Morphology of gold nanoparticles synthesized by filamentous cyanobacteria from gold(I)-thiosulfate and gold(III)--chloride complexes

Plectonema boryanum UTEX 485, a filamentous cyanobacterium, has been reacted with aqueous Au(S(2)O(3))(2)(3)(-) and AuCl(4)(-) solutions ( approximately 400-550 mg/L Au) at 25-100 degrees C for up to 1 month and at 200 degrees C for 1 day. The interaction of cyanobacteria with aqueous Au(S(2)O(3))(2)(3)(-) promoted the precipitation of cubic (100) gold nanoparticles (<10-25 nm) at membrane vesicles and admixed with gold sulfide within cells and encrusted on the cyanobacteria, whereas reaction with AuCl(4)(-) resulted in the precipitation of octahedral (111) gold platelets ( approximately 1-10 microm) in solutions and nanoparticles of gold (<10 nm) within bacterial cells. Functional groups imaged by negative ion TOF-SIMS on (111) faces of the octahedral platelets were predominantly Cl and CN, with smaller amounts of C(2)H and CNO.     

Shape evolution and size-controllable synthesis of Cu2O octahedra and their morphology-dependent photocatalytic properties

Octahedral Cu(2)O crystals with tunable edge length were synthesized by reducing copper hydroxide with hydrazine without using any surfactant. Systematic experiments were carried out to investigate the factors which impact on the morphology and size of the products. The molar ratios of the reagents (NH(3):Cu(2+) and OH(-):Cu(2+)) determined the morphology and size of the corresponding products via affecting the coordination between NH(3) and Cu(2+). It is demonstrated that the ratio of growth rate along 111 versus 100 was varied by adjusting the molar ratio of NH(3) to Cu(2+), thus Cu(2)O crystals with different morphologies such as spheres, cubelike, and octahedra were obtained. The edge lengths of octahedra can be easily tuned from 130 to 600 nm by adjusting the molar ratio of OH(-) to Cu(2+). It is an effective and facile method for the controlled synthesis of octahedral Cu(2)O. The obtained octahedral Cu(2)O particles show improved ability on adsorption and photodegradation of methyl orange compared with cubic Cu(2)O particles.     

Water-gas-shift reaction on metal nanoparticles and surfaces

Density functional theory was employed to investigate the water-gas-shift reaction (WGS, CO+H2O-->H2+CO2) on Au29 and Cu29 nanoparticles seen with scanning tunneling microscopy in model AuCeO2(111) and CuCeO2(111) catalysts. Au(100) and Cu(100) surfaces were also included for comparison. According to the calculations of the authors, the WGS on these systems operate via either redox or associative carboxyl mechanism, while the rate-limiting step is the same, water dissociation. The WGS activity decreases in a sequence: Cu29>Cu(100)>Au29>Au(100), which agrees well with the experimental observations. Both nanoparticles are more active than their parent bulk surfaces. The nanoscale promotion on the WGS activity is associated with the low-coordinated corner and the edge sites as well as the fluxionality of the particles, which makes the nanoparticles more active than the flat surfaces for breaking the O-H bond. In addition, the role of the oxide support during the WGS was addressed by comparing the activity seen in the calculations of the authors for the Au29 and Cu29 nanoparticles and activity reported for XCeO2(111) and XZnO(000i)(X=Cu or Au) surfaces.     

Shape evolution of Cu2O nanostructures via kinetic and thermodynamic controlled growth

We report the shape evolution process of Cu(2)O nanocrystals upon slow oxidation of Cu under ambient conditions, yielding novel hexagonal and triangular platelike morphologies. The shape of the obtained nanocrystals evolves from hexagonal to triangular to octahedral; the growth patterns are governed by kinetically and thermodynamically controlled growth. Preferential adsorption of I(-) on {111} planes of Cu(2)O nanoparticles induced the selective crystal growth of metastable platelike structures with {111} faces as the basal planes. On aging, the growth process appeared to shift into the thermodynamic regime and the thermodynamically stable octahedral shape is obtained. The possible growth mechanisms were investigated by varying the synthetic conditions. The band gap of Cu(2)O nanooctahedrons was determined by the classical Tauc approach to be 2.24 eV, which is blue shifted with respect to the bulk Cu(2)O value (2.17 eV). Results suggest that the slow oxidation process and use of crystallographic selective surfactants are essential for the appearance of anisotropic metastable shapes. In general, surface energy control by surfactant molecules might provide a convenient channel for tailoring nanocrystal shapes of metal oxides.     

Morphological evolution of Cu2O nanocrystals in an acid solution: stability of different crystal planes

The morphological evolution of uniform Cu(2)O nanocrystals with different morphologies in a weak acetic acid solution (pH = 3.5) has been studied for cubic, octahedral, rhombic dodecahedral, {100} truncated octahedral, and {110} truncated octahedral nanocrystals. Cu(2)O nanocrystals undergo oxidative dissolution in weak acid solution, but their morphological changes depend on the exposed crystal planes. We found that the stability of Cu(2)O crystal planes in weak acid solution follows the order of {100} ? {111} > {110} and determines how the morphology of Cu(2)O nanocrystals evolves. The stable {100} crystal planes remain, and new {100} facets form at the expense of the less stable {111} and {110} crystal planes on the surface of Cu(2)O nanocrystals. Density functional theory calculations reveal that the Cu-O bond on Cu(2)O(100) surface has the shortest bond length. These results clearly exemplify that the morphology of inorganic crystals will evolve with the change of local chemical environment, shedding light on fundamentally understanding the morphological evolution of natural minerals and providing novel insights into the geomimetic synthesis of inorganic materials in the laboratory.     

在光催化还原CO2中具有高催化效率的八面体Cu2O修饰的TiO2纳米管

光催化还原CO2生成烃类燃料是一种可同时解决全球变暖和能源危机问题的最有效途径之一。尽管这方面的研究已经取得了一定的进展,但是整体的光催化转换效率还非常低。因此,需要发展更加高效的催化剂。由于半导体材料禁带宽度与太阳光谱相匹配,人们已经对其进行了广泛研究。其中TiO2因具有无毒、强氧化性以及良好的光学和电学性质等而成为最主要的研究对象。但是对于光催化还原CO2反应来说, TiO2仍存在很多不足,如只能吸收太阳光谱中的紫外光,光生载流子会快速结合,以及光生空穴的强氧化能力等,这些都限制了其光催化还原CO2的效率。采用窄禁带宽度半导体修饰TiO2是解决上述不足的有效途径之一。本文采用简单的电化学方法成功制备了一种由窄禁带半导体Cu2O修饰的TiO2纳米管(TNTs)的复合物,并运用扫描电子显微镜(SEM)、X射线衍射(XRD)以及X射线光电子能谱(XPS)表征了所制备复合物的形貌、化学组成和结晶度。表征结果显示,所制备的TiO2为整齐排列的纳米管阵列结构;复合物中的纳米颗粒为Cu2O;当电化学沉积Cu2O的时间为5 min时,得到的Cu2O纳米颗粒初步呈类八面体结构。随着沉积时间的增加, Cu2O颗粒尺寸增加,具有八面体结构。 XRD和XPS结果表明, TiO2纳米管为锐钛矿,八面体Cu2O纳米颗粒的主要暴露晶面为(111)面。我们还进一步研究了不同量Cu2O纳米颗粒修饰的TiO2纳米管复合物在可见光以及模拟太阳光下光催化还原CO2的能力。在可见光下,由于自身的禁带宽度,纯净的TiO2纳米管没有任何光催化还原CO2的能力;经过Cu2O纳米颗粒的修饰,复合物显现出明显的光催化还原CO2的能力,其中经过30 min Cu2O沉积的TNTs具有最高的光催化效率。在模拟太阳光下,经过15 min Cu2O沉积的TNTs具有最高的光催化效率。在所有光催化还原CO2过程中,主要碳氢产物为甲烷。为了深入地理解该复合体系在还原CO2中的高催化效率,我们对催化剂进行了进一步的表征。紫外-可见漫反射光谱表明, Cu2O八面体纳米颗粒的沉积将TNTs的吸收光谱拓展到了可见光区域,提高了复合物对太阳光的吸收能力。此外,我们还通过测试所制样品的光电流反应、荧光发射光谱以及电化学阻抗谱,研究了催化剂中光生电子和空穴的分离和迁移能力。结果表明,适量的Cu2O沉积提高了复合物对光的吸收能力,增加了光生载流子的数量,从而使更多的光生载流子参与光催化反应。综上,本文首次报道了八面体Cu2O纳米颗粒修饰TNTs复合物的光催化还原CO2的能力。在一定量的Cu2O纳米颗粒修饰下,该复合物在光催化还原CO2生成烃类反应中表现出高效性。经过一系列详细的表征和讨论,我们认为其高效性主要源于三个方面：(1) TNTs的管状结构为反应物的吸附提供了大量的活性位点,同时一维的管状结构更有利于光生载流子的运载,从而提高了电子和空穴的分离;(2) Cu2O纳米颗粒的修饰提高了催化剂对光的吸收,促进催化剂最大程度地利用太阳光;(3) TiO2和Cu2O之间导带以及价带位置的匹配,在减少光生载流子复合的同时也降低了TiO2价带上空穴的氧化能力,从而抑制了CO2还原产物的再氧化过程。     

Cu2O/Ag纳米复合物的表面增强拉曼光谱

用一种简单的化学还原方法制备了银纳米粒子包覆的氧化亚铜（Cu2O）纳米复合物。扫描电子显微镜显示Cu2O 为八面体型的纳米粒子,表面光滑,结构对称。包覆的Ag部分占据Cu2O粒子表面。通过比较Ag/Cu2O纳米复合物、Ag溶胶及Cu纳米粒子表面吸附的4-巯基吡啶（4-Mpy）分子表面增强拉曼光谱（SERS）发现,利用此方法得到了Cu2O粒子表面吸附分子的拉曼光谱。银纳米粒子所产生的电磁场增强又增强了吸附在Cu2O上的4-Mpy拉曼信号。这种方法为初步研究Cu2O表面吸附分子性质提供了依据,扩宽了SERS的使用范围,使SERS应用在纳米半导体材料上成为可能。     

Reusable Cu2O/PPh3/TBAB system for the cross-couplings of aryl halides and heteroaryl halides with terminal alkynes

An efficient and reusable Cu2O/PPh3/TBAB (n-Bu4NBr) system for the cross-coupling reactions of aryl and heteroaryl halides with terminal alkynes has been developed. Four types of Cu2O, including bulky Cu2O, cubic Cu2O nanoparticles, octahedral Cu2O nanoparticles, and spherical Cu2O nanoparticles, were examined, and the octahedral Cu2O nanoparticles were found to be the most effective catalyst for the reaction. In the presence of the octahedral Cu2O nanoparticles, PPh3, and TBAB, a variety of aryl and heteroaryl halides were reacted with alkynes including alkynols smoothly in moderate to good yields. Noteworthy is that the Cu2O/PPh3/TBAB system can be recovered and reused several times without loss of any activities.     

Thermodynamic, electronic and structural properties of Cu/CeO2 surfaces and interfaces from first-principles DFT+U calculations

The thermodynamic, structural and electronic properties of Cu-CeO(2) (ceria) surfaces and interfaces are investigated by means of density functional theory (DFT+U) calculations. We focus on model systems consisting of Cu atoms (i) supported by stoichiometric and reduced CeO(2) (111) surfaces, (ii) dispersed as substitutional solid solution at the same surface, as well as on (iii) the extended Cu(111)/CeO(2)(111) interface. Extensive charge reorganization at the metal-oxide contact is predicted for ceria-supported Cu adatoms and nanoparticles, leading to Cu oxidation, ceria reduction, and interfacial Ce(3+) ions. The calculated thermodynamics predict that Cu adatoms on stoichiometric surfaces are more stable than on O vacancies of reduced surfaces at all temperatures and pressures relevant for catalytic applications, even in extremely reducing chemical environments. This suggests that supported Cu nanoparticles do not nucleate at surface O vacancies of the oxide, at variance with many other metal/ceria systems. In oxidizing conditions, the solid solutions are shown to be more stable than the supported systems. Substitutional Cu ions form characteristic CuO(4) units. These promote an easy and reversible O release without the reduction of Ce ions. The study of the extended CeO(2)(111)/Cu(111) interface predicts the full reduction of the interfacial ceria trilayer. Cu nanoparticles supported by ceria are proposed to lie above a subsurface layer of Ce(3+) ions that extends up to the perimeter of the metal-oxide interface.     

Electrocatalytic and magnetic properties of ultrathin nanostructured iron-melanin films on Au(111)

We have prepared ultrathin, nanostructured melanin films on Au(111) by means of electrochemical self-assembly. These films were characterized by using Auger electron spectroscopy, X-ray absorption near-edge structure spectroscopy, scanning tunneling microscopy, magnetic force microscopy, and electrochemical techniques. Two types of nanostructures are present in the film: melanin nanoparticles and Fe(3)O(4) nanoparticles. The melanin nanoparticles contain Fe bonded to oxygen-containing phenolic groups in an octahedral configuration similar to that found in Fe(2)O(3). The inorganic-organic composite exhibits magnetic properties and catalyzes the electroreduction of hydrogen peroxide in alkaline and neutral electrolyte solutions. The electrocatalytic activity depends on the Fe-bound melanin and appears to be similar to that found for Fe-porphyrins.     

单原子分散的Au/Cu(111)表面合金的表面结构与吸附性质

Au-Cu双金属合金纳米颗粒对包括CO氧化和CO2还原等在内的多个反应有较好的催化活性,然而关于其表面性质的研究却相当匮乏。在此工作中,我们通过对低覆盖度的Au/Cu(111)和Cu/Au(111)双金属薄膜退火,制备出了单原子级分散的Au/Cu(111)和Cu/Au(111)合金化表面,并利用高分辨扫描隧道显微镜(STM)和扫描隧道谱(STS)进一步研究了掺杂原子的电子性质及其对CO吸附行为的影响。研究发现,分散在Cu(111)表面的表层和次表层Au单原子在STM上表现出不同衬度。在-0.5 e V附近,前者表现出相较于Cu(111)明显增强的电子态密度,而后者则明显减弱。吸附实验表明表层Au单原子对CO的吸附能力并没有得到增强,甚至会减弱其周围Cu原子的吸附能力。与Au在Cu(111)表面较好的分散相反,Cu原子倾向于钻入Au(111)的次表层,并且形成多原子聚集体。且Cu原子受Au(111)衬底吸电子作用的影响,其对CO的吸附能力明显减弱。这个研究结果揭示了合金表面的微观结构与性质的关联,为进一步阐明Au-Cu双金属催化剂的表面反应机理提供参考。     

CO oxidation on inverse CeO(x)/Cu(111) catalysts: high catalytic activity and ceria-promoted dissociation of O2

A Cu(111) surface displays a low activity for the oxidation of carbon monoxide (2CO + O(2) → 2CO(2)). Depending on the temperature, background pressure of O(2), and the exposure time, one can get chemisorbed O on Cu(111) or a layer of Cu(2)O that may be deficient in oxygen. The addition of ceria nanoparticles (NPs) to Cu(111) substantially enhances interactions with the O(2) molecule and facilitates the oxidation of the copper substrate. In images of scanning tunneling microscopy, ceria NPs exhibit two overlapping honeycomb-type moire? structures, with the larger ones (H(1)) having a periodicity of 4.2 nm and the smaller ones (H(2)) having a periodicity of 1.20 nm. After annealing CeO(2)/Cu(111) in O(2) at elevated temperatures (600-700 K), a new phase of a Cu(2)O(1+x) surface oxide appears and propagates from the ceria NPs. The ceria is not only active for O(2) dissociation, but provides a much faster channel for oxidation than the step edges of Cu(111). Exposure to CO at 550-750 K led to a partial reduction of the ceria NPs and the removal of the copper oxide layer. The CeO(x)/Cu(111) systems have activities for the 2CO + O(2) → 2CO(2) reaction that are comparable or larger than those reported for surfaces of expensive noble metals such as Rh(111), Pd(110), and Pt(100). Density-functional calculations show that the supported ceria NPs are able to catalyze the oxidation of CO due to their special electronic and chemical properties. The configuration of the inverse oxide/metal catalyst opens new interesting routes for applications in catalysis.     

Reaction of SO2 with AuCeO2(111): importance of O vacancies in the activation of gold

Synchrotron-based high-resolution photoemission was used to study the adsorption and chemistry of SO(2) on AuCeO(2)(111) and AuO(x)CeO(2) surfaces. The heat of adsorption of the molecule on Au nanoparticles supported on stoichiometric CeO(2)(111) was 4-7 kcalmol larger than on Au(111). However, there was negligible dissociation of SO(2) on the AuCeO(2)(111) surfaces. The full decomposition of SO(2) was observed only after introducing O vacancies in the ceria support. AuO(x)CeO(2) surfaces were found to be much less chemically active than AuCeO(2)(111) or AuCeO(2-x)(111) surfaces. The active sites in {Au + AuO(x)}ceria catalysts should involve pure gold nanoparticles in contact with O vacancies.     

Elucidating the effect of additives on the growth and stability of Cu2O surfaces via shape transformation of pre-grown crystals

A new strategy of using pre-grown crystals to study preferential adsorption of various additives is demonstrated for the electrocrystallization of Cu2O. In this method, micron-size Cu2O crystals with well-defined cubic and octahedral shapes were first electrochemically grown, and their crystallization was resumed in a medium containing the additive to be investigated (e.g., Na+, NH4+, SO42-, Cl-, dodecyl sulfate). This method makes it possible to systematically study the interaction of additives with specific planes (e.g., {100} of a cube and {111} of an octahedron) already present. By observing shape transformation over time, the relative stabilities of {100}, {111}, and {110} planes of Cu2O in various growth media could be determined. During this study, a general scheme of forming new crystal shapes containing crystallographic planes that cannot be directly stabilized by preferential adsorption alone was also established (i.e., rhombicuboctahedral shape of Cu2O containing {110} planes). This method can be extended to other crystal systems, which will enable us to classify common features of additives (e.g., charges, type of atoms) and crystallographic planes (e.g., atomic arrangement, surface termination, surface charge) required to allow for strong preferential adsorption.     

Static investigation of adsorption and hetero‐diffusion of copper,silver, and gold adatoms on the (111) surface

In this work, we have used the static molecular simulations combined with an interatomic potential derived from the embedded‐atom method to study the adsorption and hetero‐diffusion on the (111) surface of Cu, Ag, and Au adatoms by using LAMMPS code. The investigation is performed for six heterogeneous systems such as Ag/Au(111), Ag/Cu(111), Au/Ag(111), Au/Cu(111), Cu/Ag(111), and Cu/Au(111). First, we have investigated the relaxation trends and the bond lengths of the atoms in the systems. The calculation results show that, the top layer spacing between the first and second layers of the Au(111), Ag(111), and Cu(111) substrates is contracted. This contraction is found to be more important in the Au(111) substrate. On the other hand, the strong reduction of the binding length is found in Au/Cu(111) for the different adsorption sites. In addition, the binding, adsorption, and static activation energies for all studied systems were examined. The results indicated that the binding and adsorption energies reached their maximum values in the Au/Cu(111) and Au/Ag(111) systems, respectively. Moreover, the static activation barriers for hopping diffusion on the (111) surfaces are found to be low compared with those found in the (100) and (110) surfaces. Therefore, our calculations showed that the difference in energy between the hcp and fcc sites on the (111) surfaces is very small. Copyright © 2017 John Wiley & Sons, Ltd.     

Studies of the optical band positions and EPR g factors for Cu(H2O)6(2+) centers in Tutton salt crystals

The optical band positions and EPR g factors g(i) (i = x, y, z) of Cu(H(2)O)(6)(2+) clusters in pure Tutton salts M(2)Cu(SO(4))(2)·6H(2)O (M = NH(4), Rb) are calculated from the complete diagonalization (of energy matrix) method based on the cluster approach. In the calculation, the superposition model with the structural data is used to obtain the crystal-field parameters. The calculated results are in reasonable agreement with the experimental values, suggesting that the complete diagonalization method and superposition model are effective in the studies of optical and EPR data. The g factors g(i) of Cu(H(2)O)(6)(2+) clusters in Cu(2+)-doped isomorphous diamagnetic Tutton salts M(2)Zn(SO(4))(2)·6H(2)O are also studied from the same method. It is found that the approximately tetragonally compressed Zn(H(2)O)(6)(2+) octahedra in the host crystals change to the approximately tetragonally elongated Cu(H(2)O)(6)(2+) octahedra in the impurity centers. The causes concerning the Jahn-Teller effect are discussed. It appears that in some cases the octahedral environment of an impurity M(I) in crystals differs from that of the replaced host ion, but is close to the one in the isomorphous pure crystals where M(I) is the host ion rather than the impurity ion.     

Sonochemical Preparation of Micro-and Nanometer Cu2O

Cu2O particles with different morphologies and scales were prepared sonochemically on the solid-liquid interface of CuCl and water, by adjusting the reaction factors. The products were characterized by powder X-ray diffraction(XRD) and scanning electron microscopy(SEM). The formation and morphology of Cu2O crystals were influenced by high-intensity ultrasound,reaction temperature,and addition of CuCl.The results indicate that micrometer Cu2O was crystallized in cubic and octahedral shapes, whereas, nanometer Cu2O was not produced in well-shaped crystals.     

Sonochemical Preparation of Micro- and Nanometer Cu2O

Cu2O particles with different morphologies and scales were prepared sonochemically on the solid-liquid interface of CuCl and water, by adjusting the reaction factors. The products were characterized by powder X-ray diffraction（XRD） and scanning electron microscopy（SEM）. The formation and morphology of Cu2O crystals were influenced by high-intensity ultrasound, reaction temperature, and addition of CuCl. The results indicate that micrometer Cu2O was crystallized in cubic and octahedral shapes, whereas, nanometer Cu2O was not produced in well-shaped crystals.     

Synthesis of TiO2 nanoparticles on the Au(111) surface

The growth of titanium oxide nanoparticles on reconstructed Au(111) was investigated by scanning tunneling microscopy and x-ray photoelectron spectroscopy. Ti was deposited by physical-vapor deposition at 300 K. Regular arrays of titanium nanoparticles form by preferential nucleation of Ti at the elbow sites of the herringbone reconstruction. The titanium oxide nanoclusters were synthesized by subsequent exposure to O(2) at 300 K. Two-and three-dimensional titanium oxide nanocrystallites form during annealing in the temperature range from 600 to 900 K. At the same time, the Au(111) surface assumes a serrated 110-oriented step-edge morphology suggesting step-edge pinning by titanium oxide nanoparticles. The oxidation state of the titanium oxide nanoparticles varies with annealing temperature. Specifically, annealing to 900 K results in the formation of stoichiometric TiO(2) nanocrystals as judged by the Ti(2p) binding energies measured in the x-ray photoelectron data. The nanodispersed TiO(2) on Au(111) is an ideal system to test the various models proposed for the enhanced catalytic reactivity of supported Au nanoparticles.     

Plasmon-enhanced photocatalytic properties of cu(2)o nanowire-au nanoparticle assemblies

Cu(2)O-Au nanocomposites (NCs) with tunable coverage of Au were prepared by a facile method of mixing gold nanoparticles (Au NPs) with copper(I) oxide nanowires (Cu(2)O NWs) in various ratios. These Cu(2)O-Au NCs display tunable optical properties, and their photocatalytic properties were dependent on the coverage density of Au NPs. The photocatalytic activity of Cu(2)O-Au NCs was examined by photodegradation of methylene blue. The presence of Au NPs enhanced the photodegradation efficiency of Cu(2)O NCs. The photocatalytic efficiency of Cu(2)O-Au NCs initially increased with the increasing coverage density of Au NPs and then decreased as the surface of Cu(2)O became densely covered by Au NPs. The enhanced photocatalytic efficiency was ascribed to enhanced light absorption (by the surface plasmon resonance) and the electron sink effect of the Au NPs.