohol (BAL) to benzyl benzoate (BBE), compared with their mono-counterparts, and provide 70% yield of BBE, the highest yield reported to date. Experimental results and density functional theory calculations suggest that the CoSi alloy structure improves the BAL conversion and that Si vacancy is the main contributor to the generation of BBE, based on which a potential reaction pathway is rationally proposed. Furthermore, the CoSi alloy maintains high stability and also exhibits high activity in the selective oxidation of various alcohols with different functional groups. This work demonstrates for the first time that semimetallic CoSi alloys can be robust catalysts for the green oxidation of various alcohols and proviedes a vast opportunity for the rational design and application of other semimetal alloy catalysts.

Studies on Catalytic and in Vitro Cytotoxicity Effects of ZnO Nanorods Containing Ag and Their Structural, Morphological, and Antimicrobial Properties

Zinc oxide (ZnO) and Ag-doped ZnO nanoparticles were synthesized using a soft chemical route, and their properties were characterized using various techniques, including X-ray diffraction (XRD), high-resolution scanning electron microscope (HRSEM), energy dispersive X-ray diffraction spectroscopy (EDS), and high-resolution transmission electron microscope (HRTEM). The ZnO (Ag[Formula: see text]Zn[Formula: see text]O (where [Formula: see text], 0.02 and 0.03) exhibited a hexagonal Wurtzite structure, and Ag doping resulted in the formation of nanorods with decreased grain size. The synthesized materials were found to have antimicrobial properties against human pathogenic bacteria and fungi. MTT assays showed that Ag-doped ZnO had higher cytotoxicity against human embryonic kidney cancer cell lines (HEK 293) compared to pure ZnO. The samples also demonstrated active activity towards the catalyst for the selective oxidation of alcohols. Finally, a statistical model was developed for antibacterial studies using ANOVA, which was consistent with the experimental findings. These results demonstrate the potential of Ag-doped ZnO nanoparticles for use in biomedical and catalytic applications.

Nanocrystal Facet Effects of Ceria in Pd/CeO2 Catalysts for Oxidation of Benzyl Alcohols

Key words ceria - palladium nanoparticles - oxidation - benzyl alcohols - benzaldehydes

Ruthenium(III) Chloride as an Efficient Catalyst for the Selective Oxidation of Fatty Alcohols to Aldehydes

AbstractThe oxidation of a series of fatty alcohols to yield the corresponding aldehydes is performed using RuCl3 ⋅ (H2O)x as a homogeneous catalyst and inexpensive trimethylamine N‐oxide (TMAO) as the oxygen source. The reaction conditions were optimized for both high conversion and high selectivity.

Partially Thiolated Au25 Cluster Anchored on Carbon Support via Noncovalent Ligand–Support Interactions: Active and Robust Catalyst for Aerobic Oxidation of Alcohols

Partially thiolated atomically precise Au cluster catalysts were developed by controlled calcination of presynthesized thiolate-protected Au clusters on a porous carbon support. X-ray absorption fine structure analysis, powder X-ray diffraction, and aberration-corrected high-angle annular dark field scanning transmission electron microscopy revealed that calcination of 1 wt % of Au25(SR)18 (RS = 2-phenylethanethiolate, 1-dodecanethiolate) on carbon at 450 °C for 8–12 h produced partially thiolated Au25 clusters Au25(SR)/C without sintering. The Au25(SR)/C catalyst exhibited comparable catalytic activity to that of the thiolate-free Au25 cluster Au25/C for benzyl alcohol oxidation, whereas Au25(SR)/C showed higher durability than Au25/C. These results suggested that the residual RS ligands were distributed at the interface between the clusters and the support and suppressed the diffusion of the clusters by multiple van der Waals interactions. Large kinetic isotope effects indicated that the hydride abstraction from the α-carbon of the alkoxide was the rate-determining step. The O2 pressure dependence on rate constants was comparable to that reported for negatively charged Au clusters stabilized by poly(N-vinyl-2-pyrrolidone). This comparison suggests that electron-rich Au atoms left behind by desorbed RS served as active sites, which was supported by density functional theory calculations on model clusters. The partially thiolated Au25 cluster catalysts oxidized various p-substituted benzyl alcohols and benzylic secondary alcohols, with turn-over numbers exceeding 1 × 104. This work demonstrates that partially ligated, atomically precise metal clusters anchored by noncovalent ligand–support interaction are promising model catalysts with both high activity and durability.