共查询到19条相似文献,搜索用时 899 毫秒
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研究了铁(Ⅱ)-L(L=C2O42-、EDTA、CN-、C5H5-、1,10-phenanthroline和2,2′-dipyridine)对苯酚羟化反应的催化作用.结果表明,催化剂的苯酚羟化活性与它们的氧化还原电位有关,电位过高和过低都不利于苯酚羟化反应的进行.本文同时提出了苯酚羟化的反应机理,对实验结果进行了合理的解释 相似文献
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苯酚羟基化合成苯二酚过程生成酚焦油的表征 总被引:1,自引:0,他引:1
对铁基复合氧化物催化苯酚羟基化合成苯二酚反应和产物分离过程生成的酚焦油进行了表征,结果表明,催化剂上所含酚焦油结构与羟基化反应过程生成焦油类似,热失重峰在320℃左右,含有C=O结构物质,形成原因在于羟化液中苯二酚的过度氧化和酚类物质的缩合.用丙酮对蒸馏所得酚焦油进行了抽提,其中溶于丙酮部分呈结晶状,抽余部分不含结晶状物质.蒸馏所得酚焦油中的条状结晶物C:O原子比为6:3,背底焦油中C:O原子比为6:1.43,废催化剂上沉积的酚焦油,C:O原子比为6:4,蒸馏所得酚焦油中氧含量较少。且背底部焦油不溶于热水和丙酮,说明脱水和精馏过程存在进一步的生焦反应。 相似文献
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八羟基喹啉铁(Ⅱ)/MCM-41对苯酚羟化的催化作用 总被引:6,自引:0,他引:6
利用MCM-41中孔分子筛为载体,制备了负载型八羟基喹啉铁(Ⅱ)/MCM-41(简记为Fe(Ⅱ)-Qx/MCM-41)催化剂.XRD,IR证明八羟基喹啉铁(Ⅱ)配合物成功地负载于MCM-41分子筛中.考察了八羟基喹啉铁(Ⅱ)/MCM-41对苯酚羟化反应的催化作用,和未负载的配合物相比,苯酚的转化率、对苯二酚的选择性以及H2O2的利用率都有显著的提高.同时也探讨了温度、反应介质及介质pH值对苯酚羟化反应的影响.结果表明,随着温度的提高,苯酚的转化率增加,但温度太高,易导致副产物增多;有机溶剂不利于羟化反应的进行,水是实验条件下苯酚羟化反应的最佳反应介质;在一定程度上,pH值越低,越有利于反应活性的提高,若pH值太低,活性反而下降,pH值升高不利于苯酚羟化反应的进行.该催化剂也具有较高的稳定性. 相似文献
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Fenton试剂是某些烃类化合物的有效氧化剂^[1],该体系对芳香化合物具有羟化作用。我们^[2]曾报道了含Cu类钙钛石型复合氧化物在苯酚烃化反应中的催化活性,并提出了相应的反应机理。高价态的过渡金属离子如C^3 [2]和Fe^3 [3]通常被认为是中间自由基的氧化剂。实际上,醌类化合物及其还原形式半醌、氢醌与生物体内许多电子转移过程密切相关^[4],如泛醌或辅酶Q在生物体呼吸链电子传递过程中起重要作用^[5]。在实验中我们观察到苯酚羟化反应中不仅有苯醌生成,而且生成的苯醌还能促进羟化反应。本文报道了醌类化合物在苯酚羟化循环中的传递电子作用。 相似文献
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苯二酚 ( DHB)是一种重要的化工原料 ,由苯酚过氧化氢羟化制苯二酚的生产路线 ,反应工艺简单 ,不污染环境 ,被认为是 2 1世纪最有价值、最有前途的工艺路线之一 .其关键在于研制高活性、高选择性的催化剂以提高产率使之实现工业化 .迄今为止 ,用于催化苯酚过氧化氢羟化制苯二酚的杂多化合物尚仅限于具有 Dawson结构的钼钒磷、钨钒磷杂多化合物[1,2 ] .本文设计合成了含稀土元素钆的二元杂多化合物 ( NH4 ) 11Gd[Gd4 Mo2 9O10 0 ( H2 O) 16]· 33H2 O,添加适量 V2 O5后应用于苯酚过氧化氢羟化制苯二酚反应 ,取得较好的催化效果 .称取 … 相似文献
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Cu修饰的MCM-41的合成、表征及对芳烃羟化反应催化作用的研究 总被引:4,自引:1,他引:3
利用MCM-41形成过程中协同自组装的特点,在合成过程中引入Cu(NH3)42+,制备出过渡金属表面修饰的纯硅介孔分子筛Cu-MCM-41,采用XRD,ICP,ESR,N2吸附等手段确定Cu处于MCM-41的表面,取代了端羟基中氢的位置,与骨架桥氧和硅羟基中的氧配位.利用苯酚羟化反应为探针,考察了Cu-MCM-41的催化活性.结果表明,Cu-MCM-41具有很高的苯酚羟化活性,与TS-1分子筛的催化效果相当,对萘酚的羟化活性也较高. 相似文献
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纳米钼钒砷杂多酸盐催化苯羟化合成苯酚的研究 总被引:1,自引:0,他引:1
过氧化氢作为一种清洁氧化剂,在苯的直接羟化的研究中受到重视。催化剂主要有含钛催化剂系列、含铁催化剂系列和含铜催化剂系列、含钒催化剂系列和其它杂原子催化剂。杂多化合物是一类酸性和氧化性较强的双功能催化剂,但由于受其低比表面积的限制,导致杂多化合物固有的高催化活性在苯的过氧化氢羟化反应中难以充分发挥。本文对所制得的4种过渡金属钼钒砷杂多酸盐纳米催化剂应用于苯的过氧化氢直接羟化合成苯酚的反应,取得了苯酚收率〉50%,选择性〉98%的结果。 相似文献
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Borah P Ma X Nguyen KT Zhao Y 《Angewandte Chemie (International ed. in English)》2012,51(31):7756-7761
Selective benzene hydroxylation: A periodic mesoporous organosilica embedded with a vanadyl(IV) acetylacetonate complex has been synthesized through a co-condensation method. This system is a catalyst for direct hydroxylation of benzene to phenol, presenting a selectivity of 100?% towards the phenol formation as well as an excellent catalytic recyclability (see scheme). 相似文献
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The cyclometalated Ir(III) complexes-catalyzed aerobic hydroxylation of arylboronic acids under visible-light has been successfully developed. This catalytic system has a broad substrate scope, affording a series of phenols smoothly with the highest isolated yield up to 95%. Moreover, this protocol is capable to synthesize several useful phenols containing bulky moieties, which are potential candidates or intermediates used as pharmaceuticals and functional materials. The Ir(III)-catalyzed hydroxylation of arylboronic acids could be applied in a one-pot synthesis of several important phenol derivatives, including 1,1′-methylene-bis(2-naphthol), 2,3-dihydro-1H-naphtho[2,1-e][1,3]oxazine and a bioactive compound LUF5771. 相似文献
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Ti—MCM—41的结构特征与芳烃羟化反应的化学亲和选择性 总被引:3,自引:0,他引:3
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。 相似文献
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Dihydroxybenzene are both very important chemical products. The oxidation of phenol to produce catechol and hydroquinone has been researched extensively since the 1970s. In this paper, the iron complex oxide was prepared by the air oxidation of aqueous suspension method and the catalytic activities were investigated in the hydroxylation of phenol with H2O2 to catechol and hydroquinone. The results showed that the catalyst had higher catalytic activities and the phenol conversion could reach 24% when the phenol/H2O2 (mole ratio) was 3 and the catechol/hydroquinone (mole ratio) 1.5 in products. Furthermore, the interaction of the catalyst with H2O2 had also been demonstrated by IR spectrometry. In the presence of H2O2 a band at 956 cm-1 appeared and disappeared when the H2O2 is replaced by H20 or the catalyst was heated over 373 K, at which temperature decomposition of iron peroxide was very likely. The band at 956 cm-1 was due to the formation of structure of iron peroxide species and the stretching vibration of surface 0-0 species. The results of IR studies suggested that the catalyst might be react with hydrogen peroxide to form iron peroxide, which decomposed to produce·OOH radical. In the presence of DMPO (5,5-dimethyl-1-pyrroline-N-oxide) the·OH radical was also successfully captured in the hydroxylation of phenol by H2O2 over iron complex oxide catalyst in the first time that has been confirmed by means of ESR spectrometry. The results of ESR suggested the process of hydroxylation of phenol with H2O2 was probably a radical process. A possible mechanism of the catalytic process was proposed. 相似文献
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CHEN Chunxia XU Chenghua FENG Liangrong SUO Jishuan & QIU Fali . Chengdu Institute of Organic Chemistry Chinese Academy of Sciences Chengdu China . Graduate School of the Chinese Academy of Sciences Beijing China 《中国科学B辑(英文版)》2005,48(6)
Phenol hydroxylation is an industrially important reaction, whose main products are catechol and hy-droquinone being diverse applications which are im-portant intermediates for perfumes, drugs, and phar-maceuticals and so on[1]. The processes using H2O2 a… 相似文献
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Fe-FSM-16 and Fe-containing mesoporous materials (Fe-JLU-15) prepared by using semifluorinated surfactant as a template, have been synthesized by microwave-hydrothermal (M-H) process and characterized by several spectroscopic techniques. The catalytic activity of these materials was tested for the phenol hydroxylation and wet phenol oxidation with H2O2 under mild reaction conditions. The effect of pH, H2O2/PhOH molar ratio and stability of the catalyst on the oxidation process was also investigated. Phenol oxidation and H2O2 decomposition show that the Fe-JLU-15 is more active than Fe-FSM-16 and more stable in aqueous solution. The total amount of dissolved iron is less than 5 wt% of the iron initially contained in the catalyst. In phenol hydroxylation, these two solids can effectively catalyze the phenol hydroxylation. Catechol and hydroquinone were observed as the major products, with a difference in the product distribution for these solids. The Fe-JLU-15 has a high selectivity for catechol (63.5 % phenol conversion, CAT/HQ = 2.7) while the Fe-FSM-16 shows a high selectivity for hydroquinone (56.8 % phenol conversion, CAT/HQ < 1) under the same reaction conditions. 相似文献
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采用变温晶化方法, 通过改变低温段晶化温度, 水热合成B-ZSM-5沸石. 以B-ZSM-5沸石为母体, 经脱硼处理后, 与TiCl4进行气固相取代反应制得Ti-ZSM-5样品. 采用扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱、紫外-可见(UV-Vis)光谱、电感耦合等离子体原子发射光谱(ICP-AES)、拉曼光谱、N2吸附-脱附及1,2,4-三甲苯物理吸附等手段对其进行了表征, 并考察了Ti-ZSM-5样品在苯酚羟基化反应中的性能. 结果表明, 合成的母体均为长方体颗粒的聚集体且具有完整的MFI拓扑结构, 但其聚集体颗粒大小、载钛量、孔容及比表面积却存在明显差异; 低温晶化最佳温度为333-353 K, 以此条件下合成出以B-ZSM-5为母体制得的Ti-ZSM-5具有更小的颗粒尺寸、较大的孔容及比表面积, 在苯酚羟基化反应中表现出更加优异的催化性能. 在苯酚与过氧化氢的摩尔比为3的条件下, 苯酚转化率最高可达到20.5%. 相似文献