COVER STORY

正Hou and coworkers in their Article on pages 136–144 reported H+/nanosheets and H+/nanoscrolls derived from K4Nb6O17with increased surface areas have a high adsorption capacity and a rapid visible-light response for the photodegradation of RhB.The materials can be easily prepared with low-cost and so,     

COVER STORY

<正>Hou and coworkers in their Article on pages 136–144 reported H+/nanosheets and H+/nanoscrolls derived from K4Nb6O17with increased surface areas have a high adsorption capacity and a rapid visible-light response for the photodegradation of RhB.The materials can be easily prepared with low-cost and so,     

Pd/TiO2 Nanospheres with Three-dimensional Hyperstructure for Enhanced Photodegradation of Organic Dye

Pd/TiO2 nanospheres assembled from nanorods with three-dimensional hyperstructure for enlianced photodegradation of organic dye was prepared by a sample solvothemial method. Further, it was used for degradation of methyl orange(MO) under the illumination of visible-light(simulated).The results show that Pd/TiO2 with 2%(mass fraction) Pd exhibits the noticeable activity in photodegrading of MO.The detailed analysis shows that this enhancement is attributed to the reduction of the rate of electron-hole recombination and surface plasmon resonance of Pd. The high activity and good stability of the obtained Pd/TiO2 nano spheres make it a promising photocatalyst for solving the environmental pollution problems.     

Double Hydrothermal Synthesis of Graphene Supported TiO2（b） Nanosheets as Anode Materials for Lithium Ion Batteries

The synthesis of graphene supported TiO2（b） nanosheets by a double hydrother- mal method for lithium storage was reported. The titanate nanosheets synthesized by the first hydrothermal progress and the graphene oxide obtained by the oxidation of graphite were hydrothermally treated together to fabricate the TiO2（b）/graphene composite. The electrochemical measurements illustrate that the graphene supporter obviously improves the cyclic performance of TiO2（b）, which can be attributed to the better dispersion and the decrease of resistance for the TiO2（b） nanosheets in the composite.     

Toward the most versatile fluorophore: Direct functionalization of BODIPY dyes via regioselective C–H bond activation

Fluorescent dyes are heavily sought for their potentials applications in bioimaging, sensing, theranostic,and optoelectronic materials. Among them, BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. The increasing success of BODIPY dyes is closely associated with their excellent and tunable photophysical properties due to their rich functionalization chemistry.Recently, growing research efforts have been devoted to the direct functionalization of the BODIPY core,because it allows the facile installation of desired functional groups in a single atom economical step. The challenges of this direct C–H derivation come from the difficulties in finding suitable functionalization agents and proper control of the regioselectivity of the functionalization. The aim of this work is to provide an overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C–H functionalization of the BODIPY framework.     

Zeolite NaY-mediated oxidation of dyes with H_2O_2: unique heterogeneous non-transition metal center cleavage of H_2O_2 under visible light irradiation

This study investigated the visible-light catalysis mediated by zeolite NaY on the oxidation of dyes with H2O2. The results demonstrated that zeolite NaY acts as a sink for the electron from the photo-excited dye in the heterogeneous catalysis. Furthermore, the electron can effectively activate H2O2 to produce ?OH radical that is a powerful oxidant for the oxidation of dye at room temperature. The effects of the framework topology, Si/Al ratio, and exchangeable cation of the zeolite on the oxidation of various dyes were also shown.     

高活性多壁碳纳米管/TiO2纳米复合物光催化剂光催化降解活性黑5染料（英文）

A nanocomposite UV-visible light-responsive multiwalled carbon nanotube (MWCNT)/titanium dioxide(TiO2) nanophotocatalyst was successfully synthesized by a modified sol-gel method using titanium isopropoxide and functionalized MWCNTs as the starting precursors. The photocatalytic activity of the TiO2 and the nanohybrid material was investigated through the photodegradation of Reactive Black 5 dye under ultraviolet light irradiation. X-ray diffraction analysis indicated that anatase phase was obtained for both the pure TiO2 and the MWCNT/TiO2 composite, while Raman spectroscopy confirmed the presence of MWCNTs in the composite. Field emission scanning elec-tron microscopy revealed that TiO2 nanoparticles with an individual diameter of about 10–20 nm were coated on the surface of the MWCNTs. The specific surface areas of the samples were found to be 80 and 181 m2/g for the pure TiO2 and MWCNT/TiO2, respectively. As a result, MWCNT/TiO2 showed better photocatalytic performance than pure TiO2 because the high surface area of MWCNTs enabled them to function as good electron acceptors for the retardation of electron-hole pair recombination.     

Ag2S-石墨烯/TiO2的声化学法合成及可见光催化活性（英文）

Ag2S‐graphene/TiO2 composites were synthesized by a facile sonochemical method.The products were characterized by X‐ray diffraction,scanning electron microscopy,energy dispersive X‐ray spectroscopy,transmission electron microscopy,and UV‐Vis diffuse reflectance spectrophotometry.During the synthesis reaction,the reduction of graphene oxide and loading of Ag2S and TiO2 particles were achieved.The Ag2S‐graphene/TiO2 composites possessed a large adsorption capacity for dyes,an extended light absorption range,and efficient charge separation properties.Hence,in the photodegradation of rhodamine B,a significant enhancement in the reaction rate was observed with the Ag2S‐graphene/TiO2 composites as compared to pure TiO2.The generation of reactive oxygen species was detected by the oxidation of 1,5‐diphenyl carbazide to 1,5‐diphenyl carbazone.The high activity was attributed to the synergetic effects of high charge mobility and the red shift in the absorption edge of the Ag2S‐graphene/TiO2 composites.     

Effect of Hydrophobic Chain of Dye Molecule and Surface of Active Crystal on the Organized Assemblies Formation of Dyes

Four derivatives of 5,5',6,6'-tetrachlorobenzimidazolocarbocyanine iodide with different long alkyl chain substituents in N-position of polymethine chromophore have been used for investigating the influence of hydrophobicity of dyes on the aggregation.It has been found that all dyes formed monomeric species in methyl alcohol. However, after addition of water to CH_3OH to change the polarity of the solvent, difference between dyes appeared.Addition of inorganic salt facilitated the J-aggregation of easy soluble dye, but it seems useless for the sparely soluble dye.Platelets cut from AgBr polycrystal or pressed AgBr powder have been used as substrate for adsorbing dyes. After addition of hexanoic acid, eventually the J-aggregate on AgBr surface could be destroyed.Voltammetry is a useful tool to investigate the interaction between dyes and AgBr. Experimental results showed that the longer the carbon chain substituents is, the stronger the interaction between AgBr and dyes would be.     

Quasi-classical Trajectory Study of the Intramolecular Isotope Effect in the Reaction O（3p）＋H2/HD

Theoretical studies of the dynamics of the reactions O（3p）＋H2/HD（ν=0, j=0）→OH＋H have been performed with quasi-classical trajectory method （QCT） on an ab initio potential surface for the lowest triplet electronic state of H2O（aA＂）. The QCT-calculated integral cross sections are in good agreement with the earlier time-dependent quantum mechanics results. The state-resolved rotational distributions reveal that the product OH rotational distributions for O＋HD have a preference for populating highly internally excited states compared with the O＋H2 reaction. Distributions of differential cross sections show that directions of scattering are strongly dependent on the choice of quantum state. The polarization dependent generalized differential cross-sections and the distributions were calculated and a pronounced isotopic effect is revealed. The calculated results indicate that the product polarization is very sensitive to the mass factor.     

A comparison of H+-restacked nanosheets and nanoscrolls derived from K4Nb6O17 for visible-light degradation of dyes

H⁺-restacked nanosheets and nanoscrolls peeled from K₄Nb₆O₁₇ display different structures and surface characters. The two restacked samples with increased surface areas have an amazing visible-light response for the photodegradation of dyes, which is superior to commercial TiO₂ (P25) and Mb₂O₅. By comparison, H⁺/nanosheets have a relatively faster photodegradation rate originated from large and smooth basal plane. The work reveals that dye adsorbed on the unfolded nanosheets can effectively harvest sunlight. Due to facile preparation, low-cost and high photocatalytic efficiency, H⁺/nanosheets and H⁺/nanoscrolls might be used for the visible light-driven degradation of organic dyes as a substitute for TiO₂ in industry.     

Kinetics of heterogeneous photocatalytic degradation of reactive dyes in an immobilized TiO2 photocatalytic reactor

The photocatalytic degradation of two reactive dyes has been investigated by UV/TiO2/H2O2 using an immobilized TiO2 photocatalytic reactor. Reactive Blue 8 (RB 8) and Reactive Blue 220 (RB 220) textile dyes were used as model compounds. Photocatalytic degradation processes were performed using a 5-L solution containing dyes. The initial concentrations of dyes were 50 mg/L. The radiation source was two 15 W UV-C lamps. A batch mode immersion photocatalytic reactor was utilized. UV-vis and ion chromatography (IC) analyses were employed to obtain the details of the photodegradation of the selected dyes. Colored synthetic waters were completely decolorized in relatively short time after UV irradiation in the presence of various concentrations of hydrogen peroxide. Formate, acetate, oxalate, and glyoxylate anions were detected as dominant aliphatic intermediates where they were further oxidized slowly to CO2. The UV/TiO2/H2O2 process was able to oxidize the dyes with partial mineralization of carbon, nitrogen, and sulfur heteroatoms into CO2, NO3-, and SO4(2-), respectively. Kinetics analysis indicates that the photocatalytic decolorization rates of the dye can be approximated by a pseudo-first-order model. The UV/TiO2/H2O2 process proved to be capable of decolorization and mineralization of the reactive dyes (RB 8 and RB 220).     

Cost-effective large-scale synthesis of ZnO photocatalyst with excellent performance for dye photodegradation

Zinc oxide with excellent photocatalytic performance for the photodegradation of dyes (superior to Degussa P25 TiO(2)) could be easily prepared in large quantity by direct calcination of zinc acetate (Zn(Ac)(2)·2H(2)O).     

Cu2+/TiO2对甲基橙的光催化降解机理

以自制的掺铜离子的混晶型二氧化钛为光催化剂,考察了甲基橙光催化降解过程中pH值和光源的影响,提出了两种不同的光催化降解机理:在高压汞灯照射下,TiO2的价带电子被激发到导带,光生电子和空穴主要通过Cu2+ 的短路循环而复合,光催化剂的活性降低;在太阳光照射下,甲基橙发生自身光敏化氧化反应,受激电子从单线态或三线态的甲基橙分子跃迁到TiO2的导带,Cu2+起到电荷传递中继站的作用,加速了注入电子向H2O2的转移,从而促进了甲基橙的光催化降解。     

Photodegradation catalyst discovery by high-throughput experiment

A high-throughput experimental methodology was developed for photocatalysis reaction. In this work, a CCD imaging analysis system and photocatalytic reactor for UV light was designed and tested. By making use of the technologies, we have screened several catalyst libraries. From the SiO2-supported single component catalyst library, we found that TiO2, ZrO2, Nb2O5, and WO3 were good candidates for highly active catalyst formulation. We designed and screened several triangle catalyst libraries and found that the WO3- and Nb2O5-codoped TiO2 catalyst showed much higher photodegradation activities for the degradation of 1,6-hexamethylenediamine than did the pure TiO2 catalyst. The doping of ZrO2 into TiO2 did not generate apparent positive effects on catalytic activity.     

The co-effect of Sb and Nb on the SCR performance of the V2O5/TiO2 catalyst

The effect of the Sb and Nb additives on the V(2)O(5)/TiO(2) catalyst for the selective catalytic reduction (SCR) of NO with NH(3) was investigated. The experimental results show that either Nb or Sb can improve the activity of V(2)O(5)/TiO(2) catalyst. Higher Nb loading led to higher N(2) selectivity. The co-doping of Sb and Nb showed higher improving effect than the single doping of Sb or Nb. The V(2)O(5)/TiO(2) catalyst doped with Sb and Nb had a better H(2)O resistance than the V(2)O(5)/TiO(2) catalyst. The addition of Sb and Nb also enhance the resistance of the V(2)O(5)/TiO(2) catalyst to K(2)O poisoning. The catalysts were characterized by BET, XRD, TEM, and XPS. The results showed that the active components of V, Sb, and Nb were well interacting with each other. The coexistence of Sb and Nb will enhance the redox ability and surface acidity and thus promote the SCR performance.     

Water-mediated promotion of dye sensitization of TiO2 under visible light

Preadsorbed water along with surrounding bulk water significantly modulates the surface electronic structure of TiO(2), switches the adsorption mode of dyes, and promotes dye sensitization of TiO(2) under visible-light irradiation. This opens a door toward facile improvement in the efficiency of photodegradation of dyes and dye-sensitized solar cells under visible-light irradiation without any complicated and expensive surface modulation.     

Ni-CH_3CH_2NH_2/H_(1.78)Sr_(0.78)Bi_(0.22)Nb_2O_7复合层状钙钛矿的合成及光催化分解水产氢性能(英文)

自从分解水产氢被首次报道以来,许多光催化剂被开发出来并用于光催化分解水产氢.然而,由于光生电子和空穴的复合率普遍较高,大部分的光催化剂分解水产氢效率都很低.因此,开发新型高效的光催化材料至关重要.具有(Bi_2O_2)~(2+)(A_(m-1)M_mO_(3m+1))~(2-)通式的Aurivillius相层状钙钛矿材料因具有独特的层状结构、元素可调性以及优异的电荷传输和分离能力而广泛应用于光催化分解水和去除有机污染物.此外,当该类层状钙钛矿被剥离成超薄纳米片时,其光催化性能进一步提高.为了进一步提高层状钙钛矿的载流子分离能力,将客体(如贵金属,半导体等)通过化学反应的途径插入到层状钙钛矿的层间区域,从而合成出复合层状钙钛矿被广泛发展和应用.然而,引入的客体主要是贵金属和半导体,这类客体的高成本和不均匀分布制约了其进一步的应用.由于廉价、无毒和稳定等优点,镍基材料如Ni,NiO,Ni_2O_3,NiS,NiS_2,Ni(OH)2和Ni(OH)x等被广泛用作增强电极材料的光电性能和催化剂的光催化分解水产氢性能的助催化剂.本文采用简单的原位化学反应法制备出镍基配合物Ni-CH_3CH_2NH_2(Ni-EA)插层的Ni-CH_3CH_2NH_2/H_(1.78)Sr_(0.78)Bi_(0.22)Nb_2O_7(Ni-EA/HSNNs)复合层状钙钛矿;然后采用X-射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、X-射线光电子能谱(XPS)、紫外-可见漫反射光谱等手段对Ni-EA/HSNNs光催化剂进行了系统的研究.XRD结果表明,引入Ni~(2+)后,HSNNs层间距减小并且平行于钙钛矿层的晶面结晶度增强,证明HSNNs沿垂直于钙钛矿层的方向出现了层层组装.FTIR和XPS结果表明,引入的Ni~(2+)与HSNNs层间和表面的乙胺分子之间存在较强的相互作用,结合高分辨透射电镜图可知,Ni的存在形态可能为配合物Ni-EA.由此可见,当向HSNNs中引入Ni~(2+)时,Ni~(2+)和HSNNs层间和表面的乙胺分子反应生成带正电的配合物Ni-EA,由于Ni-EA与HSNNs的钙钛矿层带有异种电荷,两者之间存在较强的静电相互作用力,从而引起钙钛矿纳米片HSNNs的层层组装,最后形成Ni-EA/HSNNs复合层状钙钛矿.光催化分解水产氢性能测试结果表明,当引入0.5 wt%Ni时,复合层状钙钛矿表现出最优的光催化性能.与HSNNs(241.58μmol/h)相比,0.5%Ni-EA/HSNNs的光催化分解水产氢速率(372.67μmol/h)提高了0.54倍,表现出与0.5%Pt/HSNNs可比拟的光催化活性,可见,非贵金属Ni具有替代贵金属Pt的能力.进一步的研究表明,镍基配合物Ni-EA显著增强了催化剂的光生载流子的传输和分离能力,从而提高了其光催化分解水产氢性能.该文为光催化分解水产氢提供了一种简便的合成非贵金属配合物助催化剂的方法.     

Exfoliated nanosheets as a new strong solid acid catalyst

Two-dimensional metal oxide sheets in HTiNbO(5) and HSr(2)Nb(3)O(10), cation-exchangeable layered metal oxides, were examined as solid acid catalysts. Exfoliation of HTiNbO(5) and HSr(2)Nb(3)O(10) in aqueous solutions formed colloidal single-crystal TiNbO(5)(-) and Sr(2)Nb(3)O(10)(-) nanosheets, which precipitated under an acidic condition to form aggregates of HTiNbO(5) nanosheets and HSr(2)Nb(3)O(10) nanosheets. Although esterification of acetic acid, cracking of cumene, and dehydration of 2-propanol were not catalyzed by original HTiNbO(5) because of the narrow interlayer distance, which prevents the insertion of organic molecules, HTiNbO(5) nanosheets functioned as a strong solid acid catalyst for the reactions. Nanosheets of HSr(2)Nb(3)O(10) exhibited no or slight catalytic activity for these reactions. NH(3) temperature-programmed desorption and (1)H magic-angle spinning nuclear magnetic resonance spectroscopy revealed that HTiNbO(5) nanosheets have strong Br?nsted acid sites, whereas HSr(2)Nb(3)O(10) nanosheets do not.     

One-pot, solvothermal synthesis of TiO(2)-graphene composite nanosheets

In this article, we propose a facile one-pot solvothermal route for synthesizing TiO(2)-graphene composite nanosheets (TGCN). In the system, ethylene glycol not only as a reducing agent can convert graphene oxide to reduced graphene oxide nanosheets, but also is employed to control the hydrolysis and condensation rates of tetrabutoxytitanium. The obtained TGCN hybrid materials are characterized by atomic force microscopy, transmission electron microscopy, UV-vis spectroscopy, Raman spectroscopy, X-ray photo-electron spectroscopy, X-ray diffraction, and thermal gravimetric analysis. It is found that the quantity of H(2)O used in the reaction is the key to obtain high-quality product. The photocatalytic activities of the products are evaluated using the photocatalytic degradation of methylene blue (MB) as a probe reaction. The results showed that the obtained TGCN have an enhanced adsorption capacity and remarkable improvements in the photodegradation rate of MB under visible light compared to P25.