球磨微米硫化零价铁活化双氧水降解有机污染物的研究

报道了机械球磨方法制备的微米硫化零价铁（S-ZVI）可以快速活化H₂O₂降解各类有机污染物.S-ZVI/H₂O₂降解苯酚的单位比表面积反应速率常数是ZVI/H₂O₂的5倍以上,且苯酚的降解不存在初始抑制阶段.探针化合物乙醇的淬灭反应结合电子顺磁共振（EPR）实验证明S-ZVI/H₂O₂体系产生的氧化活性物质为·OH.反应前后S-ZVI颗粒的扫描电子显微镜（SEM）和X射线衍射（XRD）表征结合电化学测试和苯酚降解结果表明S-ZVI中FeS取代ZVI表面的钝化膜（铁氧化物）,加速了电子从Fe⁰传递到H₂O₂,更快地释放Fe²⁺,引发Fenton反应.在这过程中FeS主要作为电子的导体而非Fe²⁺的释放源.     

Fe3O4@MIL-101(Fe)类芬顿降解盐酸四环素性能研究

通过水热合成法制备了Fe₃O₄@MIL-101(Fe)复合材料。采用扫描电子显微镜、傅里叶红外光谱仪和X射线衍射仪对其表面形貌和结构进行表征;以盐酸四环素(TC)为目标污染物,考察了反应温度、H₂O₂浓度、Fe₃O₄@MIL-101(Fe)投加量和pH对TC降解的影响和在不同离子存在条件下对TC降解性能的影响进行了探讨。结果表明:Fe₃O₄@MIL-101(Fe)晶体结构完整、结晶度良好、并呈现典型的八面体结构;当TC初始浓度100 mg/L,反应温度40℃,H₂O₂浓度20 mmol/L,Fe₃O₄@MIL-101(Fe)投加量0.15 g/L,TC溶液初始pH5时,TC的降解率达到89.50%;5次循环实验后,Fe₃O₄@MIL-101(Fe)对TC的降解率仍达56.51%,具有...     

富Mn鸢尾生物炭的制备及在类Fenton体系中的应用

通过在N₂气氛围下热裂解富集Mn的鸢尾可得到Mn/生物炭(BC)材料, 并按植物叶(Leaf)和根部(Root)分别将其分别命名为BC-L0, BC-L1, BC-L2, BC-R0, BC-R1和BC-R2. 采用扫描电子显微镜(SEM)、 能谱分析(EDS)仪、 X射线衍射(XRD)仪、 X射线光电子能谱(XPS)、 傅里叶变换红外光谱(FTIR)、 原子吸收光谱(AAS)和比表面积分析(BET)仪等对Mn/生物炭材料的Mn含量、 化学组成与形貌进行了表征, 发现鸢尾叶部为Mn主要富集部位, 最大富集量为13.0 mg/g, 且Mn以Mn₂O₃薄片存在于生物炭表面. 利用Mn/生物炭与H₂O₂构建了类Fenton体系, 在中性条件下BC-L2-H₂O₂体系对有机污染物罗丹明B(RhB, 3×10 ^-5 mol/L)的降解率达到50%(180 min), 表明该体系具备氧化去除RhB的能力, 并推测了该体系对RhB的催化氧化机理. 结果表明, 先将Mn超富集植物转化为Mn/生物炭材料, 再通过添加H₂O₂能构建具有氧化能力的类Fenton体系, 可用于对有机污染物的降解, 实现“以废治废”的绿色循环思路, 为Mn富集的植物后续处理提供一种新的转化及应用方式.     

纳米四氧化三铁碳片对亚甲基蓝废水的催化脱色

碳材料上掺杂纳米Fe₃O₄颗粒所形成的复合材料可发挥各自优点,进而拓宽其在印染废水处理中的应用。以葡萄糖和氯化铁为原料,通过共沉淀后碳化煅烧,成功制备了纳米四氧化三铁碳片(Fe₃O₄@GC),利用XRD、TEM、BET和磁滞回线对Fe₃O₄@GC碳片进行了形貌表征,并将其用于亚甲基蓝(MB)废水的催化脱色处理。结果表明,Fe₃O₄@GC碳片上的Fe₃O₄结晶性较好,颗粒呈球形且分散均匀,其平均粒径为22 nm。Fe₃O₄@GC碳片能够活化H₂O₂产生氢氧自由基(HO·)并高效氧化降解MB。在pH为2～3,材料投加量为1.0 g/L,H₂O₂用量为9 mmol/L的条件下,60min内Fe₃O₄@G...     

Al2O3改性CuO/Fe2O3催化剂水煤气变换反应性能

采用分步共沉淀法制备了不同Al₂O₃含量(0%-15% (w))的CuO/Fe₂O₃催化剂, 并进行水煤气变换反应(WGSR)评价测试. 制得的催化剂中含有复合物CuFe₂O₄, 其晶粒尺寸, 氧化还原性质和表面Cu分散通过相应表征手段加以研究. X 射线粉末衍射(XRD), 拉曼(Raman)光谱, N₂物理吸附, N₂O分解和CO₂程序升温脱附(CO₂-TPD)等表征技术说明适量Al₂O₃的加入可以促进尖晶石CuFe₂O₄发生由四方相向立方相的转变, 阻止催化剂中Cu烧结, 增大表面Cu分散, 增加弱碱性位点的数量. 此外, 采用H₂程序升温还原(H₂-TPR)技术探究改性的CuO/Fe₂O₃催化剂的还原性能. 关联结果发现, Al₂O₃掺杂在增大铜物种的耗氢量, 降低其还原温度方面起着重要的作用. 即Al₂O₃的添加促进CuO/Fe₂O₃催化剂中铜铁物种之间的协同作用. 结合活性测试和表征结果,适量的Al₂O₃ (10%(w))改性的催化剂具有较小的Cu颗粒尺寸、较大的Cu分散、较强的还原性能、较多数量的弱碱性位点, 因此具有更好的初始活性和热稳定性.     

抗坏血酸提高稀土复合材料催化降解染料性能研究

本文以β-环糊精(CD)为载体,通过负载Fe₃O₄和稀土铈(Ce),制备了稀土复合材料Ce-Fe-CD,形成了可有效降解有机物的非均相芬顿反应Ce-Fe-CD/H₂O₂体系。为提高催化降解效果,本文用两种方式引入还原剂抗坏血酸(AA):(1)在非均相芬顿反应过程中直接投加AA,形成AA/Ce-Fe-CD/H₂O₂体系;(2)利用AA活化稀土复合材料,获得AA-Ce-Fe-CD复合材料,形成AA-Ce-Fe-CD/H₂O₂体系。实验结果表明,AA-Ce-Fe-CD/H₂O₂和AA/Ce-Fe-CD/H₂O₂对染料的降解率分别为86.9%和83.0%,比未使用AA时分别提高了34.4%和30.5%,且AA-Ce-Fe-CD/H₂O₂体系有更高的H₂O₂     

过渡金属修饰Fe2O3/Al2O3氧载体的Redox性能研究

采用冷冻干燥法分别制备了经Cu、Co、Mn、Ni修饰的Fe₂O₃/Al₂O₃氧载体。利用化学吸附仪,通过程序升温还原(H₂-TPR)和程序升温氧化(TPO)来研究经不同过渡金属修饰的Fe₂O₃/Al₂O₃与H₂和O₂的反应性能。实验发现,在Fe₂O₃/Al₂O₃中加入Cu、Co、Ni以后,氧载体与H₂的反应性都有提高,但是当在Fe₂O₃/Al₂O₃中加入Mn以后,氧载体的反应性和载氧能力反而下降。经Cu修饰的Fe₂O₃/Al₂O₃与H₂的反应性最高,且具有很好的反应稳定性,适合用于化学链燃烧。     

自然水体生物膜体系中过氧化氢浓度的影响因素

以过氧化氢(H₂O₂)为自然水体生物膜产生的活性氧(ROS)的代表, 通过模拟实验, 研究了水-自然水体生物膜体系中光/暗变化、 生物膜的避光预处理与数量、 有机配体和pH值对体系中H₂O₂浓度的影响. 结果表明, 光照可快速增加体系中H₂O₂浓度, 光照转为无光时体系H₂O₂浓度下降(约为光照时的2/3); 避光预处理会显著降低体系中H₂O₂的产生速率和浓度; 生物膜数量的增减会导致体系H₂O₂浓度的相应增减; 有机配体的存在会使体系内H₂O₂浓度下降(约1/2~1/3); pH=7和5的体系中H₂O₂的浓度高于pH=9的体系(高出约1.5倍). 上述各因素主要通过影响生物膜生产H₂O₂、 H₂O₂自然分解和生物膜去除H₂O₂ 3种作用来影响体系H₂O₂浓度.     

Ta/Al-Fe2O3薄膜电极的制备及其光电催化降解亚甲基蓝性能

采用简单的涂滴法制备出新型的Al、Ta 共掺杂的三元铁氧化物(Ta/Al-Fe₂O₃)可见光响应型光催化薄膜. 运用X射线光电子能谱(XPS)和紫外-可见(UV-Vis)光谱等手段对其进行了表征, 考察了其光电化学性能, 并研究了复合电极光电催化降解亚甲基蓝(MB)废水的反应性能. 由表面谱学分析可知, Ta 和Al 成功掺入Fe₂O₃中, Ta 会改变催化剂表面Al 和O的化学环境. 在可见光照射下的光电催化(PEC)反应中, Ta/Al-Fe₂O₃降解MB的反应速率约为Al-Fe₂O₃的2 倍, 光电催化共作用的效果优于单纯光催化作用(PC)和电催化(EC)作用的效果.结果表明, Ta掺杂有利于提高Ta/Al-Fe₂O₃薄膜的光电催化活性.     

非贵金属催化电极Ni/C@CF的制备及绿色类Fenton性能

传统芬顿(Fenton)法利用Fe²⁺催化H₂O₂产生具有强氧化性的羟基自由基(·OH),可以高效氧化降解水中有机污染物,但其操作pH范围窄(pH≈3)和易产生铁絮凝沉淀的缺点限制了其应用发展.原子氢H*作为一种单电子供体,可以将电子快速转移到H₂O₂中,生成·OH,适用于广泛的pH值,没有铁污泥产生,是一种新型高效绿色芬顿法.然而,原子H*更易相互结合形成H₂,极不稳定,因此,探索合适的电催化剂对H*绿色Fenton的应用起着至关重要的作用.本文以炭黑作为载体,通过液相还原法制备了具有催化活性高、性能稳定的Ni/C@碳毡(Ni/C@CF)非贵金属电催化材料,制备的Ni纳米粒子均匀分散在炭黑上.以此电极材料为阴极,构建绿色Fenton催化体系,能够催化H₂O和H+生成H*,进而催化H₂O₂产生·OH,高效降解去除水中抗生素污染物.通过调节制备方法、电压、溶液pH值及外加氧化剂量,确定了该体系...     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.