异质结型AgBr/CuO光催化剂的合成、光催化活性及再生

采用沉淀法制备了具有p-n异质结结构的AgBr/CuO可见光催化剂,对其结构进行了表征,通过甲基橙溶液的降解率评价了AgBr/CuO的光催化活性,并通过活性物种测试及能带结构分析推测了其光催化机理,采用3%(质量分数)溴水对使用后的AgBr/CuO进行了再生处理.结果表明,在可见光照射下,0.1 g AgBr/CuO光催化剂30 min对甲基橙溶液(初始浓度为15 mg/L)的降解率高达92%,远高于同等条件下的AgBr.AgBr/CuO光催化活性提高的原因是Ag Br与CuO的复合一方面使催化剂的禁带宽度变宽,提高了光生电子与光生空穴的氧化还原能力;另一方面,在两者之间形成了p-n型异质结结构,有利于光生电子的转移及光生电子与空穴的分离.采用绿色环保的溴水再生法可显著恢复催化剂的光催化活性.     

离子交换法制备AgBr/Ag_2WO_4复合催化剂及其可见光催化性能

以Ag2WO4为载体,采用离子交换法合成了新型的AgBr/Ag2WO4复合光催化剂.利用XRD、SEM和UV-Vis对AgBr/Ag2WO4催化剂进行了表征,在可见光条件下(500 W、λ>420nm)、以甲基橙(MO)为染料模型研究了Ag-Br/Ag2WO4的光催化活性.结果表明,AgBr/Ag2WO4具有比单独的AgBr和Ag2WO4更佳的催化活性,其中30%-AgBr/Ag2WO4复合催化剂具有最大光催化活性.机理研究表明,在MO的降解过程中,.O2-起主要作用,h+次之而.OH可以忽略.AgBr和Ag2WO4之间构成的异质结有效分离了光生电子和空穴,提高了催化剂的活性.     

异质结型AgI/AgBr/TiO_2催化剂的制备及其光催化性能

首先以沉积-沉淀法制备AgBr/TiO2复合催化剂,然后采用离子交换法制备出新型的异质结型AgI/AgBr/TiO2光催化剂.利用XRD和UV-Vis对AgI/AgBr/TiO2光催化剂进行了表征.以甲基橙为染料模型,在可见光条件下(500 W、λ420 nm)研究了AgI的含量对AgI/AgBr/TiO2催化活性的影响.结果表明,AgI拓展了催化剂的吸收光谱范围;AgI生成量为AgBr的5%时,AgI/AgBr/TiO2的催化活性最高.AgI/AgBr异质结的形成有利于光生电子和空穴的分离,提高AgI/AgBr/TiO2的催化活性.     

g-C3N4-BiOBr复合材料制备及可见光催化性能

利用原位沉积法将Bi OBr纳米片生长到g-C_3N_4表面,制得g-C_3N_4-Bi OBr p-n型异质结复合光催化剂。采用X射线衍射(XRD)、红外光谱(FTIR)、场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、紫外可见漫反射(UV-Vis-DRS)和荧光光谱(PL)等测试对光催化剂结构和性能进行表征。通过可见光辐照降解甲基橙水溶液检测评估复合光催化剂光催化活性。研究结果表明:复合光催化剂由Bi OBr和g-C_3N_4两相组成,Bi OBr纳米片在片状g-C_3N_4表面快速形核生长形成面-面复合结构。相比于纯相g-C_3N_4和Bi OBr,g-C_3N_4-Bi OBr复合材料具有更强可见光吸收能力,吸收带边红移。在可见光辐照100 min后,性能最佳的2:8 gC_3N_4-Bi OBr复合光催化剂光催化活性分别是纯相g-C_3N_4和Bi OBr的1.8和1.2倍,经过4次循环实验后,其降解率仍达84%,说明复合结构光催化剂催化性能和稳定性增强。复合光催化剂的荧光强度显著降低,说明光生载流子复合得到了有效抑制。复合光催化剂催化性能的提高归因于p-n型异质结促进电荷有效分离、抑制电子-空穴复合和吸收光波长范围的扩展,相比单一成分材料具有更好的催化活性和稳定性。自由基捕获实验证明,可见光降解甲基橙光催化过程中的主要活性成分为空穴,并据此提出了可能的光催化机理。     

负载型AgBr/CaWO_4催化剂的制备及其可见光催化活性

采用化学取代的方式将AgBr负载到Ca WO4载体上形成新型的AgBr/Ca WO4复合结构光催化剂.利用XRD、SEM和UV-Vis对AgBr/Ca WO4催化剂进行了表征.在可见光条件下(500 W、λ420 nm)研究了AgBr的负载量、催化剂用量对甲基橙(MO)溶液的催化降解性能.结果表明,AgBr/Ca WO4在可见光下表现出良好的催化活性,甲基橙溶液的降解遵从假一级动力学方程.AgBr的负载量和催化剂用量分别增加时,AgBr/Ca WO4催化剂对甲基橙的催化活性增强,均趋向于最大值.     

AgBr/TiO_2异质结型复合可见光催化剂的制备及其光催化活性

以钛酸四丁酯、KBr、AgNO3为前体,合成了具有异质结结构的纳米AgBr/Ti O2复合可见光催化剂.利用XRD、TEM、HRTEM和UV-Vis等方法对催化剂的晶相组成、形貌、粒度、微观结构、吸光性能等进行了表征.光催化降解亚甲基蓝活性结果表明,复合与单组分催化剂的光催化活性顺序为:AgBr/Ti O2AgBrAg-Br/P25P25Ti O2.含光敏剂AgBr的复合及单组份催化剂由于具有对可见光的良好吸收性能而具有较高的光催化活性.对于AgBr/Ti O2光催化剂,随mAgNO3/mTi O2比的增加,光催化活性先增强后减弱,当mAgNO3/mTi O2=3.35时光催化活性最高,分析结果表明,该复合催化剂粒径约15 nm,分散均匀且形成了紧密接触的AgBr/Ti O2异质结微结构,在紫外可见区(250～800 nm)都具有最强的光吸收.     

不同煅烧温度制备的n-p型CeO_2/BiOBr光催化性能研究

采用微乳法制备了n-p型CeO_2/BiOBr异质结,其中十六烷基三甲基溴化铵(CTAB)既作为Br源,又作为"桥"使CTA~+修饰在CeO_2表面形成了稳定的油包水微乳体系.利用XRD、SEM、HRTEM、UV-Vis DRS、BET、XPS等对样品进行结构、形貌和光学性质进行表征,并对复合光催化剂进行了可见光下降解甲基橙(MO)的光催化活性研究.考察了不同煅烧温度对合成CeO_2/BiOBr的影响.结果表明:CeO_2/BiOBr异质结相比于单体CeO_2和BiOBr来说,它的光响应范围大大增加,在可见光下降解MO具有更高的光催化活性.450℃下煅烧可使MO达到最佳的降解率,而高温则会使催化剂发生烧结.机理研究表明,在CeO_2与BiOBr复合体中,使有机物矿化的主要为CeO_2价带上的光生空穴.CeO_2/BiOBr催化活性增强主要是由于在CeO_2与BiOBr之间形成了n-p型的异质结.     

BiPO4@Ag3PO4核/壳异质结的制备及光催化性能

采用简单的水热法结合离子交换法制备了BiPO4@Ag3PO4核/壳异质结光催化剂,采用场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、紫外-可见漫反射光谱仪(DRS)和X射线光电子能谱仪(XPS)等对催化剂的形貌、组成、晶型和光物理性质等进行了研究,用罗丹明B(RhB)为模拟水体中有机污染物分别在可见光和模拟太阳光照条件下对催化剂的催化活性进行了测试.结果表明,负载Ag3PO4的BiPO4微米棒具有较高的可见光响应,其核/壳异质结结构有利于光生电子-空穴对的有效分离和提高对RhB的光催化降解效率,在可见光和模拟太阳光照射条件下分别在60和40 min可使RhB完全脱色降解.活性物种检测实验结果证明,该催化剂在污染物降解过程中主要的机理是光生空穴的直接氧化.     

1D/2D TiO2/ZnIn2S4S型异质结光催化剂及其高效制氢性能

通过半导体催化剂利用太阳能分解水制氢被认为是解决人类面临的环境问题和能源危机的有效途径.在众多的半导体光催化剂中,TiO₂由于其良好的光化学稳定性、无毒性、丰富的形貌以及低廉的价格,在光催化制氢领域备受关注.然而TiO₂的内在缺陷,如较宽的带隙、较窄的光响应范围,光生电子空穴对的快速复合,极大限制了其太阳能制氢效率.构建异质结结构被认为是解决以上问题的一个有效方法,通过将TiO₂与另一个半导体复合可以提升催化剂对太阳光的吸收范围,也可降低光生电子空穴对的复合速率.但构建一个成功的异质结结构不仅要满足上述的要求,还需要保留异质结催化剂体系中光生电子和空穴的氧化还原能力.研究表明,S型异质结是将两个具有合适能带结构的半导体进行耦合,由于费米能级的差异,两个半导体间将发生电子转移,从而引起能带弯曲并形成内建电场.光照条件下,具有较弱还原能力的光生电子在内建电场和能带弯曲的作用下与较弱氧化能力的光生空穴复合,实现异质结催化剂体系中各个半导体内部光生载流子有效分离的目标,同时保留了异质结催化剂体系中较强氧化能力和较强还原能力的光生电子和空穴,进而实现光催化活性的提高.本文采用水热合成方法,将具有更强还原能力和可见光响应特性的半导体(ZnIn₂S₄)原位生长在TiO₂纳米纤维表面,构建了1D/2DTiO₂/ZnIn₂S₄S型异质结光催化剂.最优比例的TiO₂/ZnIn₂S₄复合材料表现出优越的光催化制氢活性(6.03mmol/h/g),分别是纯TiO₂和纯ZnIn₂S₄制氢活性的3.7倍和2倍.TiO₂/ZnIn₂S₄复合材料光催化活性的提高可以归因于紧密的异质结界面、光生载流子的有效分离、丰富的反应活性位点以及增强的光吸收能力.通过原位XPS和DFT计算研究了异质结内部光生电子的转移机制.结果表明,在光照条件下电子由TiO₂向ZnIn₂S₄迁移,遵循了S型异质结内部电子的转移机制,实现了TiO₂和ZnIn₂S₄内部光生载流子的有效分离,同时保留了具有较强还原能力的ZnIn₂S₄价带电子和较强氧化能力的TiO₂导带空穴,从而显著提升光催化制氢效率.综上,本文制备的TiO₂/ZnIn₂S₄S型异质结光催化剂很好地克服了TiO₂在光催化制氢领域所面临的诸多障碍,为设计和制备高效异质结光催化剂提供了新的思路.     

新型可见光响应的InVO_4-Cu_2O-TiO_2三元纳米异质结:制备及其光催化性能（英文）

由于日益严重的环境和能源危机,可见光催化剂的开发已成为当今最具挑战和紧迫的任务之一.将TiO_2和其它窄禁带半导体复合,已被证明是一种有效的可提高其可见光光催化性能的策略.Cu_2O是一种禁带宽度为2.0 eV的p型窄禁带半导体,InVO_4则是一种禁带宽度为2.0 eV的n型半导体,因它们可用于可见光光解水产氢和有机污染物的可见光降解而在过去的数年中引起了人们广泛的关注.但是纯的Cu_2O和InVO_4由于光生电子空穴对在其内部快速地复合,光催化活性通常都比较低.基于能带工程的策略本文设计了一种新型的可见光响应的InVO_4-Cu_2O-TiO_2三元纳米异质结,并通过普通的湿化学法进行制备:先通过水热法制备InVO_4,再通过溶胶-凝胶法制备InVO_4-TiO_2二元复合物,最后通过沉淀和还原过程制备得到InVO_4-Cu_2O-TiO_2三元纳米异质结.在10%InVO_4-40%Cu_2O-50%TiO_2三元纳米异质结的X-射线衍射谱中没有观察到明显的杂质峰;通过透射电子显微技术和高分辨透射电子显微技术观察到了它们之间异质结的形成,纳米颗粒的尺寸范围在5-20 nm;经紫外可见漫反射光谱估算得到10%InVO_4-40%Cu_2O-50%TiO_2的禁带宽度为2.78 e V,在可见光区域具有较强的吸收.以普通的9 W节能灯作为可见光光源光照甲基橙5 h后,纯的InVO_4,TiO_2和Cu_2O几乎没有光催化活性;10%InVO_4-90%TiO_2的光催化活性也很低,甲基橙降解率为8%;70%Cu_2O-30%TiO_2对甲基橙降解率达84%,但初始活性较低;10%InVO_4-40%Cu_2O-50%TiO_2对甲基橙降解率接近90%,并且循环使用6次后,其光催化活性的保持率还维持在90%以上,而50%Cu_2O-50%TiO_2光催化活性的保持率只有74%.经对使用过的10%InVO_4-40%Cu_2O-50%TiO_2进行X射线光电子能谱表征发现,存在一弱小的Cu(II)震动卫星峰,表明在InVO_4-Cu_2O-TiO_2的光催化过程中Cu_2O的光蚀并不严重.从能带工程的角度分析,InVO_4-Cu_2O-TiO_2三元纳米异质结具有优异的可见光催化性能的主要原因为:InVO_4的导带电极电位约为-0.5 e V(vs.SHE,下同),价带电位约为+1.5 e V,Cu_2O的分别约为-1.6和+0.4 e V,与TiO_2(导带和价带电极电位分别约为-0.23和+2.97 e V)相比,它们的导带位置更负,将它们组装成三元复合结构,可见光激发的导带电子就可能从InVO_4和Cu_2O的导带迁移到TiO_2的导带上去.同时,n型的TiO_2和InVO_4都与p型的Cu_2O形成p-n异质结,n型的TiO_2和InVO_4之间形成n-n异质结,由于p-n异质结中内电场的存在以及不同能级相互耦合,可进一步促进可见光激发的导带电子从InV O4和Cu_2O的导带迁移到TiO_2的导带上去,以及可见光激发的价带空穴从InVO_4的价带迁移到Cu_2O的价带上去,从而实现光生载流子空间上的有效分离.本文有望为新型可见光响应的半导体复合催化剂的设计和制备提供新的思路.     

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.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.