Gold-Catalyzed Aerobic Oxidation of Benzyl Alcohol: Effect of Gold Particle Size on Activity and Selectivity in Different Solvents

The effect of the size of gold particles deposited on CeO₂ and TiO₂ supports on their catalytic behavior in the aerobic oxidation of benzyl alcohol in different solvents (mesitylene, toluene, and supercritical carbon dioxide) has been investigated. The size of supported gold particles deposited via a colloidal route was in the range 1.3–11.3 nm, as determined by means of EXAFS and HAADF-STEM measurements. The catalytic performance of the supported gold catalysts in the different solvents revealed a significant effect of the gold particle size. Optimal activity was observed for catalysts with medium particle size (ca. 6.9 nm) whereas smaller and bigger particles showed inferior activity. Identical trends for the activity–particle size relationship were found using Au/CeO₂ and Au/TiO₂ for the reaction at atmospheric pressure in conventional solvents (mesitylene, toluene) as well as under supercritical conditions (scCO₂). Selectivity to benzaldehyde was only weakly affected by the gold particle size and mainly depended on reaction conditions. In supercritical CO₂ (scCO₂) selectivity was higher than in the conventional solvents under atmospheric pressure. All catalysts tested with particle sizes ranging from 1.3 to 11.3 nm showed excellent selectivity of 99% or higher under supercritical conditions.     

Solvent-free Oxidation of Primary Alcohols to Aldehydes using Supported Gold Catalysts

Supported Au catalysts are investigated for the oxidation of primary alcohols under solvent-free conditions in the absence of base. Three representative primary alcohols have been investigated: benzyl alcohol, octan-1-ol and geraniol using a range of supports for gold nanocrystals prepared using coprecipitation, deposition precipitation and impregnation. For benzyl alcohol and octan-1-ol selective oxidation to the corresponding aldehydes is observed, particularly with Au/CeO₂, whereas for more acidic supports, e.g. Fe₂O₃, subsequent oxidation of the aldehydes to the corresponding acids, forming an ester (benzyl benzoate, octyl octanoate, respectively) by reaction with the alcohol, by a standard acid-catalysed mechanism. Alternatively, the mechanism of ester generation could involve hemiacetal formation between the aldehyde and residual alcohol, followed by direct oxidation to the observed ester. The reaction of geraniol is much more complex and the reaction is carried out in the presence and absence of acids to gain a full understanding of the interplay between oxidation and isomerisation reactions. Comparison with other active catalysts reveals that using Au catalysts in solvent free conditions gives very high turnover frequencies for the synthesis of the aldehydes with 100% selectivity (150 h⁻¹ and 26 h⁻¹ for benzyl alcohol and octan-1-ol, respectively), which are comparable to the best reported to date for these reactions.     

Solvent-free oxidation of benzyl alcohol with oxygen using zeolite-supported Au and Au–Pd catalysts

The oxidation of benzyl alcohol to benzaldehyde has been investigated in the absence of solvent using zeolite-supported Au and Au–Pd catalysts. Three zeolites were investigated, ZSM-5, zeolite β and zeolite Y, and these were contrasted with the titanoslicalite TS-1 and TiO₂ as supports. For the Au catalysts the best results are obtained with zeolite β as the support and the conversions were comparable or better than those observed with TiO₂ in terms of turn over frequencies. However, the selectivities observed with the acidic zeolites were lower than the non-acidic TS-1 and TiO₂. This is due to the subsequent reaction of benzaldehyde via acid catalysed reactions to give benzyl benzoate and its dibenzyl acetal, and, in some cases dibenzylether. Initial catalysts were evaluated with a gold loading of 2 wt% and increasing this to 4 wt% showed the expected increase in activity, indicating that there is scope to improve the performance of these catalysts. The most active catalysts were prepared by impregnation and catalysts prepared by deposition precipitation were considerably less active. Introduction of Pd into the catalyst improved the activity without significantly affecting the selectivity.     

Selective Oxidation of Benzyl-Alcohol over Biomass-Supported Au/Pd Bioinorganic Catalysts

We report a novel biochemical method based on the sacrificial hydrogen strategy to synthesise bimetallic Au/Pd nanoparticles supported on bacterial cells. The synergistic effect of Au/Pd over monometallic preparations was demonstrated in the oxidation of benzyl alcohol. The bioinorganic catalysts outperformed a commercial Pd catalyst (5% Pd/C) showing no deactivation and high selectivity towards benzaldehyde.     

Physicochemical and catalytic properties of nanosized Au/CeO2 catalysts for eco-friendly oxidation of benzyl alcohol

In this work, benzyl alcohol oxidation was investigated over Au/CeO₂-homogeneous deposition–precipitation (ACH) and Au/CeO₂-direct anionic-exchange (ACD) catalysts. Various characterization techniques were employed to study their physicochemical properties. TEM images revealed presence of 5.3 and 7.4 nm Au nanoparticles in ACH and ACD catalysts, respectively. Raman studies showed that only ACH sample exhibits oxygen deficiency (0.0574). Amongst, the ACH catalyst exhibited better catalytic performance owing to smaller gold nanoparticles and abundant oxygen vacancies. The alcohol conversion and product selectivity were strongly dependent on temperature and time-on-stream conditions. The catalytic activity decreased after repeated use due to aggregation of Au nanoparticles.     

Gold–palladium supported on porous steel fiber matrix: Structured catalyst for benzyl alcohol oxidation and benzyl amine oxidation

Au, Pd and Au-Pd alloy are deposited on porous steel fiber matrices via sputtering technique. By this technique the preparation of the heterogeneous catalysts is clean, simple and fast as noble metal complexes, solvents or reducing agents are not needed. The studied Au-Pd catalyst exhibits good activity in the aerobic oxidation of benzyl alcohol and benzyl amines. Especially in the oxidation of benzyl amines, the Au-Pd catalyst shows a great synergistic enhancement in the activity.     

Enhancing the catalytic activity of carbon nanotubes by nitrogen doping in the selective liquid phase oxidation of benzyl alcohol

Nitrogen-doped carbon nanotubes (N-CNTs) were prepared by chemical vapor deposition method and employed as carbon-based catalysts for selective oxidation of benzyl alcohol to benzaldehyde with molecular oxygen as the terminal oxidant under the mild reaction conditions. The results showed that the N-CNTs exhibited much higher activity than the undoped CNTs, and the improved catalytic activity was probably attributed to the introduction of electron-rich nitrogen atoms in the graphitic domains enhanced electron transfer. Moreover, N-CNTs displayed excellent stability without an obvious loss in activity and selectivity for benzyl alcohol oxidation after eight cycling reactions. The results presented herein pave the way for the development of novel carbon catalyst for the liquid-phase oxidation of benzyl alcohol.     

Mixed Alcohol Synthesis from Syngas on K–Co–Mo/C Catalyst Prepared by a Sol–Gel Method

A kind of K–Co–Mo/C catalyst with homogenous components distribution and small particle size was prepared by sol–gel method with citric acid as complexant. Its structure and catalytic performance for mixed alcohol synthesis were investigated. By heat treating the dried gel in argon, the decomposition of citric acid resulted in the formations of amorphous carbon and low-valence MoO₂ species. The incorporation of potassium and cobalt increased significantly the alcohol synthesis activity, especially improved the C₂₊OH selectivity. The optimal atomic composition of catalyst was: 0.10 K: 0.50 Co: 1.0 Mo. Comparing with the similar catalysts reported in literatures, the sol–gel derived K–Co–Mo catalyst showed better performance, especially much higher C₂₊OH selectivity for mixed alcohol synthesis. A 150 h reaction test indicated that the catalyst had good stability during the entire experimental period. It suggested that the homogenous components distribution and small particle size enhanced the synergistic effect of promoters and created more active species, leading to a high catalytic performance. The formation of MoO₂ species was also favorable to improve the catalytic activity because the low-valence Mo⁴⁺ was known to be more active in CO hydrogenation.     

Structure–activity relationships in supported Au catalysts

Au-based catalysts have great potential because of their unique activity and selectivity for a variety of important reactions. The special catalytic properties of supported Au nano-particles depend critically upon the particle morphology, i.e. size, shape and thickness, as well as support effects. This paper reviews the current understanding of CO oxidation on supported Au catalysts. The electronic structure of Au particles at various nucleation sites and on different supports is summarized, and the effect these changes have on catalytic performance is discussed. Recent results from our laboratories have demonstrated the synthesis of well-ordered Au mono- and bi-layer films on a titanium oxide support and show that the active Au structure for CO oxidation is an electron-rich, Au bi-layer. In contrast, the monolayer structure, which may involve the TiO_x support, is significantly less active (by less than an order of magnitude) than the Au bi-layer. The oxidation state of the Au and how this relates to the catalytic activity are also discussed.     

Alcohol oxidations in aqueous solutions using Au,Pd, and bimetallic AuPd nanoparticle catalysts

Alcohol oxidations under mild conditions using polyvinylpyrrolidone (PVP)-stabilized Au, Pd and bimetallic AuPd nanoparticle catalysts in aqueous solutions have been investigated. The catalytic activities of the nanoparticles towards the oxidation of benzyl alcohol, 1-butanol, 2-butanol, 2-buten-1-ol and 1,4-butanediol indicate that bimetallic 1:3 Au:Pd nanoparticles have higher catalytic activities than Au, Pd and other bimetallic AuPd nanoparticles, and that selectivities towards specific products can often be tuned using bimetallic particles. In addition, advantages and disadvantages for the use of such nanoparticle catalysts as mild, environmentally-friendly oxidation catalysts are examined.     

Catalytic activity of ethylene oxidation over Au,Ag and Au–Ag catalysts: Support effect

Au, Ag and Au–Ag catalysts on different supports of alumina, titania and ceria were studied for their catalytic activity of ethylene oxidation reactions. An addition of an appropriate amount of Au on Ag/Al₂O₃ catalyst was found to enhance the catalytic activity of the ethylene epoxidation reaction because Au acts as a diluting agent on the Ag surface creating new single silver sites which favor molecular oxygen adsorption. The Ag catalysts on both titania and ceria supports exhibited very poor catalytic activity toward the epoxidation reaction of ethylene, so pure Au catalysts on these two supports were investigated. The Au/TiO₂ catalysts provided the highest selectivity of ethylene oxide with relatively low ethylene conversion whereas, the Au/CeO₂ catalysts was shown to favor the total oxidation reaction over the epoxidation reaction at very low temperatures. In comparisons among the studied catalysts, the bimetallic Au–Ag/Al₂O₃ catalyst is the best candidate for the ethylene epoxidation. The catalytic activity of the gold catalysts was found to depend on the support material and catalyst preparation method which govern the Au particle size and the interaction between the Au particles and the support.     

Hydrogenation of 1,3-butadiene and of crotonaldehyde over highly dispersed Au catalysts

When Au is deposited as nano-particles on select metal oxides, it exhibits surprisingly high catalytic activity for many oxidation reactions. Therefore, there is also the possibility to improve the activities of Au catalysts for hydrogenation using the appropriate preparation methods like the gas-phase grafting method (GG) and the deposition precipitation method (DP). In this work, we investigated the hydrogenation of 1,3-butadiene and of crotonaldehyde over Au catalysts prepared by GG and DP and discussed the structure sensitivity of these reactions. From these experiments, it was found that the catalytic activities for the hydrogenation of 1,3-butadiene over Au catalysts was almost structure insensitive in terms of the size effect of Au particles and the influence of metal oxides supports and the crotonaldehyde hydrogenation over Au catalysts was slightly sensitive to the selection of the support in the view point of the product selectivity.     

Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: Effect of Au–Pd ratio on catalytic performance

The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO₂ was found to be the most active catalyst, whereas the Au/TiO₂ catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions.     

Effect of Particle Size on Monometallic and Bimetallic (Au,Pd)/C on the Liquid Phase Oxidation of Glycerol

The influence of metal particle size of monometallic and bimetallic supported catalysts (Au, Pd, Au–Pd)/C was studied using as a model reaction the liquid phase oxidation of glycerol. By tuning the metal particle size from 2 to 16 nm a progressive decrease of activity and simultaneously an increase in the selectivity to sodium glycerate was observed. Moreover, the influence of the temperature was studied and it was found that by increasing the temperature, only with a large particle size the formed glycerate was retained and not over-oxidized to tartronate.     

TiO2 Supported Nano—Au Catalysts Prepared via Solvated Metal Atom Impregnation for Low-Temperature CO Oxidation

TiO₂ supported nano-Au catalysts were prepared by solvated metal atom impregnation (SMAI) method. The catalysts were characterized by means of AAS, TPD, H₂ reduction desorption (H₂-RD), XRD, TEM, XPS and tested for low-temperature CO oxidation. XRD and TEM results showed that the pretreatment temperature had an influence on the particle size of Au/TiO₂catalysts. The average particle size increased with the increase in pretreatment temperature. XPS indicated that gold in the catalysts was presented in the form of metallic state clusters. Catalytic studies showed these catalysts were very active and stable in low-temperature CO oxidation. The CO oxidation activity of the catalysts increased as the Au particle size decreased. The measurement results of AAS, TPD and H₂-RD revealed that there were some organic fragments on the surface of Au particles which might be responsible for the high stability of the Au/TiO₂ catalysts.     

Lattice oxide ion-transfer effect demonstrated in the selective oxidation of propene over silica-supported bismuth molybdate catalysts

Silica-supported bismuth molybdate catalysts were prepared by impregnation in a highly dispersed state and by coprecipitation in a largely crystallized state. Their catalytic behavior was investigated in the oxidation of propene to acrolein. The highly dispersed bismuth molybdate catalysts on silica were found to be intrinsically active but poorly selective to acrolein. When we increased the loading amount the oxidation activity drastically increased. The poor acrolein selectivity of this catalyst was improved by continuous use in the catalytic oxidation for making the particle size of the dispersed bismuth molybdate larger. The catalytic activity and selectivity were little influenced by the loading amount in the cases of the coprecipitated catalysts. The results demonstrate that, for the activity and selectivity, bismuth molybdate catalysts need to be of a certain particle size which can provide sufficient lattice oxide ions during the catalytic redox cycle.     

Au/Ti-SBA-15 catalysts in CO and preferential (PROX) CO oxidation

The Au/Ti-SBA-15 catalysts were found promising for CO oxidation, including preferential CO oxidation in the presence of H₂ (PROX). The catalytic performance and Au particle size depending on the Ti content: 100% selectivity to CO₂ in PROX at 90% CO conversion was found for the catalysts of the Ti content below 1.32 wt.% Ti.     

Au-Pd/ZrO2可见光下催化苯甲醇氧化反应条件探索

利用硼氢化钠还原法制备出Au-Pd/ZrO₂负载型双金属纳米催化剂,采用XRD、UV-vis DRS、TEM等手段对催化剂的结构、吸光能力、粒度、形貌等性能进行表征。结果显示,金、钯成功负载于二氧化锆上,且金、钯以球形颗粒均匀分散。可见光照射下,研究了Au-Pd/ZrO₂双金属纳米催化剂对苯甲醇氧化生产苯甲醛反应的适宜条件。实验结果显示,可见光照射下,反应时间为12 h、反应温度为（35±3） ℃、5.0 mL异丙醇为溶剂、50 mg Au-Pd（2:1）/ZrO₂为催化剂、1.0 mmol氢氧化钾为碱源的条件下,苯甲醇氧化生产苯甲醛产率最佳。     

无定型MnO2的制备及其催化苯甲醇选择氧化性能

用KMnO₄和MnSO₄为原料，通过简单的氧化还原过程合成了无定形MnO₂，并用于催化苯甲醇氧化制苯甲醛，发现制得的无定形MnO₂在催化苯甲醇氧化制苯甲醛中表现出较高的活性和苯甲醛选择性（100%）。考察了反应温度、氧浓度、催化剂用量以及反应时间对苯甲醇氧化的影响。结果表明，较高的反应温度和氧浓度以及合适的催化剂用量有利于无定形MnO₂催化苯甲醇氧化生成苯甲醛，在反应温度110 ℃、常压和通氧条件下反应3 h, 苯甲醇转化率和苯甲醛选择性均为100%。     

Acetylene Hydrogenation on Au-Based Catalysts

Hydrogenation of acetylene has been investigated on Au/TiO₂, Pd/TiO₂ and Au-Pd/TiO₂ catalysts at high acetylene conversion levels. The Au/TiO₂ catalyst (avg. particle size: 4.6 nm) synthesized by the temperature-programmed reduction-oxidation of an Au-phosphine complex on TiO₂ showed a remarkably high selectivity to ethylene formation even at 100% acetylene conversion. Au/TiO₂ prepared by the conventional incipient wet impregnation method (avg. particle size: 30 nm), on the other hand, showed negligible activity for acetylene hydrogenation. Although the Au catalysts showed a high selectivity for ethylene, the acetylene conversion activity and catalyst stability were inferior to the Pd-based catalysts. Au-Pd catalysts prepared by the redox method showed high acetylene conversions as well as high selectivity for ethylene. Interestingly Au-Pd catalysts prepared by depositing Pd via the incipient wetness method on Au/TiO₂ showed very poor selectivity (comparable to mono-metallic Pd catalysts) for ethylene. High-resolution transmission electron microscopy (TEM) studies coupled with energy dispersive X-ray spectroscopy (EDS) showed that while the redox method produced bimetallic Au-Pd catalysts, the latter method produced individual Pd and Au particles on the support.