Fe对NaNbO3的晶格掺杂和同步异质结改性及其光催化性能

运用溶剂热法及继之的高温晶化法制备钙钛矿结构NaNbO₃,并在此基础上同步获得了NaNbO₃晶格内Fe³⁺的掺杂和NaNbO₃晶格外α-Fe₂O₃的异质结复合.观察到了同步改性NaNbO₃对水体罗丹明B（RhB）光催化降解效率的显著提升,最适Fe含量的改性NaNbO₃对罗丹明B 1 h内的降解率可达95%,表观一级动力学速率常数为改性前NaNbO₃的近7倍.运用X射线衍射（XRD）、扫描电子显微（SEM）、X光电子能谱（XPS）、光致发光（PL）光谱、低温N₂吸附-脱附（BET法）,电子自旋共振光谱（ESR）,紫外-可见漫反射光谱（DRS）及光致电流检测等表征和测量探明改性体系的组成及结构,并表明Fe³⁺对Nb⁵⁺的掺杂取代可通过杂质能级形成、电子和空穴捕获以及溶氧吸附的促进从而有利于对罗丹明B的光催化降解;适量α-Fe₂O₃晶格外复合改性NaNbO₃可通过NaNbO₃与α-Fe₂O₃异质结间电子的跃迁和流动提高复合催化剂的光量子效率.Fe对NaNbO₃晶格内外改性促活的实质可能在于光生载流子迁移的促进和对其复合的抑制.     

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.     

Metal-organic framework as a multi-component sensor for detection of Fe3+, ascorbic acid and acid phosphatase

In this research,a hydroxyl group functionalized metal-organic framework(MOF),UiO-66-(OH)₂,was synthesized as a "on-off-on" fluore scent switching nanoprobe for highly sensitive and selective detection of Fe³⁺,ascorbic acid(AA) and acid phosphatase(ACP).UiO-66-(OH)₂ emits yellow-green light under ultraviolet light,when Fe³⁺ was added,Fe³⁺ was chelated with hydroxyl group,the electrons in the excited state S_1 of the MOF transferred to the half-filled 3 d orbits of Fe³⁺,resulting in fluorescence quenching because of the nonradiative electron/hole recombination annihilation.AA could reduce Fe³⁺ to Fe²⁺,which can destroy the electron transfer between UiO-66-(OH)₂ and Fe³⁺ after AA adding,resulted in nonoccurrence of the nonradiative electron transfer,leading to the recovery of UiO-66-(OH)₂ fluorescence intensity.The probe can also be used to detect ACP based on the enzymolysis of 2-phospho-L-ascorbic acid(AAP) to produce AA.Benefitting from the hydroxyl group and the characteristics of UiO-66,including the high porosity and large surface area,the developed UiO-66-(OH)₂ showed extensive advantages as a fluorescent probe for detection of multi-component,such as high sensitivity and selectivity,colorimetric detection,fast response kinetics and easy to operate,economical and secure.This is the first time to use active group functionalized MOFs as a multicomponent sensor for these three substances detection.     

X-射线吸收谱原位表征Cu-Zn/SiO2催化剂Cu价态

铜基催化剂的价态组成与制备方法、还原温度有关,也是决定其催化性能的关键因素.本文对比研究Cu-Zn/SiO₂和Cu/SiO₂催化剂前驱体在不同还原温度下的价态组成及其醋酸甲酯加氢性能.采用同步辐射X射线吸收谱原位表征催化剂前驱体的Cu K边的X射线近边吸收谱（XANES）,通过线性组合分析方法（LCF）拟合XANES吸收谱得到了催化剂前驱体在不同还原温度下氧化态（Cu²⁺、Cu⁺）和金属态（Cu⁰）的组分含量.结果表明：（1）采用蒸氨法添加Zn制备的Cu-Zn/SiO₂催化剂前驱体铜组分还原度高;（2）催化剂前驱体在还原过程中Cu⁺主要存在于低温还原阶段（<250℃）,且Cu⁰+Cu⁺含量较低（≤ 40%）;（3）金属态铜是醋酸酯加氢反应的活性中心.     

新型金属有机气凝胶的合成、 表征及气体吸附性能

利用高稳定性的UiO-66系列金属有机骨架多孔材料制备金属有机气凝胶材料, 制得的UiO-66系列金属有机气凝胶材料具有多级孔结构和较高的比表面积, 在气体吸附分离领域具有较大应用潜力. 气体吸附实验结果表明, UiO-66-NH₂金属有机气凝胶材料具有极佳的CO₂吸附性能和CO₂/CH₄分离性能, 通过理想吸附溶液理论计算得出其吸附选择性高达18.3.     

g-C3N4/Fe3O4/BiOI磁性材料的制备及其可见光助芬顿催化性能

采用共沉淀-回流法制成g-C₃N₄/Fe₃O₄/BiOI磁性复合材料作为异相光助芬顿(Fenton)催化剂。运用扫描电镜(SEM)、透射电镜(TEM)、X-射线衍射(XRD)、振动样品磁强计(VSM)和N₂吸附-脱附等手段分别对催化剂的形貌、结构、组成、磁性和比表面积等进行了表征，并以罗丹明B(RhB)为模型污染物考察了材料的可见光催化性能。实验结果表明，当BiOI的负载质量为50%时，在可见光照射下，复合材料具有最好的光催化性能，180 min内对RhB的降解效率可达到99.20%。较高的光催化性能归因于所制备材料对RhB较强的吸附、强烈的可见光响应以及异质结构促进了光生载流子的分离。进一步在光催化体系中加入适量的H₂O₂后，可极大提高三元复合材料可见光助Fenton降解RhB的效率，30 min内即可达到98.44%,这得益于体系中发生Fenton反应产生较多具有强氧化性的羟基自由基，同时光生电子可加速Fe³⁺     

可见光/Fenton光催化降解有机染料

采用Fenton试剂(Fe³⁺/H₂O₂)在可见光条件下(λ＞450nm)光催化降解目标染料化合物罗丹明B(RhodamineB,RhB).在pH＜3.0体系中用可见光照射,能使RhB染料在光敏化作用下有效降解,反应160min后矿化率达到71.8%.采用ESR和溴甲酚绿(Bromocresolgreen,BCG)法跟踪测定活性氧化物种,通过对RhB降解过程的紫外-可见光谱、红外光谱分析及总有机碳量(TOC)跟踪测定,结果表明,Fe³⁺/H₂O₂/RhB体系在可见光照射下主要的活性氧化物种为羟基自由基,能有效地降解RhB.     

Fe3+掺杂TiO2/凹凸棒复合光催化剂的制备和光催化活性

用酸催化溶胶-凝胶法制备了Fe³⁺掺杂TiO₂/凹凸棒（Fe³⁺-TiO₂/ATP）复合光催化剂,对其结构、微观形貌、光吸收性能和可见光下的光催化性能进行了表征。XRD和TEM测试结果表明,Fe³⁺-TiO₂/ATP具有较好的热稳定性,经450 ℃热处理后的ATP晶体结构基本保持不变,锐钛矿TiO2均匀的分布在ATP表面,TiO2颗粒之间无团聚,且平均粒径小于纯TiO₂。UV-Vis-DRS测试结果表明,Fe³⁺的掺杂可明显增强复合光催化剂对可见光的吸收,光响应范围拓展到了整个紫外-可见光区。在可见光下,Fe³⁺-TiO₂/ATP复合光催化剂对亚甲基蓝具有很好的催化降解活性。Fe³⁺-TiO₂/ATP的反应速率常数分别为TiO₂/ATP、P25和纯TiO2的1.37、4.83和6.51倍。复合光催化剂的沉降性能优于纯TiO2和P25,易于分离。     

氮缺陷石墨相氮化碳的制备及其光催化降解环境有机污染物性能

通过在三聚氰胺热分解过程中加入NaHCO₃制备出具有氮缺陷的石墨相氮化碳（g-C₃N₄）,利用X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、N₂吸附-脱附、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-vis DRS）和固体荧光光谱（PL）等方法对其进行表征,并在可见光（λ> 420nm）照射下,以水相中罗丹明B（RhB）的降解为模型反应,研究了该氮缺陷g-C₃N₄对有机污染物降解的光催化活性。结果表明,引入氮缺陷可以提高g-C₃N₄对可见光的吸收以及电子-空穴对的分离效率,进而提高g-C₃N₄的可见光催化活性。催化剂CNK0.005、CNK0.01和CNK0.05在30min内对RhB的降解率分别为79.8%、100.0%和87.6%;而在相同条件下,没有氮缺陷的g-C₃N₄对RhB的降解率仅为59.8%。     

乙酸修饰Ag/TiO2复合光催化剂的制备及协同催化性能

利用光化学还原法制备了Ag/TiO₂,然后通过乙酸浸渍制备了HAc-Ag/TiO₂复合光催化剂.利用X射线衍射（XRD）、透射电子显微镜（TEM）、傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）和紫外-可见漫反射光谱（UV-Vis DRS）等手段表征了催化剂的性质.以降解水溶液中的甲基橙（MO）为探针反应,考察了催化剂在可见光下的光催化性能.结果表明,乙酸对TiO₂的修饰在TiO₂禁带中产生了"带尾",使TiO₂的禁带宽度发生了显著的缩减;Ag纳米粒子和乙酸共同修饰的HAc-Ag/TiO₂样品具有更窄的禁带宽度和更正的价带顶位置;Ag和乙酸的协同作用使HAc-Ag/TiO₂具有良好的可见光催化活性：可见光照射2 h后,甲基橙在HAc-Ag/TiO₂上的降解率接近100%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.