Preparation of Hydrophobic Au Catalyst and Application in One-Step Oxidative Esterification of Methacrolein to Methyl Methacrylate.

The water produced during the oxidative esterification reaction occupies the active sites and reduces the activity of the catalyst. In order to reduce the influence of water on the reaction system, a hydrophobic catalyst was prepared for the one-step oxidative esterification of methylacrolein (MAL) and methanol. The catalyst was synthesized by loading the active component Au onto ZnO using the deposition-precipitation method, followed by constructing the silicon shell on Au/ZnO using tetraethoxysilane (TEOS) to introduce hydrophobic groups. Trimethylchlorosilane (TMCS) was used as a hydrophobic modification reagent to prepare hydrophobic catalysts, which exhibited a water droplet contact angle of 111.2°. At a temperature of 80 °C, the hydrophobic catalyst achieved a high MMA selectivity of over 95%. The samples were characterized using XRD, N2 adsorption, ICP, SEM, TEM, UV-vis, FT-IR, XPS, and water droplet contact angle measurements. Kinetic analysis revealed an activation energy of 22.44 kJ/mol for the hydrophobic catalyst.

First example of organocatalysis by cathodic N-heterocyclic carbene generation and accumulation using a divided electrochemical flow cell.

In this paper we present the first electrochemical generation of NHC carried out in a divided flow cell. The flow cell operated in the recycle mode. The need for a divided cell derived from the anodic electroactivity of the electrogenerated carbene. In order to have NHC accumulation in the catholyte, the Nafion membrane (cell separator) was pretreated with an alkaline solution. The formation of NHC was quantified as its reaction product with elemental sulfur. The NHC was successfully used as organocatalyst in two classical umpolung reactions of cinnamaldehyde: its cyclodimerization and its oxidative esterification.

Electro-Oxidative Selective Esterification of Methylarenes and Benzaldehydes.

A mild and green electro-oxidative protocol to construct aromatic esters from methylarenes and alcohols is herein reported. Importantly, the reaction is free of metals, chemical oxidants, bases, acids, and operates at room temperature. Moreover, the design of the electrolyte was found critical for the oxidation state and structure of the coupling products, a rarely documented effect. This electro-oxidative coupling process also displays exceptional tolerance of many fragile easily oxidized functional groups such as hydroxy, aldehyde, olefin, alkyne, as well as neighboring benzylic positions. The enantiomeric enrichment of some chiral alcohols is moreover preserved during this electro-oxidative coupling reaction, making it overall a promising synthetic tool.

Zn Promoted Mg-Al Mixed Oxides-Supported Gold Nanoclusters for Direct Oxidative Esterification of Aldehyde to Ester.

The synthesis of ester compounds is one of the most important chemical processes. In this work, Zn-Mg-Al mixed oxides with different Zn2+/Mg2+ molar ratios were prepared via co-precipitation method and supported gold nanoclusters to study the direct oxidative esterification of aldehyde and alcohol in the presence of molecular oxygen. Various characterization techniques such as N2-physical adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and CO2 temperature programmed desorption (TPD) were utilized to analyze the structural and electronic properties. Based on the results, the presence of small amounts of Zn2+ ions (~5 wt.%) provoked a remarkable modification of the binary Mg-Al system, which enhanced the interaction between gold with the support and reduced the particle size of gold. For oxidative esterification reaction, the Au25/Zn0.05MgAl-400 catalyst showed the best performance, with the highest turnover frequency (TOF) of 1933 h-1. The active center was believed to be located at the interface between metallic gold with the support, where basic sites contribute a lot to transformation of the substrate.

Photocatalytic C-H Activation and Oxidative Esterification Using Pd@g-C3N4.

Graphitic carbon nitride supported palladium nanoparticles, Pd@g-C3N4, have been synthesized and utilized for the direct oxidative esterification of alcohols using atmospheric oxygen as a co-oxidant via photocatalytic C-H activation.

Efficient and simple approaches towards direct oxidative esterification of alcohols.

The present article describes novel oxidative protocols for direct esterification of alcohols. The protocols involve successful demonstrations of both "cross" and "self" esterification of a wide variety of alcohols. The cross-esterification proceeds under a simple transition-metal-free condition, containing catalytic amounts of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy)/TBAB (tetra-n-butylammonium bromide) in combination with oxone (potassium peroxo monosulfate) as the oxidant, whereas the self-esterification is achieved through simple induction of Fe(OAc)2 /dipic (dipic=2,6-pyridinedicarboxylic acid) as the active catalyst under an identical oxidizing environment.

Mechanism regulation over dual-atom catalyst enables high-performance oxidative alcohol esterification.

The development of heterogeneous catalysts with well-defined uniform isolated or multiple active sites is of great importance for understanding catalytic performances and studying reaction mechanisms. Herein, we present a CoCu dual-atom catalyst (CoCu-DAC) where bonded Co-Cu dual-atom sites are embedded in N-doped carbon matrix with a well-defined Co(OH)CuN6 structure. The CoCu-DAC exhibits higher catalytic activity and selectivity than the Co single-atom catalyst (Co-SAC) and Cu single-atom catalyst (Cu-SAC) counterparts in the catalytic oxidative esterification of alcohols and a variety of methyl and alkyl esters have been successfully synthesized. Kinetic studies reveal that the activation energy (29.7 kJ mol-1) over CoCu-DAC is much lower than that over Co-SAC (38.4 kJ mol-1) and density functional theory (DFT) studies disclose that two different mechanisms are regulated over CoCu-DAC and Co-SAC/Cu-SAC in three-step esterification of alcohols. The bonded Co-Cu and adjacent N species efficiently catalyze the elementary reactions of alcohol dehydrogenation, O2 activation and ester formation, respectively. The stepwise alkoxy pathway (O-H and C-H scissions) is preferred for both alcohol dehydrogenation and ester formation over CoCu-DAC, while the progressive hydroxylalkyl pathway (C-H and O-H scissions) for alcohol dehydrogenation and simultaneous hemiacetal dehydrogenation are favored over Co-SAC and Cu-SAC. Characteristic peaks in the Fourier transform infrared spectroscopy analysis may confirm the formation of the metal-C intermediate and the hydroxylalkyl pathway over Co-SAC.

Synthesis of enantiomerically pure N-(2,3-dihydroxypropyl)arylamides via oxidative esterification.

A highly efficient synthesis of enantiomerically pure (S) and (R)-isomers of N-(2,3-dihydroxypropyl)arylamides has been developed with good overall yields in a two step process. The key step involves the ring opening of the chiral epoxide with a nitrogen heterocyclic carbene (NHC) and further rearrangement to chiral N-(2,3-dihydroxypropyl)arylamides in high yields and enantioselectivity. During the reaction, no erosion in chiral purity was observed.

Gold/Substituted Hydroxyapatites for Oxidative Esterification: Control of Thin Apatite Layer on Gold Based on Strong Metal-Support Interaction (SMSI) Results in High Activity.

Gold nanoparticles (Au NPs) deposited on various cation- and anion-substituted hydroxyapatites (Au/sHAPs) show oxidative strong metal-support interaction (SMSI), wherein a thin layer of the sHAP covered the surface of the Au NPs by heat treatment in an oxidative atmosphere. Calcination of Au/sHAPs at 300 °C caused a partial SMSI and that at 500 °C gave fully encapsulated Au NPs. We investigated the influence of the substituted ions in sHAP and the degree of the oxidative SMSI on the catalytic performance of Au/sHAPs for oxidative esterification of octanal or 1-octanol with ethanol to obtain ethyl octanoate. The catalytic activity depends on the size of the Au NPs but not on the support used, owing to the similarity of the acid and base properties of sHAPs except for Au/CaFAP. The presence of a large number of acidic sites on CaFAP lowered the product selectivity, but all other sHAPs exhibited similar activity when the Au particle size was almost the same, owing to the similarity of the acid and base properties. Au/sHAPs_O2 with SMSI exhibited higher catalytic activity than Au/sHAPs_H2 without SMSI despite the fact that the number of exposed surface Au atoms was decreased by the SMSI. In addition, the oxidative esterification reaction proceeded even though the Au NPs were fully covered by the sHAP layer when the thickness of the layer was controlled to be less than 1 nm. The substrate can access the surfaces of the Au NPs covered by the thin sHAP layer (<1 nm), and the presence of the sHAP structure in close contact with the Au NPs resulted in significantly higher catalytic activity compared with that for fully exposed Au NPs deposited on the sHAPs. This result suggests that maximizing the contact area between the Au NPs and the sHAP support based on the SMSI enhances the catalytic activity of Au.

A convenient green protocol for oxidative esterification of arylaldehydes over Pd NPs decorated polyplex encapsulated Fe3O4 microspheres.

A mild, competent and eco-friendly protocol has been developed for oxidative esterification of various aldehydes over a post-synthetically modified and Pd fabricated chitosan-starch dual functionalized Fe3O4 microspheres as a magnetically isolable heterogeneous and biocompatible nanocatalyst. Molecular O2 was used as an oxidant in the reaction. A series of aldehydes was directly esterified with MeOH in excellent yields without any pre-activation and involvement of harsh chemicals/conditions. Structural features of the catalyst were assessed through FT-IR, FE-SEM, TEM, EDX, molecular mapping, XRD, VSM and ICP-OES techniques. Due to magnetic core, the catalyst was easily isolated using an external magnet and reused for 8 times in succession, retaining its morphology and catalytic activity.

Control in Local Coordination Environment Boosting Activating Molecular Oxygen with an Atomically Dispersed Binary Mn-Co Catalyst.

Activation of molecular oxygen plays a crucial role in natural organisms and the modern chemical industry. Herein, we report a Mn-Co dual-single-atom catalyst that exerts a specific synergy in boosting O2 activation by collaboration between two distinct types of activation sites. Taking the oxidative esterification of the biomass platform 5-hydroxymethylfurfural (HMF) as the model reaction, the activation of O2 is demonstrated through transforming O2 into a reactive superoxide anion radical (O2•-) on Co-N4 sites and, meanwhile, by reversible consumption and supplement of coordinated surface oxygen as a new type of reactive oxygen species (ROS) on N,O-coordinated single-atom Mn sites (Mn-NxOy). EXAFS analysis results show a longer average Mn-O bond distance at near 2.19 Å, which makes the breaking and formation of surface Mn-O bonds easier to cycle. Control experiments support that such Mn-O bonding conditions could facilitate H-elimination of C-H in HMF. The co-existence of two types of ROS effectively matches the oxidation of hydroxyl and aldehyde groups, and thus, the overall reaction is boosted in excellent yield of diester (95.8%) with an extremely high carbon balance. This study represents a rare example of taking advantage of the synergy of the diatomic catalyst for activating O2 by two types of activation pathways.

Crystal Facet Structure Dependence and Promising Pd-Based Catalytic Materials for Resistance toward Deactivation and Catalytic Performance in Direct Oxidative Esterification.

Designing an effective Pd-based catalytic material with higher stability and catalytic performance for direct oxidative esterification is a great challenge. In this work, a systematic study on the activation mechanism of H2O on the different crystal facets of monometallic Pd, bimetallic Pd-Pb(Bi), and trimetallic Pd-Pb-Bi catalysts was first performed, which showed that the (111) crystal facet of Pd-Pb-Bi had stronger stability of resistance toward deactivation induced by H2O. Further, a detailed direct oxidative esterification mechanism on the screened crystal facet was investigated, where Pd-Pb-Bi catalytic materials showed higher stability and intrinsic catalytic performance for direct oxidation esterification, which was attributed to a dimer Pd-active unit and the synergistic effect of Pb and Bi compared to that of Pd-Pb(Bi) and Pd and also applied to other aldehydes with electron-donating groups producing corresponding esters. Meanwhile, the essential relationship between structures of Pd-based catalytic materials and catalytic performance for direct oxidation esterification was obtained. This work opens up a new simultaneous path for improving the stability of resistance toward deactivation and catalytic performance for direct oxidative esterification of Pd-based catalytic materials, which can be realized by regulating the surface-active unit with dimer Pd adsorbed more O-preadsorbed using Pb and Bi promoters.

Ultrafine Copper Oxide Particles Dispersed on Nitrogen-Doped Hollow Carbon Nanospheres for Oxidative Esterification of Biomass-Derived 5-Hydroxymethylfurfural.

One-pot synthesis of furan-2,5-dimethylcarboxylate (FDMC) from 5-hydroxymethylfurfural (HMF) is highly demanding for the commercial production of polyethylene furanoate (PEF). Herein, a direct synthesis of FDMC is reported from oxidative esterification of HMF using ultrafine CuO particles dispersed on nitrogen-doped hollow carbon nanospheres (CuO/N-C-HNSs) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidizing and methylating reagent. The CuO/N-C-HNSs was prepared through a template protection-sacrifice strategy using SiO2 as a sacrificial template and histidine as the precursor for N and C. N-doping facilitated a strong interaction between the support and copper species, affording formation of CuO nanoparticles of less than 10 nm in size. By virtue of the highly dispersed CuO nanoparticles and a high BET surface area 373 m2 /g, the CuO/N-C-HNSsshows excellent catalytic performance in the selective conversion of HMF into FDMC affording 93 % yield of the desired product with a TON value of 49. Furthermore, the oxidative esterification involving SP3 C-H bond functionalization is also demonstrated using the same catalyst.

A Multifunctional Au/CeO2-Mg(OH)2 Catalyst for One-Pot Aerobic Oxidative Esterification of Aldehydes with Alcohols to Alkyl Esters.

Au nanoparticles bound to crystalline CeO2 nanograins that were dispersed on the nanoplate-like Mg(OH)2, denoted as Au/CeO2-Mg(OH)2, were developed as the highly active and selective multifunctional heterogeneous catalyst for direct oxidative esterification of aldehydes with alcohols to produce alkyl esters under base-free aerobic conditions using oxygen or air as the green oxidants. Au/CeO2-Mg(OH)2 converted 93.3% of methacrylaldehyde (MACR) to methyl methacrylate (MMA, monomer of poly(methyl methacrylate)) with 98.2% selectivity within 1 h, and was repeatedly used over eight recycle runs without regeneration. The catalyst was extensively applied to other aldehydes and alcohols to produce desirable alkyl esters. Comprehensive characterization analyses revealed that the strong metal-support interaction (SMSI) among the three catalytic components (Au, CeO2, and Mg(OH)2), and the proximity and strong contact between Au/CeO2 and the Mg(OH)2 surface were prominent factors that accelerated the reaction toward a desirable oxidative esterification pathway. During the reaction, MACR was adsorbed on the surface of CeO2-Mg(OH)2, upon which methanol was simultaneously activated for esterifying the adsorbed MACR. Hemiacetal-form intermediate species were subsequently produced and oxidized to MMA on the surface of the electron-rich Au nanoparticles bound to partially reduced CeO2-x with electron-donating properties. The present study provides new insights into the design of SMSI-induced supported-metal-nanoparticles for the development of novel, multifunctional, and heterogeneous catalysts.

Controlled Metal-Support Interactions in Au/CeO2-Mg(OH)2 Catalysts Activating the Direct Oxidative Esterification of Methacrolein with Methanol to Methyl Methacrylate.

The strong metal-support interaction (SMSI) between the three components in Au/CeO2-Mg(OH)2 can be controlled by the relative composition of CeO2 and Mg(OH)2 and by the calcination temperature for the direct oxidative esterification of methacrolein (MACR) with methanol to methyl methacrylate (MMA). The composition ratio of CeO2 and Mg(OH)2 in the catalyst affects the catalytic performance dramatically. An Au/CeO2 catalyst without Mg(OH)2 esterified MACR to a hemiacetal species without MMA production, which confirmed that Mg(OH)2 is a prerequisite for successful oxidative esterification. When Au/Mg(OH)2 was used without CeO2, the direct oxidative esterification of MACR was successful and produced MMA, the desired product. However, the MMA selectivity was much lower (72.5%) than that with Au/CeO2-Mg(OH)2 catalysts, which have an MMA selectivity of 93.9-99.8%, depending on the relative composition of CeO2 and Mg(OH)2. In addition, depending on the calcination temperature, the crystallinity of the CeO2-Mg(OH)2 and the surface acidity/basicity can be remarkably changed. Consequently, the Au-nanoparticle-supported catalysts exhibited different MACR conversions and MMA selectivities. The catalytic behavior can be explained by the different metal-support interactions between the three components depending on the composition ratio of CeO2 and Mg(OH)2 and the calcination temperature. These differences were evidenced by X-ray diffraction, X-ray photoelectron spectroscopy, and CO2 temperature-programmed desorption. The present study provides new insights into the design of SMSI-induced supported metal catalysts for the development of multifunctional heterogeneous catalysts.

Oxidative Esterification of 5-Hydroxymethylfurfural with an N-doped Carbon-supported CoCu Bimetallic Catalyst.

The direct fabrication of furan-2,5-dimethylcarboxylate (FDMC), a promising renewable monomer, from biomass-derived 5-hydroxymethylfurfural (HMF) is a cutting-edge process. In this contribution, an elaborately designed N-doped carbon-supported CoCu bimetallic catalyst (Cox Cuy -NC; x/y=9:1, 7:3, 4:6, which represents the designed molar ratio of Co and Cu in the catalyst), which could offer a desirable FDMC yield of 95 % under mild and base-free conditions (Co7 Cu3 -NC, 2 bar O2 , 80 °C, 4 h) is described for the oxidative esterification of HMF. Notably, an FDMC formation rate of 6.1 molFDMC molCo -1 h-1 was achieved over Co7 Cu3 -NC, which represents the highest catalytic efficiency so far among Co-based catalytic systems. It has been demonstrated that Cu-doping in Co7 Cu3 -NC catalyst brings about more active sites (Co-Nx species) with stronger molecular oxygen activation ability. The increase of surface N content of Co7 Cu3 -NC also improves basicity of the catalyst, which favors the hydrogen abstraction process during the HMF oxidative esterification reaction. These findings may pave an efficient and green way for the synthesis of sustainable bio-based polymer monomers.

Pd-Colloids-Catalyzed/Ag2 O-Oxidized General and Selective Esterification of Benzylic Alcohols.

Palladium colloids obtained from the degradation of Hermann-Beller palladacycle proved to be an efficient catalytic system in combination with silver oxide as a selective oxidant for the oxidative esterification of differently substituted benzyl alcohols in MeOH as solvent. Excellent reactivity exhibited by the catalytic system also allowed the alcoholic coupling partner to be changed from MeOH to a wide range of alcohols having diverse functionalities. The mildness of the developed protocol also made it possible to employ propargyl alcohol as the coupling partner without any observation of any interference of the terminal alkyne. Selective oxidative coupling of a primary alcoholic functional group over secondary in the case of glycols and glycerols was also made possible using the developed catalyst system. To test the relevancy of Pd/Ag combined catalysis mixed Pd/Ag colloids were synthesized, characterized by TEM, XRD and XPS and applied to oxidative-esterification successfully.

Ultrahigh-Content Nitrogen-doped Carbon Encapsulating Cobalt NPs as Catalyst for Oxidative Esterification of Furfural.

It is an attractive and challenging topic to endow non-noble metal catalysts with high efficiency via a nitrogen-doping approach. In this study, a nitrogen-doped carbon catalyst with high nitrogen content encapsulating cobalt NPs (CoOx @N-C(g)) was synthesized, and characterized in detail by XRD, HRTEM, N2 -physisorption, ICP, CO2 -TPD, and XPS techniques. g-C3 N4 nanosheets act as nitrogen source and self-sacrificing templates, giving rise to an ultrahigh nitrogen content of 14.0 %, much higher than those using bulk g-C3 N4 (4.4 %) via the same synthesis procedures. As a result, CoOx @N-C(g) exhibited the highest performance in the oxidative esterification of biomass-derived platform furfural to methylfuroate under base-free conditions, achieving 95.0 % conversion and 97.1 % selectivity toward methylfuroate under 0.5 MPa O2 at 100 °C for 6 h, far exceeding those of other cobalt-based catalysts. The high efficiency of CoOx @N-C(g) was closely related to its high ratio of pyridinic nitrogen species that may act as Lewis basic sites as well as its capacity for the activation of dioxygen to superoxide radical O2 .- .

Insight into the Effective Aerobic Oxidative Cross-Esterification of Alcohols over Au/Porous Boron Nitride Catalyst.

Boron nitride (BN) has attracted great attention with an unexpected ability in aerobic catalysis. Still, its related probe reactions are relatively rare, and the effect of the BN-supported metal catalyst on O2 activation is still ambiguous, and opinions are varied. In this work, the porous BN (pBN)-supported Au catalyst with a porous structure and exposed edges exhibits high activity in the oxidative cross-esterification reactions between the aromatic and C1-C3 aliphatic alcohols at ambient temperature. The turnover frequency value for methyl benzoate is 118 h-1 at 30 °C, and the calculated apparent activation energy (Ea, 58 kJ/mol) is comparable to that of AuPd/TiO2, Ru/Al2O3, and PdBiTe catalysts. Combined with temperature-programmed  desorption (TPD) results, the loading of Au enhances the desorption of O2 and the interaction with alcohols; thus, a synergistic effect between the O-rich pBN and Au is considered. The free-radical scavenger can dramatically suppress the conversion (∼6%), suggesting that the reaction proceeds via the O2* radicals. According to the vibration of νO-O, δOO-H, and νB-O-O-B detected by attenuated total reflectance-infrared spectroscopy (ATR-IR), we are prone to consider the oxygen activation route by the edge B atoms. Then, a possible L-H reaction mechanism was proposed: benzyl alcohol and O2 adsorb on the Au/pBN initially, then O2 is converted to O2*, and the α-H elimination proceeds; as the semi-acetal formed, another α-H elimination proceeds and methyl benzoate is finally formed.

Ultrasound assisted direct oxidative esterification of aldehydes and alcohols using graphite oxide and Oxone.

A sonochemical procedure for direct oxidative esterification of aldehydes and alcohols using graphite oxide and Oxone in an alcoholic solvent is described. Mild reaction conditions, short reaction times, cost-effectiveness, and facile isolation of the products make the present system as a practical method.