Combustion synthesis and characterization of nanocrystalline WO3

The energy payback time associated with the semiconductor active material is an important parameter in a photovoltaic solar cell device. Thus lowering the energy requirements for the semiconductor synthesis step or making it more energy-efficient is critical toward making the overall device economics more competitive relative to other nonpolluting energy options. In this communication, combustion synthesis is demonstrated to be a versatile and energy-efficient method for preparing inorganic oxide semiconductors such as tungsten trioxide (WO3) for photovoltaic or photocatalytic solar energy conversion. The energy efficiency of combustion synthesis accrues from the fact that high process temperatures are self-sustained by the exothermicity of the combustion process, and the only external thermal energy input needed is for dehydration of the fuel/oxidizer precursor mixture and bringing it to ignition. Importantly, we show that, in this approach, it is also possible to tune the optical characteristics of the oxide semiconductor (i.e., shift its response toward the visible range of the electromagnetic spectrum) in situ by doping the host semiconductor during the formative stage itself. As a bonus, the resultant material shows enhanced surface properties such as markedly improved organic dye uptake relative to benchmark samples obtained from commercial sources. Finally, this synthesis approach requires only very simple equipment, a feature that it shares with other "mild" inorganic semiconductor synthesis routes such as sol-gel chemistry, chemical bath deposition, and electrodeposition. The present study constitutes the first use of combustion synthesis for preparing WO3 powder comprising nanosized particles.     

Macroporous WO3 thin films active in NH3 sensing: role of the hosted Cr isolated centers and Pt nanoclusters

Macroporous WO(3) films with inverted opal structure were synthesized by one-step procedure, which involves the self-assembly of the spherical templating agents and the simultaneous sol-gel condensation of the semiconductor alkoxide precursor. Transition metal doping, aimed to enhance the WO(3) electrical response, was carried out by including Cr(III) and Pt(IV) centers in the oxide matrix. It turned out that Cr remains as homogeneously dispersed Cr(III) centers inside the WO(3) host, while Pt undergoes reduction and aggregation to form nanoclusters located at the oxide surface. Upon interaction with NH(3), the electrical conductivity of transition metal doped-WO(3) increases, especially in the presence of Pt dopant, resulting in outstanding sensing properties (S = 110 ± 15 at T = 225 °C and [NH(3)] = 74 ppm). A mechanism was suggested to explain the excellent electrical response of Pt-doped films with respect to the Cr-doped ones. This associates the easy chemisorption of ammonia on the WO(3) nanocrystals, promoted by the inverted opal structure, with the catalytic action exerted by the surface Pt nanoclusters on the N-H bond dissociation. The overall results indicate that in Pt-doped WO(3) films the effects of the macroporosity positively combine with the electrical sensitization promoted by the metal nanoclusters, thus providing very lightweight materials which display high functionality even at relatively low temperatures. We expect that this synergistic effect can be exploited to realize other functional hierarchical metal oxide structures to be used as gas sensors or catalysts.     

Assembling molecular species into 3D frameworks: Computational design and structure solution of hybrid materials

We present here the computational prediction of hybrid organic–inorganic extended lattices. The production of candidate crystal structures is successfully performed by direct-space assembly of building-units using the AASBU (Automated Assembly of Secondary Building Units) method, mixing independent organic and inorganic units. Hybrid candidates that are compatible with the imposed metal:organic ratio are generated with their cell parameters, space group, atomic positions, along with their simulated diffraction pattern. Since no explicit limit regarding the nature, number, and size of the inorganic and organic units, or hybrid building-block is involved, the method offers boundless potential for exploring hybrid frameworks in terms of the topological diversity. The most appealing development arises from the computer-assisted design of hybrid frameworks. Indeed, in a significant number of systems, it is well-known that controlled synthesis conditions can promote the occurrence of specific building-units, which serve to “propagate” the infinite crystal structure. We believe that the computational approach presented herein is valuable to create virtual libraries of viable hybrid polymorphs. We further show how it has proven to be, for the first time in the realm of hybrids, a tangible route towards structure solution in direct space, exemplified here with the computational structure determination of two complex hybrid structures, MIL-100 and MIL-101. This challenging area is of special interest when high quality diffraction data are not available or when very large cell sizes are involved. The development of a structural model in direct space, starting with minimal knowledge such as the metal:organic ratio, is shown here to be possible. With such a method in hand, formerly intractable structural problems when using methods based on conventional reciprocal space become feasible in direct space.     

基于插层化学的单晶氧化钨纳米片的制备、表征与形成机制

结合插层化学与湿化学方法的优点, 建立了一种高比表面积、大径厚比、易分散的二维氧化钨(WO3)纳米片单晶的制备新方法. 微米级WO3与Bi2O3在800 ℃通过固相反应生成层状化合物Bi2W2O9; 所得到的Bi2W2O9经盐酸选择性溶出[Bi2O2]层后得到质子化形式的H2W2O7·xH2O相. 以H2W2O7·xH2O为钨源, 以辛胺插层所得无机-有机混杂纳米带为前驱物, 经硝酸氧化除去前驱物中的有机组分后得到正交相WO3·H2O纳米片; 将所得到的WO3·H2O纳米片在250~ 450 ℃和空气气氛中热处理2~5 h(升温速率为2 ℃/min), 得到单斜相WO3单晶纳米片. TEM与SEM分析结果表明, 单晶WO3·H2O与WO3纳米片的形貌相似, 其大小为(200~500) nm×(200~500) nm, 厚度为10~30 nm; 所得WO3·H2O与WO3纳米片单晶的厚度方向分别为[010]和[001]. N2吸附结果表明, WO3·H2O与WO3纳米片的比表面积分别可达到250与180 m2/g.     

Synthesis of Multifunctional Metal‐ and Metal Oxide Core@Mesoporous Silica Shell Structures by Using a Wet Chemical Approach

We demonstrate a facile wet chemical approach for fabricating spherical metal/metal‐oxide core@mesoporous silica shell hybrid nanoparticles with different core and shell thicknesses. Vertically aligned mesoporous silica (mSiO₂) shells were fabricated over the pre‐synthesized spherical SiO₂ nanoparticles through a three‐step strategy: 1) synthesis of core materials, 2) covering the core with an organic–inorganic composite layer, and 3) removing the organic template through calcinations in air. The mechanisms of hybrid structure formation are proposed. The multifunctional nature of the hybrid structures could be induced by incorporating guest ions/molecules, such as Ag, Mn, and TiO₂, into the pores of an mSiO₂ shell. Mn and TiO₂ cluster‐ incorporated composite structures have been tested to be antioxidizing agents and effective photocatalysts through electron spin resonance, radical scavenging tests, and the photocatalytic degradation of rhodamine B. The possibility of incorporating several hetero‐element guest clusters in these mesoporous composite particles makes them highly attractive for multifunctional applications.     

A precursor route to single-crystalline WO3 nanoplates with an uneven surface and enhanced sensing properties

A W-containing inorganic-organic nanohybrid with a plate-like morphology has been successfully prepared through a nonaqueous synthetic route using WCl(6) as the tungsten source and benzyl alcohol as the solvent. The as-prepared hybrid nanomaterial was used directly as an efficient precursor for the formation of WO(3) nanoplates via a simple thermal treatment process. The as-obtained WO(3) material maintains the plate-like morphology of the precursor and possesses a unique uneven surface structure. It is noted that the use of a inorganic-organic hybrid precursor is essential for the creation of an uneven surface on the WO(3) nanoplates, which exhibit high sensitivity and selectivity for the detection of acetone vapour at a relatively low operating temperature (200 °C). The excellent sensing performance of the WO(3) nanomaterial is attributed to its unique uneven surface structure besides the small particle size and ultrathin morphology.     

Synthesis and spectroscopic properties of silica-dye-semiconductor nanocrystal hybrid particles

We prepared silica-dye-nanocrystal hybrid particles and studied the energy transfer from semiconductor nanocrystals (= donor) to organic dye molecules (= acceptor). Multishell CdSe/CdS/ZnS semiconductor nanocrystals were adsorbed onto monodisperse Sto?ber silica particles with an outer silica shell of thickness 2-23 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the energy transfer efficiency, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of nanocrystals with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with numerically calculated FRET efficiencies and by control experiments confirming attractive interaction between the nanocrystals and Texas Red freely dissolved in solution.     

Photocatalytic single electron transfer reactions on TiO2 semiconductor

The use of inorganic semiconductor particles such as titanium dioxide(TiO_2) has received relatively less attention in organic chemistry, although semiconductor particles have been widely used as a single electron transfer photocatalyst in waterpurification, air-cleaning, and self-cleaning. In recent years, the photocatalysis on semiconductor particles has become an active area of research even in organic chemistry, since the heterogeneous semiconductor photocatalysis leads to the unique redox organic reactions. In an early stage, the semiconductor photocatalysis was applied to the oxidation of organic molecules.Semiconductor particles have also the potential to induce the reductive chemical transformations in the absence of oxygen(O_2),by using the suitable sacrificial hole scavenger. In this review, we summarize the representative examples of the reductive and oxidative organic reactions using semiconductor particles and the recent applications to the stereoselective reactions.     

OXIDATION OF HYDROCARBONS UNDER THE MILD CONDITIONS

The oxidation of organic substrates leads to the production of many functionalised molecules which are of great commercial and synthetic importance. The conventional mode of oxidation which involves stoichiometric ammount of Cr or Mn salts has been staked out because of the environmental hazadrous process. The transition to cleaner, safer, and more efficient plants is a new paradigm in the synthetic organic chemistry. Nowadays, hydrogen peroxide and oxygen as oxidizing agents were extreamely valuable and attractive. It is increasingly recognized, when polymers are used as supports for catalysts or organic reagents, the reactivity and selectivity of the supported catalysts or reagents may be seriously changed by so-called "polymer effects". As metal catalyzed oxidation of organic substrates with oxygen, we arc planing the incorporation of transition metals into polymer. In oxidaton organic compound has little resistant, so syntheses of organic-inorganic hybrid polymer from silica gel and montmorillonite by the modification with silane coupling reagents and the complexation of transition metal ions into hybrid polymer obtained above were investigated.     

Efficient synthesis of substituted pyrroles through iron-mediated oxidation reaction of 3-methylenehexane-2,5-dione with primary amines

An efficient route has been developed for the synthesis of multiple substituted pyrrole derivatives from the readily available agents through iron-mediated oxidative aromatization process in good to excellent yields. This method is well tolerated with a diverse broad range of substrates and a complementary approach to currently available synthetic methods.     

合成聚丙酰胺-硫属半导体复合纳米材料的新技术

在水溶液体系中采用同步聚合-水解技术（Simultaneous Polymerization-Hydrolysis）制备聚丙烯酰胺-半导体纳米复合材料。该SPH技术是基于丙烯酰胺单体的聚合和MS(M=Cd,Pb,Zn)纳米粒子的形成同步发生,使生成的半导体纳米粒子可均匀分散在聚丙烯酰胺基质中。该技术还为制备其它有机聚合物-金属硫化物纳米复合物提供了一种新途径。     

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3(PTP/WO3)organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction(XRD),transmission electron microscopy(TEM)and thermo-gravimetric analysis(TGA).The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.     

Ligand-mediated formation of Cu/metal oxide hybrid nanocrystals with tunable number of interfaces

Combining domains of different chemical nature within the same hybrid material through the formation of heterojunctions provides the opportunity to exploit the properties of each individual component within the same nano-object; furthermore, new synergistic properties will often arise as a result of unique interface interactions. However, synthetic strategies enabling precise control over the final architecture of multicomponent objects still remain scarce for certain classes of materials. Herein, we report on the formation of Cu/MO_x (M = Ce, Zn and Zr) hybrid nanocrystals with a tunable number of interfaces between the two domains. We demonstrate that the organic ligands employed during the synthesis play a key role in regulating the final configuration. Finally, we show that the synthesized nanocrystals serve as materials platforms to investigate the impact of the Cu/metal oxide interfaces in applications by focusing on the electrochemical CO₂ reduction reaction as one representative example.

We report on the formation of Cu/metal oxide hybrid nanocrystals with a tunable number of interfaces between the two domains. We demonstrate that the organic ligands employed during the synthesis play a key role in regulating the final configuration.     

Growth of (WO3)n rectangular structures through a LMO-organic precursor route

A LMO-organic (LMO = layered metal oxide) hybrid precursor route has been developed to synthesize rectangular (WO3)n structures. In the present work, regular rectangular orthorhombic (WO3)n has been fabricated by a thermal decomposition of the as-synthesized rectangular [WO3(bpy)0.5]n (bpy = 4,4'-bipyridine) precursor, which is formed by a process of intercalation, coordination, and self-assembly using the hydrothermal treatment of (WO3)n and 4,4'-bipyridine. The precursor and final products were characterized by field-emission scanning electron microscopy, transmission electron microscopy, electron-induced X-ray fluorescence analysis, X-ray diffraction analysis, derivative thermogravimetry analysis, and thermogravimetric analysis.     

Improved photocatalytic efficiency of a WO3 system by an efficient visible-light induced hole transfer

Amorphous Cu(II) nanoclusters grafted WO(3) particles were coated on a smooth TiO(2) film, and site selective depositions of PbO(2) and metal Ag particles by photocatalytic processes were observed on TiO(2) and WO(3) due to transfer of holes to TiO(2), and accumulation of electrons in WO(3) respectively. As a result, the photocatalytic activity of TiO(2) modified Cu(II)-WO(3) increased ~3.5 fold higher than that of Cu(II)-WO(3).     

Designing p‐Type Semiconductor–Metal Hybrid Structures for Improved Photocatalysis

A practical strategy is proposed to facilitate the migration of holes in semiconductor (the low rate of which limits photocatalytic efficiency) by taking advantage of the Schottky barrier between p‐type semiconductor and metal. A high work function is found to serve as an important selection rule for building such desirable Schottky junction between semiconductor surface facets and metal. The intrinsic charge spatial distribution has to be taken into account when selecting the facets, as it results in accumulation of photoexcited electrons and holes on certain semiconductor facets. Importantly, the facets have a high work function, the same characteristic required for the formation of Schottky junction in a p‐type semiconductor–metal hybrid structure. As a result, the semiconductor crystals in the hybrid design may be better enclosed by single facets with high work function, so as to synergize the two effects: Schottky barrier versus charge spatial separation.     

钨酸铋担载钯纳米粒子光催化甲苯及其衍生物到醛的氧化反应

甲苯及其衍生物的选择性氧化是化学工业中重要的一环.氧化产物醛、酮和酸类化合物是各种农药、染料、防腐剂、阻燃剂、香料、塑料的合成中间体.在传统的化工过程中,通常在苛刻的条件下,如高温、高压以及酸性溶剂中进行甲苯的选择性氧化.光催化有机合成作为一种"绿色"的合成方法受到越来越多的关注.我们发现钨酸铋作为可见光响应的光催化剂,可以利用氧气作为氧化剂,对甲苯及其衍生物进行催化氧化反应.通过调节水热法合成钨酸铋的酸碱条件,控制其成核生长过程,改变其形貌,发现在pH值为0.49时,得到花状钨酸铋粉末活性最高.X射线衍射、扫描电镜、紫外可见吸收光谱和比表面测定结果发现,花状钨酸铋粉末表现出最佳的甲苯氧化活性很可能是与它最大的比表面积有关系.为了进一步提高催化的活性,我们将助催化剂担载在钨酸铋粉末上,发现Pd的担载量为0.1 wt%时甲苯氧化反应活性最高.将邻、间、对位甲基取代以及对位甲氧基和氯取代的甲苯衍生物进行反应,发现均可高选择性地得到目标产物.在加入电子牺牲剂硝酸银和空穴牺牲剂草酸铵到反应体系后,发现反应被完全禁阻,说明在甲苯氧化反应过程中电子和空穴都起到了相应的作用.通过电化学测试发现,钯作为助催化剂担载在钨酸铋表面后,产生更强的氧化和还原信号,说明其在电子和空穴发生反应的过程中都起到了相应的促进作用.由此推测,在甲苯的氧化反应中,钨酸铋材料表面吸收可见光,产生光生电子和空穴,而钯的担载则促进了电子和空穴进行氧气还原和甲苯氧化的过程.     

Synthesis of multifunctional metal- and metal oxide core@mesoporous silica shell structures by using a wet chemical approach

We demonstrate a facile wet chemical approach for fabricating spherical metal/metal-oxide core@mesoporous silica shell hybrid nanoparticles with different core and shell thicknesses. Vertically aligned mesoporous silica (mSiO(2) ) shells were fabricated over the pre-synthesized spherical SiO(2) nanoparticles through a three-step strategy: 1)?synthesis of core materials, 2)?covering the core with an organic-inorganic composite layer, and 3)?removing the organic template through calcinations in air. The mechanisms of hybrid structure formation are proposed. The multifunctional nature of the hybrid structures could be induced by incorporating guest ions/molecules, such as Ag, Mn, and TiO(2) , into the pores of an mSiO(2) shell. Mn and TiO(2) cluster- incorporated composite structures have been tested to be antioxidizing agents and effective photocatalysts through electron spin resonance, radical scavenging tests, and the photocatalytic degradation of rhodamine B. The possibility of incorporating several hetero-element guest clusters in these mesoporous composite particles makes them highly attractive for multifunctional applications.     

Pd/WO_3-RGO纳米催化剂对甲酸氧化的电催化性能

采用表面修饰技术将WO_3晶粒引入到氧化石墨烯(GO)表面,通过硼氢化钾还原法制备了载钯催化剂Pd/WO_3-RGO.对催化剂进行了结构和形貌表征,并考察了该催化剂对甲酸氧化的电催化性能.结果表明,Pd/WO_3-RGO催化剂由石墨烯、单斜态WO_3和立方面心Pd晶粒组成,Pd颗粒均匀分散在载体上;使用Pd/20%WO_3-RGO催化剂电极时的甲酸氧化最大峰电流密度大幅增加,是Pd/RGO催化剂电极甲酸氧化峰电流密度的2.5倍;Pd/WO_3-RGO催化剂稳定性大大增强,且具有更加优异的抗CO中毒能力;Pd晶粒与WO_3晶粒的相互交叠有利于它们之间的催化协同效应,增强催化剂的催化性能.     

Deactivation of the TiO2 photocatalyst by coupling with WO3 and the electrochemically assisted high photocatalytic activity of WO3

Patterned TiO2 stripes were formed on a sol-gel crystalline WO3 film by using a chemically modified sol-gel method (pat-TiO2/WO3), and the coupling effect on the photocatalytic activity was studied. Although the photoinduced electron transfer from TiO2 to WO3 was confirmed by labeling and visualization of the reduction sites with Ag particles, the photocatalytic activities of TiO2 for both the gas-phase oxidation of CH3CHO and the liquid-phase oxidation of 2-naphthol decreased significantly with the coupling. This finding was rationalized in terms of the decrease in the rate of the electron transfer from the semiconductor-(s) to 02 with the coupling, which was estimated from the kinetic analysis of the photopotential relaxation. When the excited electrons were removed by a SnO2 underlayer, the WO3 film exhibited a high photocatalytic activity exceeding that of TiO2 for the oxidation of 2-naphthol.