Symmetry-breaking synthesis of Janus Au/CeO2 nanostructures for visible-light nitrogen photofixation

Precise manipulation of the reactive site spatial distribution in plasmonic metal/semiconductor photocatalysts is crucial to their photocatalytic performance, but the construction of Janus nanostructures through symmetry-breaking synthesis remains a significant challenge. Here we demonstrate a synthetic strategy for the selective growth of a CeO₂ semi-shell on Au nanospheres (NSs) to fabricate Janus Au NS/CeO₂ nanostructures with the assistance of a SiO₂ hard template and autoredox reaction between Ag⁺ ions and a ceria precursor. The obtained Janus nanostructures possess a spatially separated architecture and exhibit excellent photocatalytic performance toward N₂ photofixation under visible-light illumination. In this scenario, N₂ molecules are reduced by hot electrons on the CeO₂ semi-shell, while hole scavengers are consumed by hot holes on the exposed Au NS surface, greatly promoting the charge carrier separation. Moreover, the exposed Au NS surface in the Janus structures offers an additional opportunity for the fabrication of ternary Janus noble metal/Au NS/CeO₂ nanostructures. This work highlights the genuine superiority of the spatially separated nanoarchitectures in the photocatalytic reaction, offering instructive guidance for the design and construction of novel plasmonic photocatalysts.

We demonstrate a synthetic strategy to selectively grow a CeO₂ semi-shell on Au nanospheres through the symmetry-breaking synthesis. The asymmetric nanostructures facilitate the charge carrier separation during the visible-light N₂ photofixation.     

Controlled synthesis and self-assembly of CeO2 nanocubes

CeO2 nanocubes (and nanorods) enclosed by six {200} planes with controlled sizes have been prepared through a facile one-pot method. The nanocubes have a strong tendency to assemble into 2D and 3D arrays with regular patterns on a substrate, which is probably driven by the dipole-dipole interaction of polar {200} planes. The possible formation mechanism of the nanocubes has been put forward as the oriented aggregation mediated precursor growth. It is possible to use the synthesized nanocubes as building blocks to achieve {200}-perfect-oriented monolayers or thickness-controlled films and to apply the preparative method in the incorporation of heterogeneous atoms or nanoparticles for semiconductor doping or heterogeneous nanostructures.     

Thermal synthesis of the CeO2-PrO2-La2O3 pigments

The synthesis of new compounds based on CeO₂-PrO₂-La₂O₃, which can be used as pigments for colouring of ceramic glazes, is investigated in our laboratory. The optimum conditions for the syntheses of these compounds have been estimated. The first information about the temperature region of the formation of the pigments investigated is provided by thermal analysis. The synthesis of these compounds is followed by thermal analysis using STA 449/C Jupiter (Netzsch, Germany). This revised version was published online in July 2006 with corrections to the Cover Date.     

Facile synthesis of anisotropic Au@SiO2 core-shell nanostructures

Anisotropic Au@SiO(2) core-shell nanostructures have been fabricated from CTABr-stabilized Au nanoparticles with a facile synthesis involving a single growth solution. This procedure circumvents tedious surface modification steps and allows for the SiO(2) shell thickness to be tuned from 5 to 20 nm by modulating the nanoparticle number density and concentration of silica precursor.     

One-pot synthesis of monodisperse CeO2 nanocrystals and superlattices

Monodisperse CeO(2) nanocrystals and superlattice-like colloidal particles have been successfully synthesized in ethanol-water mixed solvent by adopting a one-pot approach using icosahedral (NH(4))(2)Ce(NO(3))(6) as precursor.     

Size-controlled synthesis and electrochemical characterization of spherical CeO2 crystallites

Spherical ceria (CeO(2)) crystallites assembled by nanoparticles were synthesized by hydrothermal treatment of Ce(NO(3))(3)6H(2)O using poly(N-vinyl-2-pyrrolidone) (PVP) as surfactant. It was found that these spheres were developed from the gradual aggregation of small nanoparticles and size of the spheres could be tailored by adjusting the reagent concentrations. Electrochemical tests indicated that thus-prepared CeO(2) spheres exhibited size-dependent discharge capacities and good cyclability in the Li/CeO(2) couple, showing their promising usages as anode materials in the lithium ion battery.     

Hydrothermal synthesis and pseudocapacitance properties of MnO2 nanostructures

The effect of varying the hydrothermal time to synthesize manganese oxide (MnO(2)) nanostructures was investigated along with their influence on structural, morphological, compositional, and electrochemical properties in supercapacitor electrode materials. XRD and TEM studies showed that the MnO(2) prepared in shorter hydrothermal dwell time was a mixture of amorphous and nanocrystalline particles, and there was an evolution of crystallinity of the nanostructures as the dwell time increased from 1 to 18 h. Interestingly, SEM, TEM, and HRTEM revealed a variety of structures ranging from nanostructured surface with a distinct platelike morphology to nanorods depending upon the hydrothermal reaction time employed during the preparation of the manganese oxide: increasing the amount of individual nanorods in the materials prepared with longer hydrothermal reaction time. The surface area of the synthesized nanomaterials varied from 100 to 150 m(2)/g. Electrochemical properties were evaluated using cyclic voltammetry (CV) and galvanostatic charge-discharge studies, and the capacitance values were in the range 72-168 F/g depending upon synthesis conditions. The formation mechanism of the nanorods and their impact on the specific capacitance were discussed in detail.     

Solvent-controlled synthesis and electrochemical lithium storage of one-dimensional TiO2 nanostructures

In this paper, one-dimensional (1-D) nanostructured TiO2 of different morphologies and structures have been selectively synthesized via a convenient, low-temperature solvothermal route and following calcination. Transmission electron microscopy, selected area electron diffraction, X-ray diffraction, and Brunauer-Emmett-Teller methods were used to characterize the morphology, crystalline structure, and specific surface area of these nanostructured TiO2. The formation of different morphologies, including nanowires and nanotubes, was achieved through a deliberate control of the cosolvent. In addition to the solvent-controlled procedures, another important feature of the synthesis in the present study was that either single-crystalline nanowires (TiO2-B) or polycrystalline nanotubes (anatase and TiO2-B) were achieved by heat treatment at 350 degrees C. The electrochemical performances of the nanowires and nanotubes were further explored in terms of their potential application as anode materials for lithium-ion batteries. The lithium-insertion reactions involved in the two materials were elucidated by means of a galvanostatic method, cyclic voltammetry, and electrochemical impedance spectroscopy. The results suggest that both the crystalline structure and the unique 1-D morphology might be responsible for their favorable electrochemical properties. This work will be valuable for the understanding of the formation of nanostructured TiO2 by the wet-chemistry process and further applications.     

Controlled synthesis of 2-D and 3-D dendritic platinum nanostructures

Seeding and autocatalytic reduction of platinum salts in aqueous surfactant solution using ascorbic acid as the reductant leads to remarkable dendritic metal nanostructures. In micellar surfactant solutions, spherical dendritic metal nanostructures are obtained, and the smallest of these nanodendrites resemble assemblies of joined nanoparticles and the nanodendrites are single crystals. With liposomes as the template, dendritic platinum sheets in the form of thin circular disks or solid foamlike nanomaterials can be made. Synthetic control over the morphology of these nanodendrites, nanosheets, and nanostructured foams is realized by using a tin-porphyrin photocatalyst to conveniently and effectively produce a large initial population of catalytic growth centers. The concentration of seed particles determines the ultimate average size and uniformity of these novel two- and three-dimensional platinum nanostructures.     

Benzothiazines in synthesis. Toward the synthesis of pseudopteroxazole

[reaction: see text] The tricyclic benzothiazine 15 was prepared in a straightforward fashion via a completely stereoselective intramolecular Friedel-Crafts alkylation. This compound represents a potential precursor to the antitubercular agent, pseudopteroxazole. Its synthesis proceeded via a completely selective, intramolecular addition of a sulfoximine-stabilized carbanion to an alpha,beta-unsaturated ester, followed by functional group manipulations.     

Controllable synthesis of conducting polypyrrole nanostructures

Wire-, ribbon-, and sphere-like nanostructures of polypyrrole have been synthesized by solution chemistry methods in the presence of various surfactants (anionic, cationic, or nonionic surfactant) with various oxidizing agents [ammonium persulfate (APS) or ferric chloride (FeCl3), respectively]. The surfactants and oxidizing agents used in this study have played a key role in tailoring the nanostructures of polypyrrole during the polymerization. It is inferred that the lamellar structures of a mesophase are formed by self-assembly between the cations of a long chain cationic surfactant [cetyltrimethylammonium bromide (CTAB) or dodeyltrimethylammonium bromide (DTAB)] and anions of oxidizing agent APS. These layered mesostructures are presumed to act as templates for the formation of wire- and ribbon-like polypyrrole nanostructures. In contrast, if a short chain cationic surfactant octyltrimethylammonium bromide (OTAB) or nonionic surfactant poly(ethylene glycol) mono-p-nonylphenyl ether (Opi-10) is used, sphere-like polypyrrole nanostructures are obtained, whichever of the oxidizing agents mentioned above is used. In this case, micelles resulting from self-assembly among surfactant molecules are envisaged to serve as the templates while the polymerization happens. It is also noted that, if anionic surfactant sodium dodeyl surfate (SDS) is used, no characteristic nanostructures of polypyrrole were observed. This may be attributed to the doping effect of anionic surfactants into the resulting polypyrrole chains, and as a result, micelles self-assembled among surfactant molecules are broken down during the polymerization. The effects of monomer concentration, surfactant concentration, and surfactant chain length on the morphologies of the resulting polypyrrole have been investigated in detail. The molecular structures, composition, and electrical properties of the nanostructured polypyrrole have also been investigated in this study.     

A sulfur-tolerant Pd/CeO2 catalyst for methanol synthesis from syngas

The catalytic activity of ceria-supported Pd for selective hydrogenation of CO is well preserved in the presence of 30 ppm H2S due to the parallel oxidation of sulfur by CeO2 under standard methanol synthesis conditions. The bifunctional nature of this catalyst opens a route for the conversion of sulfur-contaminated gas streams such as the integrated gasification combined cycle syngas or biogas into liquid fuels if desulfurization by conventional means is not practical.     

The synthesis of zinc oxide nanostructures

It was proposed to synthesize quasi-one-dimensional nano-sized zinc oxide crystals by the vapor-liquid-crystal mechanism during the gas phase epitaxy. An array of nanowhiskers randomly distributed throughout the polished surface of silicon wafer was grown. The structure and properties of whiskers were determined.     

Large-scale synthesis of single-crystalline perovskite nanostructures

Single-crystalline perovskite nanostructures with reproducible shape have been prepared using a simple, readily scaleable solid-state reaction in the presence of NaCl and a nonionic surfactant. Pristine BaTiO3 nanowires have diameters ranging from 50 to 80 nm with an aspect ratio larger than 25. Single-crystalline SrTiO3 nanocubes with a mean edge length of 80 nm have been produced using a similar procedure.     

Improving the ammonia synthesis activity of Ru/CeO2 through enhancement of the metal-support interaction

The metal-support interactions induced by high-temperature hydrogen reduction have a strong influ-ence on the catalytic performance of ceria-supported Ru cataly...     

Interface-controlled synthesis of CeO2(111) and CeO2(100) and their structural transition on Pt(111)

Ceria-based catalytic materials are known for their crystal-face-dependent catalytic properties. To obtain a molecular-level understanding of their surface chemistry, controlled synthesis of ceria with well-defined surface structures is required. We have thus studied the growth of CeO_x nanostructures (NSs) and thin films on Pt(111). The strong metal-oxide interaction has often been invoked to explain catalytic processes over the Pt/CeO_x catalysts. However, the Pt-CeO_x interaction has not been understood at the atomic level. We show here that the interfacial interaction between Pt and ceria could indeed affect the surface structures of ceria, which could subsequently determine their catalytic chemistry. While ceria on Pt(111) typically exposes the CeO₂(111) surface, we found that the structures of ceria layers with a thickness of three layers or less are highly dynamic and dependent on the annealing temperatures, owing to the electronic interaction between Pt and CeO_x. A two-step kinetically limited growth procedure was used to prepare the ceria film that fully covers the Pt(111) substrate. For a ceria film of ~3–4 monolayer (ML) thickness on Pt(111), annealing in ultrahigh vacuum (UHV) at 1000 K results in a surface of CeO₂ (100), stabilized by a c-Ce₂O₃(100) buffer layer. Further oxidation at 900 K transforms the surface of the CeO₂(100) thin film into a hexagonal CeO₂(111) surface.     

A sulfur-tolerant Pd/CeO2 catalyst for methanol synthesis from syngas

The catalytic activity of cefia-supported Pd for selective hydrogenation of CO is well preserved in the presence of 30 ppm H2S due to the parallel oxidation of sulfur by CeO2 under standard methanol synthesis conditions. The bifunctional nature of this catalyst opens a route for the conversion of sulfur-contaminated gas streams such as the integrated gasification combined cycle syngas or biogas into liquid fuels if desulfurization by conventional means is not practical.     

Surfactant-assisted hydrothermal synthesis of CoMn2O4 nanostructures for efficient supercapacitors

Journal of Solid State Electrochemistry - Mixed transition metal oxides/spinels are excellent energy storage electrode materials that can deliver sizeable specific capacitance, excellent cyclic...     

CeO2/NaNbO3复合物的水热合成及其光催化性能的提高

钙钛矿型NaNbO3由于其非线性光学、铁电、离子导电性、高声速、光催化性能和光折变等优良性能而备受关注. 在光催化反应中, 宽禁带宽度(≈ 3.24 eV)使NaNbO3具有较高的导带底(CBM)和较低的价带顶(VBM). 因此, 它表现出强烈的光氧化和光还原能力. 众所周知, 钙钛矿型光催化剂光电子激发和传输能力的增强归因于其较高的对称性. 因此, 具有高对称性的立方NaNbO3有利于电子激发和转移. 但是, 一些固有的缺点, 包括电荷分离效率低、量子产率差和光催化活性差等, 限制了其在光催化领域的实际应用. 为了解决这些问题, 一种有效的方法是与其他半导体结合, 形成具有改善光催化活性的异质结复合物. CeO2作为传统的催化剂在光催化领域得到了广泛研究. CeO2具有稳定、无毒的特点, 是一种n型半导体. 目前, 研究人员已经发现CeO2与不同半导体的耦合可以提高CeO2的光催化活性. 这归因于能级水平的适当匹配.本文通过简易水热法制备了高活性的CeO2/NaNbO3异质结复合物, 并采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM, HRTEM)和紫外-可见漫反射光谱(DRS)等表征技术研究了所制光催化剂的物相结构、样品形貌和光学性能. 所制样品的光催化活性通过光催化降解无色抗菌环丙沙星(CIP)和染料罗丹明B(RhB)证实. 结果表明,在紫外和可见光照射, CeO2/NaNbO3复合物比纯NaNbO3具有更高的光催化活性. 此外, CeO2/NaNbO3复合物中CeO2的最佳质量比为2.0 wt%. 紫外光照射下光催化性能的显著提高是由于CeO2/NaNbO3异质结的形成不仅提高了光生电荷在界面范围内的迁移速率, 而且降低了光激发产生的电子和空穴的复合率. 可见光照射下内置电场的存在促进了电子和空穴的分离, 提高了光催化性能. 此外, 利用光致发光(PL)光谱、光电流、电化学阻抗谱和捕获实验证明了样品的光催化反应机理.捕获实验结果表明, ·OH自由基、·O2-自由基和空穴都参与了RhB的光催化降解过程. 最后, 探讨了提高光催化活性的可能机理.