One-step synthesis of phenol by O- and OH- emission material

A novel approach to the direct synthesis of phenol from benzene was obtained with high benzene conversion (30%) and phenol selectivity (approximately 90%) by using a microporous material [Ca24Al28O64]4+.4O-(C12A7-O-) as catalyst with oxygen and water; active O- and OH- anions are proposed to play important roles in the formation of phenol by hydroxylating the aromatic ring of benzene.     

Direct photo-oxidation of benzene to phenol over Ti/Si binary oxide prepared by sol-gel method

Titanium-silicon (Ti/Si) binary oxides having a varying Ti content were prepared using the sol-gel method and used as photocatalysts. The photo-oxidation of benzene to phenol was carried out using Ti/Si binary oxide catalysts in the presence of benzene, water and gaseous oxygen. The amounts of benzene used hardly affected the phenol yield. On the other hand, the addition of sulfuric acid into reaction solution led to the improvement of phenol formation. The H₂O₂ formation rate seemed to be related to the phenol yeilds. The photocatalytic reactivity of Ti/Si binary oxide having different TiO₂ contents was investigated and it was found to be dramatically enhanced in the range of lower TiO₂ contents. XANES, ESR and XRD spectroscopic investigations of these Ti/Si binary oxide catalysts indicated that Ti species were highly dispersed in SiO₂ matrices and existed in a tetrahedral coordination. The photo-irradiation of catalysts having tetrahedral Ti species seemed to effectively lead to the formation of H₂O₂ as an intermediate.     

Electronic structure of monosubstituted benzenes and X-ray emission spectroscopy

The electronic structure of the phenol molecule in the gas phase was studied by X-ray emission spectroscopy (using the O-Kα and C-Kα spectra). MNDO calculations were performed, which made it possible to construct theoretical spectra and interpret experimental spectra. The structure of the molecular orbitals of phenol was compared with those of benzene and water. The π-interaction of the phenyl fragment with the oxygen-containing substituent was investigated. The contribution of the 2p atomic orbital of the oxygen atom to the π-HOMO of phenol is considerably less than that to lower-lying orbitals. For Part 3, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2187–2193, December, 1997.     

The presumptive detection of benzene in water in the presence of phenol with an active membrane-UV photo-ionisation differential mobility spectrometer

Studies with a new technique, active membrane-differential mobility spectrometry, with aqueous standards of benzene and phenol are described. The atmospheric pressure photo-ionisation chemistries of benzene and phenol in the presence of oxygen are similar in that benzene forms phenol radicals that subsequently react to yield diphenylether and 4-phenoxyphenol products. Further phenol sequesters charge from benzene ions leading to a significant loss of sensitivity. This is an important consideration in the development of screening techniques for the presence of benzene in environmental water samples. This challenge was addressed by including a pre-separation stage prior to photo-ionisation, and a 10 cm long polydimethylsiloxane active membrane inlet using nitrogen as a carrier gas was used to sample, concentrate and deliver low resolution separations to the 10.6 eV UV-ionisation region of a differential mobility spectrometer. Acetone was also proposed as a charge carrier for the UV photo-ionisation source; to promote phenol protonation and inhibit charge sequestration from benzene. The responses of the system to aqueous standards of benzene and phenol with and without acetone doping at 10.2 mg m(-3) were evaluated and four to five-fold increases in sensitivity were obtained with acetone doping. With a sampling time of 60 s and a total measurement cycle of 180 s it was possible to obtain quantitative responses to single standards over the concentration range 6 to 177 microg cm(-3) with linear correlations with R(2) values ranging from 0.97 to 0.99. The effects of the heating rate of the membrane and the dispersion field strength of the differential mobility spectrometer on sensitivity and the differentiation of benzene from phenol responses were optimised, leading to a configuration where a voltage heating programme of 4.75 V s(-1) was applied to a 124 microm stainless steel wire heating element within the active membrane, and a dispersion field strength of 22 kV cm(-1) was used to test a mixture of benzene (14 microg cm(-3)) and phenol (6 microg cm(-3)) in water. The presence of benzene was identified through the presence of a peak corresponding to a benzene response, V(C) = -9 V FWHM = 1 V, that followed the thermal desorption profile of benzene.     

Chemical dosimetry system for γ-ray irradiation based on the formation of phenol from aqueous benzene solutions

A chemical dosimetry system based on the radiochemical formation of phenol from aqueous benzene solutions was applied to measure the intensity of γ-ray irradiation. Using a simple and sensitive isocratic fluorometric HPLC system, radiochemically generated phenol was determined. The radiochemical formation of phenol was linear up to 100 Gy and the lower limit of detection calculated from the detection limits of phenol was estimated to be 7 mGy. The phenol formation rates were not affected by the oxygen saturation. The chemical dosimetry system investigated in this study was sensitive and was easier to use than traditional chemical dosimeters.     

一种可能形成POPs途径的初探-气相苯的氯化反应

用串联质谱碰撞室模拟大气环境研究了持久性有机污染物(POPs)形成过程,实验发现,经离子-分子反应可以生成氯苯类化合物。 以中性苯与酰氯为反应物在离子源进行反应,在苯含量为4×10^-3Pa、酰氯含量为4×10^-4Pa时,氯苯的生成量为5×10^-8Pa,远远高于背底浓度5×10^-9Pa。对氯苯类化合物的形成,大气环境明显优于质谱环境,实验结果表明,在大气中经离子分子反应形成POPs是可能的。     

Fully conversing and highly selective oxidation of benzene to phenol based on MOFs-derived CuO@CN photocatalyst

Developing highly efficient photocatalysts for selective oxidation of benzene to phenol is of great significance. However, it is still challenging to simultaneously achieve high conversion rate and selectivity. Herein, we demonstrate 99.9% of benzene photoconversion and 99.1% of phenol selectivity under the illumination of AM 1.5 for 12 h. For this purpose, an advanced CuO@CN photocatalyst has been fabricated by loading tubular carbon nitride (CN) with CuO nanoparticles thermally polymerized from Cu-based metal-organic frameworks (MOFs). The sluggish photocharge carrier recombination rate and the excellent stability indicate that the as-prepared nanocomposite is an ideal photocatalyst for benzene oxidation application. This work paves a new avenue for designing novel photocatalyst based on MOFs and carbon nitride materials.     

分子氧催化氧化苯直接合成苯酚

苯酚是重要的有机合成中间体,当前主要通过异丙苯法合成苯酚的技术路线存在制备流程长、消耗丙烯、副产丙酮等不足。以分子氧为氧化剂由苯氧化直接合成苯酚则具有潜在重大的经济效益、社会效益和环境效益,已成为催化与有机合成等研究领域中极具挑战性的热点课题之一。本文较为系统地总结了分子氧氧化苯通过一步法合成苯酚的研究工作,着重综述了用于该反应的催化剂如Pd、Cu、V等金属或其化合物,也归纳了影响此反应的主要因素,并介绍相应的反应机理。最后,对分子氧催化氧化苯合成苯酚反应的研究提供了一些建议和展望。     

2,2,6,6-四甲基哌啶-1-氧自由基促进的钒基催化剂催化苯直接氧化制苯酚

以钒基化合物为催化剂,在TEMPO(2,2,6,6-四甲基哌啶-1-氧自由基)存在下,能形成快速催化分子氧氧化苯制苯酚的催化体系.在反应过程中,由类似芬顿试剂反应过程生成的羟基自由基亲核进攻苯环,形成羟基环己二烯自由基;该羟基氢可在TEMPO存在的催化体系中消除,同时苯环氢可立即转移至氧原子而生成苯酚.在以[(CH3)...     

Significant roles of oxygen and unbound <Superscript>•</Superscript>OH radical in phenol formation during photo-catalytic degradation of benzene on TiO<Subscript>2</Subscript> suspension in aqueous system

Studies on photo-catalytic degradation of benzene using TiO₂ photo-catalyst as a suspension in water is reported. Degradation studies have been carried out using 350 nm UV light. Phenol, a photo-catalytic product of benzene, was monitored under varying experimental conditions such as amount of TiO₂, concentration of benzene, photolysis time, ambient (air, O₂, Ar, N₂O and N₂O–O₂ mixture), etc. The phenol yields in both aerated and O₂-purged systems increased with the photolysis time. In contrast to oxygenated systems, the yields of phenol in deoxygenated (viz. Ar-purged and N₂O-purged) systems were quite low (~30 μM) and remained steady. H₂O₂ yields in all these systems were also monitored, and found lower than an order of magnitude as compared to phenol yields for the respective systems. The rate of phenol production in aerated 1 mM benzene solution containing 0.05% TiO₂ suspension was evaluated at 12.3 μM min⁻¹ which is lower than the rate obtained in an O₂-saturated system (22.4 μM min⁻¹). The low yields of phenol in both Ar- and N₂O-purged systems, and also the increasing trends in oxygenated systems, together reveal that, for the phenol formation with an enhanced rate, oxygen is essential. In the present study, it is implied that the photo-generated hole, which is mainly an ^•OH radical, is either freely available in the aqueous phase or migrates to the aqueous phase from the catalyst surface, to react with benzene to produce HO-adduct radical. Later, following reaction with oxygen, the adduct produces phenol. On the other hand, h⁺ and surface adsorbed ^•OH radical, being trapped/bonded due to rigid association with the catalyst surface, were not able to generate phenol under similar experimental conditions. The mechanism of phenol formation with TiO₂ photolysis in an aqueous system is rechecked, on the basis of present results on h⁺/surface adsorbed ^•OH radical/unbound ^•OH radical scavenging by benzene, collectively with previous reports on various systems.     

Phenol production in benzene/air plasmas at atmospheric pressure. Role of radical and ionic routes

Benzene can be efficiently converted into phenol when it is treated by either corona or dielectric barrier discharge (DBD) plasmas operating at atmospheric pressure in air or mixtures of N(2) and O(2). Phenol produced by corona discharge in an atmospheric pressure chemical ionization source (APCI) has been detected as the corresponding radical cation C(6)H(5)OH(+*) at m/z 94 by an ion trap mass spectrometer. On the other hand, phenol has been observed also as neutral product by gas chromatography-mass spectrometry analysis (GC-MS) after treatment in a DBD plasma. Experiments aimed at shading light on the elementary processes responsible for benzene oxidation were carried out (i) by changing the composition of the gas in the corona discharge source; (ii) by using isotopically labeled reagents; and (iii) by investigating some relevant ion-molecule reactions (i.e. C(6)H(6)(+*) + O(2), C(6)H(5)(+) + O(2)) via selected guided ion beam measurements and with the help of ab initio calculations. The results of our approach show that ionic mechanisms do not play a significant role in phenol production, which can be better explained by radical reactions resulting in oxygen addition to the benzene ring followed by 1,2 H transfer.     

Pyrolysis of poly(vinyl chloride)

A pyrolysis–gas chromatography–mass spectrometric technique has been developed to study the thermal degradation of poly(vinyl chlorides) polymerized at different temperatures. Hydrogen chloride and benzene evolution during successive stages of pyrolysis have been quantitatively determined and correlated to the tacticity and molecular weight of the polymer. It was found that lowering the temperature of polymerization and molecular weight depresses benzene evolution and increases char weight but does not affect the HCl yield. It is suggested that the syndiotactic trans microstructure favored at low temperature of polymerization yields polyenes which cannot cyclize to form benzene. As the molecular weight decreases, the increase in number of vinyl chain ends facilitates pyrolytic crosslinking and char formation.     

Chemo‐ and Regioselective Dihydroxylation of Benzene to Hydroquinone Enabled by Engineered Cytochrome P450 Monooxygenase

Hydroquinone (HQ) is produced commercially from benzene by multi‐step Hock‐type processes with equivalent amounts of acetone as side‐product. We describe an efficient biocatalytic alternative using the cytochrome P450‐BM3 monooxygenase. Since the wildtype enzyme does not accept benzene, a semi‐rational protein engineering strategy was developed. Highly active mutants were obtained which transform benzene in a one‐pot sequence first into phenol and then regioselectively into HQ without any overoxidation. A computational study shows that the chemoselective oxidation of phenol by the P450‐BM3 variant A82F/A328F leads to the regioselective formation of an epoxide intermediate at the C3=C4 double bond, which departs from the binding pocket and then undergoes fragmentation in aqueous medium with exclusive formation of HQ. As a practical application, an E. coli designer cell system was constructed, which enables the cascade transformation of benzene into the natural product arbutin, which has anti‐inflammatory and anti‐bacterial activities.     

聚酯酰亚胺漆包线漆的组分分析

用甲醇醇解法将聚酯酰亚胺降解成小分子化合物。用气质联用仪（GC-MS）对蒸馏出来的溶剂和醇解液进行检测,用红外光谱、原子发射光谱对漆包线漆中的固体成分进行分析,最终得到该种漆包线漆的化学组分。分析结果为：该种聚酯酰亚胺是由对苯二甲酸,乙二醇,偏苯三甲酸和4,4’-二胺基二苯基甲烷合成的;溶剂主要是苯酚,1,2,3-三甲基苯和1-乙基-2,3-二甲基苯组成;助剂为正肽酸丁酯。     

Catalytic conversion of benzene to phenol

Phenol is very useful intermediate in the manufacture of petrochemicals, drugs, agrochemicals, and plastics. Commercially, phenol is produced by a three-step, high-energy consumption process known as the cumene process. The conversion of a chemical to a value-added product is always economically desirable. More than 90% of phenol consumption in the world is manufactured by the multistep cumene process, in which acetone is coproduced in 1: 1 molar ratio with respect to phenol. However, the drawbacks of the three-step cumene process have spurred the development of more economical routes to decrease energy consumption, avoid the formation of explosive cumene hydroperoxide, and increase the yield. The objective of this article is to highlight benzene-to-phenol conversion technologies with emphasis on direct conversion methods. Gas phase and liquid phase reactions are the two main routes for direct oxidation of benzene to phenol. Indirect methods, such as the cumene process, and direct methods of benzene-to-phenol conversion are discussed in detail. Also discussed is the single-step reaction of benzene to phenol using oxidants such as O₂, N₂O, and H₂O₂. Catalytic conversion of benzene to value-added phenol using a chemically converted graphene-based catalyst, a cost-effective carbon material, is discussed.     

Oxidation of aromatic hydrocarbons with oxygen in a radiofrequency plasma

The reactions of three aromatic hydrocarbons, benzene, toluene, and styrene, with oxygen in a radiofrequency (r) plasma were investigated. Benzene was oxidized to yield phenol as a single volatile organic product. Similarly, toluene gave the ring oxidation products, cresols, as well as considerable amounts of methyl oxidation products, consisting mainly of benzaldehyde and benzyl alcohol. In contrast, the oxidation of styrene took place predominantly on the olefinic double bond to produce styrene oxide On basis of the products and effects of reaction variables, r power and flow rates of hydrocarbons and oxygen, on the reaction rate, the oxidation mechanism was discussed, particularly focusing on the intermediate species responsible for the formation of major products.     

Ti—MCM—41的结构特征与芳烃羟化反应的化学亲和选择性

以不同硅源合成了Si/Ti比不同的Si-Ti－MCM－41,并在引入Ti的同时引入Al,合成了Si/Al比不同的Si-Ti-Al-MCM-41。XRD、TEM、低温N2吸附的表征结果说明,Ti-MCM-41具有长程有序一维孔道,且比表面积较高,FT－IR光谱表征说明,Ti对骨架Si的取代使MCM－41表面出现缺陷羟基。Al的引入有利于Ti-MCM-41有序结构的形成。且可调变Ti-MCM-41的表面性质。Ti-MCM-41在不同极性芳烃化合物的羟化过程中表现出化学亲和选择性,且调变Ti-MCM-41的表面性质可实现对化学亲和选择性的控制。     

Direct selective oxidation of benzene to phenol using molecular oxygen in the presence of palladium and heteropolyacids

The use of heteropolyacids as a reoxidant for palladium in the direct oxidation of benzene to phenol with molecular oxygen was studied as a function of the variables involved. It was shown that the oxidation system is very effective even if a molar ratio of HOAc:H₂O of 1:2 is used. After 4 h at 130°C the benzene conversion is 15% and the selectivity for phenol is above 70%. The quantity of palladium acetate can be drastically reduced allowing turnover numbers as high as 800.     

Fe-ZSM-5 分子筛催化剂上N2O一步氧化苯制苯酚的积炭动力学

 采用等温固定床反应器和热重分析相结合的方法研究了 Fe-ZSM-5 分子筛上 N2O 一步氧化苯制苯酚的积炭行为, 考察了反应时间、温度和原料配比对积炭量的影响. 依据实验现象和积炭物组分分布的气相色谱-质谱分析结果, 提出了 Fe-ZSM-5 分子筛上 N2O 一步氧化苯制苯酚的积炭机理. 结果表明, Fe-ZSM-5 分子筛上的积炭物种主要来源于氧化产物苯酚的深度氧化, 属连串失活. 基于所提出的积炭机理和实验结果, 建立了 Fe-ZSM-5 分子筛催化剂的积炭动力学模型, 统计检验和残差分布检验表明, 所建模型与实验结果相容, 可靠性强.     

Thermodynamic properties of the benzene-phenol dimer in dilute aqueous solution

Precise vapor pressure-solubility measurements have been obtained for dilute solutions of benzene and phenol in water at 15, 25, 35 and 45°C. All of the results are consistent with a mass action model that attributes deviations from ideal solution behavior to the formation of benzene dimers and hetero-dimers between benzene and phenol. The benzene-phenol dimer forms endothermically at 25°C, with a very large negative heat capacity, and a formation constant that reaches a maximum value of 0.66 l-mol^?1 at approximately 35°C. Thermodynamic properties of the benzene-phenol dimer are reported and compared with those of other aggregates that are believed to be stabilized primarily by hydrophobic interactions.