Activation of Supported Pd Metal Catalysts for Selective Oxidation of Hydrogen to Hydrogen Peroxide

Catalytic activity of supported Pd metal catalysts (Pd metal deposited on carbon, alumina, gallia, ceria or thoria) showing almost no activity in the liquid-phase direct oxidation of H₂ to H₂O₂ (at 295 K) in acidic medium (0.02 M H₂SO₄) can be increased drastically by oxidizing them using different oxidizing agents, such as perchloric acid, H₂O₂, N₂O and air. In the case of the Pd/carbon (or alumina) catalyst, perchloric acid was found to be the most effective oxidizing agent. The order of the H₂-to-H₂O₂ conversion activity for the perchloric-acid-oxidized Pd/carbon (or alumina) and air-oxidized other metal oxide supported Pd catalysts is as follows: Pd/alumina < Pd/carbon < Pd/CeO₂ < Pd/ThO₂ < Pd/Ga₂O₃. The H₂ oxidation involves lattice oxygen from the oxidized catalysts. The catalyst activation results mostly from the oxidation of Pd metal from the catalyst producing bulk or sub-surface PdO. It also caused a drastic reduction in the H₂O₂ decomposition activity of the catalysts. There exists a close relationship between the H₂-to-H₂O₂ conversion activity and/or H₂O₂ selectivity in the oxidation process and the H₂O₂ decomposition activity of the catalysts; the higher the H₂O₂ decomposition activity, the lower the H₂-to-H₂O₂ conversion activity and/or H₂O₂ selectivity.     

Characterization and Activity of Cu/ZSM5 Catalysts for the Oxidation of Phenol with Hydrogen Peroxide

The heterogeneous catalytic wet peroxide oxidation (CWPO), involving total oxidation of organic compounds to CO₂ and H₂O is a possible path for the treatment of toxic and bio‐refractory wastewater streams. The aim of this work was to synthesize and characterize three Cu/ZSM5 catalysts prepared by direct hydrothermal synthesis. The mass ratio of the active metal component in the zeolite ranged from 1.62–3.24 wt %. These materials were tested for CWPO of aqueous phenol in a stainless steel Parr reactor, in batch operation under mild conditions (at atmospheric pressure and a temperature of 353 K). The catalyst weight was 0.1 g dm^–3 and the initial concentration of phenol and hydrogen peroxide were 0.01 mol dm^–3 and 0.1 mol dm^–3, respectively. The catalysts were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), AAS and ICP‐MS. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversion, hydrogen peroxide decomposition, by‐product distribution and the degree of copper leached into the aqueous solution. The experimental results indicated that within 180 min, these catalysts facilitated almost complete elimination of phenol and a significant removal of chemical oxygen demand, without significant leaching of Cu ions from the zeolite. The Cu/ZSM5‐DHS3 catalyst with the highest copper loading was proven to be the best candidate. The useful fraction of hydrogen peroxide that contributed to the removal of the organic compounds quantified in terms of selectivity, S, indicated that the CWPO selectivity was always less than 100 %, which meant that there was some self‐degradation of oxidant. It was also shown that oxidation of phenol took place on the catalyst surface via a heterogeneous mechanism, and that the contribution of any homogeneous reaction mechanism was not significant.     

双氧水作用下的芳香基烯烃氧化

芳香基烯烃是重要的石油化工原料,其氧化产物是常用的有机中间体。为进行芳烯氧化反应的研究,先以苯乙烯为原料,着重讨论了催化剂、氧化剂用量和溶剂用量对氧化反应的影响。在0.52 g(5.0 mmol)苯乙烯、0.02 g催化剂水滑石、2.6 m L溶剂乙腈、2.4 m L氧化剂双氧水、70℃下反应10 h,苯乙烯转化率为93%,苯乙酮产率为87%。并且在相同的反应条件下,其他芳香基烯烃也可氧化生成相应的酮类。实验结果表明,由双氧水、水滑石、乙腈构成的反应体系能很好地进行苯乙烯等芳香基烯烃的氧化。     

Direct Synthesis of Hydrogen Peroxide Using Ruthenium Catalysts

The direct synthesis of hydrogen peroxide is investigated using ruthenium containing catalysts. Ruthenium is not soluble in Au but forms alloys with palladium. We have therefore investigated Ru?CAu, Ru?CPd as well as trimetallic formulations supported on titania. The addition of ruthenium enhances the direct synthesis activity for all the catalysts studied and the effect is dependent on the amount of ruthenium added. The calcination conditions are shown to affect both activity and reusability.     

Aerobic Oxidation of Glucose with Gold Catalyst: Hydrogen Peroxide as Intermediate and Reagent

Careful analytical determinations show that the gold‐catalysed aerobic oxidation of glucose occurs through a two‐electrons mechanism leading to gluconate and hydrogen peroxide. This latter decomposes before reaching the critical concentration for competing with O₂ in glucose oxidation. A mechanism of glucose oxidation on gold nanoparticles is presented.     

微波辐射下过氧化氢氧化环己烯制环氧环己烷的研究

研究了微波辐射下30%过氧化氢氧化环己烯为环氧环己烷中反应时间、溶剂和催化剂等因素对环氧环己烷的选择性和转化率的影响。微波辐射50minWO42-/PO43-/cetyl催化环氧化选择性为93.1%转化率为75.2%,与常规条件相比反应时间明显缩短且环氧环己烷的选择性和转化率有所提高。     

过氧化氢做为氧化剂的Baeyer-Villiger氧化反应在合成中的应用

综述了醛、酮在过氧化氢做为氧化剂的条件下的Baeyer-Villiger氧化。介绍了环境友好型氧化剂过氧化氢在不同催化剂的催化下对醛、酮的Baeyer-Villiger氧化。     

过氧化氢氧化法合成己二酸

分别以钨酸盐、过氧杂多化合物、杂多酸为催化剂 ,过氧化氢氧化法合成己二酸。详细介绍了该法的最新进展 ,认为过氧化氢工艺的开发和研究是己二酸清洁合成的方向     

Selective Catalytic Oxidation of Alcohols,Aldehydes, Alkanes and Alkenes Employing Manganese Catalysts and Hydrogen Peroxide

The manganese‐containing catalytic system [Mn^IV,IV₂O₃(tmtacn)₂]²⁺ ( 1 )/carboxylic acid (where tmtacn=N,N′,N′′‐trimethyl‐1,4,7‐triazacyclononane), initially identified for the cis‐dihydroxylation and epoxidation of alkenes, is applied for a wide range of oxidative transformations, including oxidation of alkanes, alcohols and aldehydes employing H₂O₂ as oxidant. The substrate classes examined include primary and secondary aliphatic and aromatic alcohols, aldehydes, and alkenes. The emphasis is not primarily on identifying optimum conditions for each individual substrate, but understanding the various factors that affect the reactivity of the Mn‐tmtacn catalytic system and to explore which functional groups are oxidised preferentially. This catalytic system, of which the reactivity can be tuned by variation of the carboxylato ligands of the in situ formed [Mn^III,III₂(O)(RCO₂)₂(tmtacn)₂]²⁺ dimers, employs H₂O₂ in a highly atom efficient manner. In addition, several substrates containing more than one oxidation sensitive group could be oxidised selectively, in certain cases even in the absence of protecting groups.

     

过氧化氢氧化苯甲醛合成苯甲酸

以苯甲醛为原料,过氧化氢作氧化剂,在水作溶剂的碱性条件下,一步反应合成苯甲酸。考察了碱的浓度、反应温度和物料摩尔比对反应产率的影响。实验结果表明:氢氧化钾浓度为30%,反应温度40℃,反应物质的量比n(苯甲醛)∶n(30%过氧化氢)=1∶4,苯甲酸收率达89%。通过测熔点,红外光谱表征了目标产物苯甲酸。     

Tin Oxide Nanorod Array-Based Electrochemical Hydrogen Peroxide Biosensor

SnO₂ nanorod array grown directly on alloy substrate has been employed as the working electrode of H₂O₂ biosensor. Single-crystalline SnO₂ nanorods provide not only low isoelectric point and enough void spaces for facile horseradish peroxidase (HRP) immobilization but also numerous conductive channels for electron transport to and from current collector; thus, leading to direct electrochemistry of HRP. The nanorod array-based biosensor demonstrates high H₂O₂ sensing performance in terms of excellent sensitivity (379 μA mM⁻¹ cm⁻²), low detection limit (0.2 μM) and high selectivity with the apparent Michaelis–Menten constant estimated to be as small as 33.9 μM. Our work further demonstrates the advantages of ordered array architecture in electrochemical device application and sheds light on the construction of other high-performance enzymatic biosensors.     

异丙醇的O3/H2O2复合氧化动力学研究

采用停流光谱仪研究了异丙醇在T=298K和pH=3～11范围内O3 / H2O2复合氧化的反应动力学.结果表明异丙醇的O3 / H2O2复合氧化反应动力学随反应体系的pH值不同而不同.在酸性和中性条件下,反应相对于O3浓度、异丙醇浓度都为1级;在碱性条件下,异丙醇较容易被O3/H2O2复合氧化降解,总反应级数为2级,相对于O3浓度、异丙醇浓度和H2O2浓度分别为1级、0级和1级,可见异丙醇的降解速率与它的浓度无关.在T=298K,当pH值从9增大到11, 反应速率常数从3486.1(mol·L-1)-1·s-1增大到38239.2(mol·L-1)-1·s-1. 表明在酸性条件下,异丙醇的O3/H2O2复合氧化是O3分子直接攻击异丙醇的反应占主导;在碱性条件下,自由基型反应占主导.     

过氧化氢与臭氧联合氧化法合成壬二酸

对以过氧化氢和臭氧联合为氧化剂,由油酸制备壬二酸的工艺进行了研究,并讨论了过氧化氢的浓度及用量、通入臭氧的浓度、时间以及考察了不同种类钨化合物与季铵盐组成的相转移催化体系催化氧化油酸的反应活性。结果表明:当温度为70℃,20 g油酸,0.6 g磷钨酸,0.7 g十六烷基三甲基溴化铵(CTAB),滴加30%过氧化氢60 mL,通入臭氧时间为8 h,壬二酸的收率为71%。     

过氧化氢氧化苯甲醛反应的研究

研究了在无催化剂及以硫酸铜、金属铜、浓硫酸为催化剂的不同条件下，过氧化氢对苯甲醛的氧化反应。考察了苯甲醛和过氧化氢的摩尔投料比、温度、浓硫酸用量和反应时间对反应的影响．结果表明：温度60℃、反应时间36h、加浓硫酸2滴(以25mL苯甲醛为基准)、投料比为2时，苯甲酸的产率可达86．5％。     

Synthesis of Molybdenum Oxide Nanohybrids as Efficient Catalysts in Oxidation of Alcohols

Novel layered materials based on molybdenum oxide have been synthesized using three amino-carboxylate ligands; terephetalic acid, p-aminobezoic acid and diaminobenzene. On the basis of X-ray diffraction, scanning electron microscopy, thermogravimetry, and infrared results, the insertion of organic ligands into the interlayer space of molybdenum oxide has been proposed. Moreover, the influence of organic guests on the oxide structure and also their catalytic performance are discussed. Furthermore, fabrication of the nanostructured molybdenum oxide is achieved by calcinations of these hybrid materials at 600 °C. Somewhat oriented nanoplatelets are viewed with different catalytic activity.     

铈磷钼钒杂多酸盐催化过氧化氢氧化环己烷

用稀土元素铈取代磷钼钒杂多酸合成了Keggin型稀土铈磷钼钒四元杂多酸盐(Ce HPMo11VO40·n H_2O),采用XRD和FTIR对该杂多酸盐的结构进行了表征。并将其作为催化剂应用于H_2O2氧化环己烷制备环己醇和环己酮的反应中,考察了催化剂用量、反应温度、反应时间、H_2O2用量对反应的影响。实验结果表明:反应最佳条件为n(环己烷)=0.1mol,n(Ce HPMo11VO40·n H_2O)=0.2 mmol、反应温度为75℃、反应时间为9 h、n(H_2O2)=0.2 mol(质量分数为30%),在此条件下,环己烷的转化率达到41.29%,环己醇和环己酮的总收率可达27.49%。