CO oxidation on nanostructured SnO(x)/Pt(111) surfaces: unique properties of reduced SnO(x)

We have investigated surface CO oxidation on "inverse catalysts" composed of SnO(x) nanostructures supported on Pt(111) using X-ray photoelectron spectroscopy (XPS), low-energy ion scattering spectroscopy (LEISS) and temperature-programmed desorption (TPD). Nanostructures of SnO(x) were prepared by depositing Sn on Pt(111) pre-covered by NO(2) layers at low temperatures. XPS data show that the SnO(x) nanoparticles are highly reduced with Sn(II)O being the dominant oxide species, but the relative concentration of Sn(II) in the SnO(x) nanoparticles decreases with increasing Sn coverage. We find that the most active SnO(x)/Pt(111) surface for CO oxidation has smallest SnO(x) coverage. Increasing the surface coverage of SnO(x) reduces CO oxidation activity and eventually suppresses it altogether. The study suggests that reduced Sn(II)O, rather than Sn(IV)O(2), is responsible for surface CO oxidation. The occurrence of a non-CO oxidation reaction path involving reduced Sn(II)O species at higher SnO(x) coverages accounts for the decreased CO oxidation activity. From these results, we conclude that the efficacy of CO oxidation is strongly dependent on the availability of reduced tin oxide sites at the Pt-SnO(x) interface, as well as unique chemical properties of the SnO(x) nanoparticles.     

Synthesis of palladium nanoparticles by sonochemical reduction of palladium(II) nitrate in aqueous solution

The sonochemical synthesis of stable palladium nanoparticles has been achieved by ultrasonic irradiation of palladium(II) nitrate solution. The starting solutions were prepared by the addition of different concentrations of palladium(II) nitrate in ethylene glycol and poly(vinylpyrrolidone) (PVP). The resulting mixtures were irradiated with ultrasonic 50 kHz waves in a glass vessel for 180 min. The UV-visible absorption spectroscopy and pH measurements revealed that the reduction of Pd(II) to metallic Pd has been successfully achieved and that the obtained suspensions have a long shelf life. The protective effect of PVP was studied using Fourier transform infrared (FT-IR) spectroscopy. It has been found that, in the presence of ethylene glycol, the stabilization of the nanoparticles results from the adsorption of the PVP chain on the palladium particle surface via the coordination of the PVP carbonyl group to the palladium atoms. The effect of the initial Pd(II) concentration on the Pd nanoparticle morphology has been investigated by transmission electron microscopy. It has been shown that the increase of the Pd(II)/PVP molar ratio from 0.13 x 10(-3) to 0.53 x 10(-3) decreases the number of palladium nanoparticles with a slight increase in particle size. For the highest Pd(II)/PVP value, 0.53 x 10(-3), the reduction reaction leads to the unexpected smallest nanoparticles in the form of aggregates.     

Revealing the mechanisms behind SnO2 nanoparticle formation and growth during hydrothermal synthesis: an in situ total scattering study

The formation and growth mechanisms in the hydrothermal synthesis of SnO(2) nanoparticles from aqueous solutions of SnCl(4)·5H(2)O have been elucidated by means of in situ X-ray total scattering (PDF) measurements. The analysis of the data reveals that when the tin(IV) chloride precursor is dissolved, chloride ions and water coordinate octahedrally to tin(IV), forming aquachlorotin(IV) complexes of the form [SnCl(x)(H(2)O)(6-x)]((4-x)+) as well as hexaaquatin(IV) complexes [Sn(H(2)O)(6-y)(OH)(y)]((4-y)+). Upon heating, ellipsoidal SnO(2) nanoparticles are formed uniquely from hexaaquatin(IV). The nanoparticle size and morphology (aspect ratio) are dependent on both the reaction temperature and the precursor concentration, and particles as small as ~2 nm can be synthesized. Analysis of the growth curves shows that Ostwald ripening only takes place above 200 °C, and in general the growth is limited by diffusion of precursor species to the growing particle. The c-parameter in the tetragonal lattice is observed to expand up to 0.5% for particle sizes down to 2-3 nm as compared to the bulk value. SnO(2) nanoparticles below 3-4 nm do not form in the bulk rutile structure, but as an orthorhombic structural modification, which previously has only been reported at pressures above 5 GPa. Thus, adjustment of the synthesis temperature and precursor concentration not only allows control over nanoparticle size and morphology but also the structure.     

Effects of the SO4 groups on the textural properties and local order deformation of SnO2 rutile structure

Sulfated tin oxide was synthesized from a hydroxylated tin oxide obtained by the precipitation method, followed by ion exchange of OH groups by SO4 species with a sulfuric acid solution. The samples were characterized by X-ray diffraction, transmission electron microscopy, thermoanalysis, and nitrogen physisorption by the Brunauer-Emmett-Teller method. The rutile crystalline structure was refined by the Rietveld method. Thermal analysis suggests the following stoichiometric formulas: SnO2-x(OH)2x and SnO2-x(OH)x(HSO4)x with X = 0.35 and 0.17 for non-sulfated and sulfated samples, respectively. The SO4 species remained strongly bonded at the SnO2 surface stabilizing its crystallite size against sintering, inhibiting the crystallite aggregation, and it acts as a structure porogen director mediating nanoparticle growth and assembly yielding a mesostructure form of SnO2 with wormhole morphology and high thermal stability. The interaction between SO4(2-) and the SnO2 surface changes the symmetry of the representative tin-oxygen octahedron. It relaxes the four tin-oxygen bond lengths located at the basal plane of the octahedron while the two apical Sn-O bonds decrease, producing a strong deformed octahedron, which could be transformed into a higher asymmetry in the electronic distribution around the Sn4+ nuclei. The elimination of SO4 groups brings about the coalescence and crystallite growth, which collapse the mesostructure form of SnO2, decreasing the surface area and porosity.     

Tin oxide dependence of the CO2 reduction efficiency on tin electrodes and enhanced activity for tin/tin oxide thin-film catalysts

The importance of tin oxide (SnO(x)) to the efficiency of CO(2) reduction on Sn was evaluated by comparing the activity of Sn electrodes that had been subjected to different pre-electrolysis treatments. In aqueous NaHCO(3) solution saturated with CO(2), a Sn electrode with a native SnO(x) layer exhibited potential-dependent CO(2) reduction activity consistent with previously reported activity. In contrast, an electrode etched to expose fresh Sn(0) surface exhibited higher overall current densities but almost exclusive H(2) evolution over the entire 0.5 V range of potentials examined. Subsequently, a thin-film catalyst was prepared by simultaneous electrodeposition of Sn(0) and SnO(x) on a Ti electrode. This catalyst exhibited up to 8-fold higher partial current density and 4-fold higher faradaic efficiency for CO(2) reduction than a Sn electrode with a native SnO(x) layer. Our results implicate the participation of SnO(x) in the CO(2) reduction pathway on Sn electrodes and suggest that metal/metal oxide composite materials are promising catalysts for sustainable fuel synthesis.     

Photoassisted tuning of silicon nanocrystal photoluminescence

Silicon is a rather inefficient light emitter due to the indirect band gap electronic structure, requiring a phonon to balance the electron momentum during the interband transition. Fortunately, momentum requirements are relaxed in the 1-5 nm diameter Si crystals as a result of quantum confinement effects, and bright photoluminescence (PL) in the UV-vis range is achieved. Photoluminescent Si nanocrystals along with the C- and SiC-based nanoparticles are considered bioinert and may lead to the development of biocompatible and smaller probes than the well-known metal chalcogenide-based quantum dots. Published Si nanocrystal production procedures typically do not allow for the fine control of the particle size. An accepted way to make the H-terminated Si nanocrystals consists of anodic Si wafer etching with the subsequent breakup of the porous film in an ultrasound bath. Resulting H-termination provides a useful platform for further chemical derivatization and conjugation to biomolecules. However, a rather polydisperse mixture is produced following the ultrasonic treatment, leading to the distributed band gap energies and the extent of surface passivation. From the technological point of view, a homogeneous nanoparticle size mixture is highly desirable. In this study, we offer an efficient way to reduce the H-terminated Si nanocrystal diameter and narrow size distribution through photocatalyzed dissolution in a HF/HNO3 acid mixture. Si particles were produced using the lateral etching of a Si wafer in a HF/EtOH/H2O bath followed by sonication in deaerated methanol. Initial suspensions exhibited broad photoluminescence in the red spectral region. Photoassisted etching was carried out by adding the HF/HNO3 acid mixture to the suspension and exposing it to a 340 nm light. Photoluminescence and absorbance spectra, measured during dissolution, show the gradual particle size decrease as confirmed by the photoluminescence blue shift. The simultaneous narrowing of the photoluminescence spectral bandwidth suggests that the dissolution rate varies with the particle size. We show that the Si nanoparticle dissolution rate depends on the amount of light adsorbed by the particle and accounts for the etching rate variation with the particle size. Significant improvement in the PL quantum yield is observed during the acid treatment, suggesting improvement in the dangling bond passivation.     

Cross-linked polynorbornene-coated gold nanoparticles: dependence of particle stability on cross-linking position and cross-linker structure

This paper describes the preparation of cross-linked polynorbornene coated gold nanoparticles. The polymer was grown radially from the particle surface using a ring opening metathesis polymerization of norbornene and an electrophilic norbornene ester, which was cross-linked using a variety of diamines. The stability of the cross-linked nanoparticles toward oxidative etching by cyanide was evaluated. The rate of etching decreases as diamines with fewer degrees of conformational freedom are used as cross-linkers. The distance of the cross-linking block from the nanoparticle surface was systematically varied. Nanoparticles with the cross-linked block furthest from the surface were etched most slowly. This is suggested to arise as a result of the polymers adopting a mushroom conformation when the cross-linking block is close to the particle surface, while more distal cross-linking results in more rigid polymer chains that are less permeable to the cyanide etchant. These results provide new insight into how fine-tuning the polymer cross-linking architecture can modulate nanoparticle stability.     

Poly(ethyleneimine) as reducing and stabilizing agent for the formation of gold nanoparticles in w/o microemulsions

This paper is focused on the use of branched poly(ethyleneimine) (PEI) as reducing as well as stabilizing agent for the formation of gold nanoparticles in different media. The process of nanoparticle formation was investigated, in the absence of any other reducing agents, in microemulsion template phase in comparison to the nucleation process in aqueous polymer solution.

On the one hand, it was shown that the polyelectrolyte can be used for the controlled single-step synthesis and stabilization of gold nanoparticles via a nucleation reaction and particles with an average diameter of 7.1 nm can be produced.

On the other hand, it was demonstrated that the polymer can also act as reducing and stabilizing agent in much more complex systems, i.e. in water-in-oil (w/o) microemulsion droplets. The reverse microemulsion droplets of the quaternary system sodium dodecylsulfate (SDS)/toluene–pentanol (1:1)/water were successfully used for the synthesis of gold nanoparticles. The polymer, incorporated in the droplets, exhibits reducing properties, adsorbs on the surface of the nanoparticles and prevents their aggregation. Consequently, nanoparticles of 8.6 nm can be redispersed after solvent evaporation without a change of their size.

Nevertheless, the polymer acts already as a “template” during the formation of the nanoparticles in water and in microemulsion, so that an additional template effect of the microemulsion is not observed.

The particle formation for both methods is checked by means of UV–vis spectroscopy and the particle size and size distribution are investigated via dynamic light scattering and transmission electron microscopy (TEM).     

Tin oxide-surface modified anatase titanium(IV) dioxide with enhanced UV-light photocatalytic activity

[Sn(acac)(2)]Cl(2) is chemisorbed on the surfaces of anatase TiO(2)via ion-exchange between the complex ions and H(+) released from the surface Ti-OH groups without liberation of the acetylacetonate ligand (Sn(acac)(2)/TiO(2)). The post-heating at 873 K in air forms tin oxide species on the TiO(2) surface in a highly dispersed state on a molecular scale ((SnO(2))(m)/TiO(2)). A low level of this p block metal oxide surface modification (~0.007 Sn ions nm(-2)) accelerates the UV-light-activities for the liquid- and gas-phase reactions, whereas in contrast to the surface modification with d block metal oxides such as FeO(x) and NiO, no visible-light response is induced. Electrochemical measurements and first principles density functional theory (DFT) calculations for (SnO(2))(m)/TiO(2) model clusters (m = 1, 2) indicate that the bulk (TiO(2))-to-surface interfacial electron transfer (BS-IET) enhances charge separation and the following electron transfer to O(2) to increase the photocatalytic activity.     

In situ time-resolved XAFS study on the structural transformation and phase separation of Pt3Sn and PtSn alloy nanoparticles on carbon in the oxidation process

The dynamic behavior and kinetics of the structural transformation of supported bimetallic nanoparticle catalysts with synergistic functions in the oxidation process are fundamental issues to understand their unique catalytic properties as well as to regulate the catalytic capability of alloy nanoparticles. The phase separation and structural transformation of Pt(3)Sn/C and PtSn/C catalysts during the oxidation process were characterized by in situ time-resolved energy-dispersive XAFS (DXAFS) and quick XAFS (QXAFS) techniques, which are element-selective spectroscopies, at the Pt L(III)-edge and the Sn K-edge. The time-resolved XAFS techniques provided the kinetics of the change in structures and oxidation states of the bimetallic nanoparticles on carbon surfaces. The kinetic parameters and mechanisms for the oxidation of the Pt(3)Sn/C and PtSn/C catalysts were determined by time-resolved XAFS techniques. The oxidation of Pt to PtO in Pt(3)Sn/C proceeded via two successive processes, while the oxidation of Sn to SnO(2) in Pt(3)Sn/C proceeded as a one step process. The rate constant for the fast Pt oxidation, which was completed in 3 s at 573 K, was the same as that for the Sn oxidation, and the following slow Pt oxidation rate was one fifth of that for the first Pt oxidation process. The rate constant and activation energy for the Sn oxidation in PtSn/C were similar to those for the Sn oxidation in Pt(3)Sn/C. In the PtSn/C, however, it was hard for Pt oxidation to PtO to proceed at 573 K, where Pt oxidation was strongly affected by the quantity of Sn in the alloy nanoparticles due to swift segregation of SnO(2) nanoparticles/layers on the Pt nanoparticles. The mechanisms for the phase separation and structure transformation in the Pt(3)Sn/C and PtSn/C catalysts are also discussed on the basis of the structural kinetics of the catalysts themselves determined by the in situ time-resolved DXAFS and QXAFS.     

Removal of Tin from Extreme Ultraviolet Collector Optics by <Emphasis Type="Italic">In</Emphasis>-<Emphasis Type="Italic">Situ</Emphasis> Hydrogen Plasma Etching

Extreme ultraviolet (EUV) lithography produces 13.5 nm light by irradiating a droplet of molten Sn with a laser, creating a dense, hot laser-produced plasma and ionizing the Sn to the + 8 through + 12 states. An unwanted by-product is deposition of Sn debris on the collector optic, which focuses the EUV light emitting from the plasma. Consequently, collector reflectivity is degraded. Reflectivity restoration can be accomplished by means of Sn etching by hydrogen radicals, which can be produced by an H₂ plasma and etch the Sn as SnH₄. It has previously been shown that plasma cleaning can successfully create radicals and restore EUV reflectivity but that the Sn removal rate is not necessarily limited by the radical density. Additionally, while Sn etching by hydrogen radicals has been shown by multiple investigators, quantification of the mechanisms behind Sn removal has never been undertaken. This paper explores the processes behind Sn removal. Experiments and modeling show that, within the parameter space explored, the limiting factor in Sn etching is not radical flux or SnH₄ decomposition, but ion energy flux. Thus the removal is akin to reactive ion etching.     

一维带状SnO2的电子传输性能

采用水辅助化学气相沉积法制备了结晶性好的一维带状SnO₂. 分别以小粒径锡粉和金修饰的小粒径锡粉作为反应原料制得带宽度不同的带状SnO₂, 小粒径锡粉作为反应原料能提高带状SnO₂的产率. 将所得SnO₂带和SnO₂纳米颗粒按不同比例混合配制成胶体, 采用刮涂法制备含不同比例纳米颗粒和纳米带的复合SnO₂薄膜并组装染料敏化太阳能电池(DSSCs)来评价带状SnO₂的电子输运性能. 组装的太阳能电池表现出与复合纳晶薄膜中一维SnO₂带的带宽度和所含比例密切相关的光电性能. 通过强度调制光电流谱的测量确定复合SnO₂薄膜的电子传输速率, 并进一步分析一维材料所具有的良好电子传输性能对光电流增加的贡献. 因为一维SnO₂带在复合纳晶薄膜中作为电子输运的快速通道可以加快电子的输运速度, 所以以适宜的比例添加具有合适宽度的一维SnO₂带可以明显提高太阳能电池的光电性能.     

Synthesis and Characterization of PANI/ZnO Nanocomposites

This paper presents our results on the successful fabrication of HCl‐doped polyaniline (PANI)/ZnO nanocomposites via an electrochemical synthesis route. Different weight percents of ZnO nanoparticles were uniformly dispersed in the PANI matrix. The interaction between the dispersed ZnO nanoparticle and PANI was studied using X‐ray diffraction, ultraviolet–visible absorption spectroscopy, photoluminescence (PL) spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, thermogravimetry, and transmission electron microscopy. It is shown that the doping state of the PANI/ZnO nanocomposite is highly improved as compared to that of PANI. The dispersed PANI/ZnO nanocomposites exhibit enhanced PL behavior and thermal stability.     

QM/MD simulation of SWNT nucleation on transition-metal carbide nanoparticles

The mechanism and kinetics of single-walled carbon nanotube (SWNT) nucleation from Fe- and Ni-carbide nanoparticle precursors have been investigated using quantum chemical molecular dynamics (QM/MD) methods. The dependence of the nucleation mechanism and its kinetics on environmental factors, including temperature and metal-carbide carbon concentration, has also been elucidated. It was observed that SWNT nucleation occurred via three distinct stages, viz. the precipitation of the carbon from the metal-carbide, the formation of a "surface/subsurface" carbide intermediate species, and finally the formation of a nascent sp(2)-hybidrized carbon structure supported by the metal catalyst. The SWNT cap nucleation mechanism itself was unaffected by carbon concentration and/or temperature. However, the kinetics of SWNT nucleation exhibited distinct dependences on these same factors. In particular, SWNT nucleation from Ni(x)C(y) nanoparticles proceeded more favorably compared to nucleation from Fe(x)C(y) nanoparticles. Although SWNT nucleation from Fe(x)C(y) and Ni(x)C(y) nanoparticle precursors occurred via an identical route, the ultimate outcomes of these processes also differed substantially. Explicitly, the Ni(x)-supported sp(2)-hybridized carbon structures tended to encapsulate the catalyst particle itself, whereas the Fe(x)-supported structures tended to form isolated SWNT cap structures on the catalyst surface. These differences in SWNT nucleation kinetics were attributed directly to the relative strengths of the metal-carbon interaction, which also dictates the precipitation of carbon from the nanoparticle bulk and the longevity of the resultant surface/subsurface carbide species. The stability of the surface/subsurface carbide was also influenced by the phase of the nanoparticle itself. The observations agree well with experimentally available data for SWNT growth on iron and nickel catalyst particles.     

A new route to self-assembled tin dioxide nanospheres: fabrication and characterization

Nearly monodispersed self-assembled tin dioxide (SnO2) nanospheres with intense photoluminescence (PL) were synthesized using a new wet chemistry technique. Instead of coprecipitating stannous salts, bulk tin (Sn) metal was oxidized at room temperature in a solution of hydrogen peroxide and deionized water containing polyvinylpyrrolidone (PVP) and ethylenediamine (EDA). SnO2 nanocrystals were produced with diameters of approximately 3.8 nm that spontaneously self-assembled into uniform SnO2 nanospheres with diameters of approximately 30 nm. Analysis was performed by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, selected area electron diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, UV-vis absorption spectroscopy, PL spectroscopy, and fluorescence lifetime measurements. The SnO2 nanospheres displayed room-temperature purple luminescence with an intense band at 394 nm (approximately 3.15 eV) and a high quantum yield of approximately 15%, likely as a result of emission from the surface states of SnO2/PVP complexes. The present study could open a new avenue to large-scale synthesis of self-assembled functional oxide nanostructures with technological applications as purple emitters, biological labels, gas sensors, lithium batteries, and dye-sensitized solar cells.     

(Sn,Sb)O2-x基纳米结构厚膜材料气敏特性及机理

对采用水热合成技术所形成的纳米(Sn,Sb)O2 x晶粒结构、厚膜材料的气敏特性及其机理进行了研究,并采用XRD、TEM手段对纳米尺度的（Sn、Sb)O2 x晶粒的结构与表面效应及晶粒形态进行了表征.结果表明,当掺杂Sb5＋的浓度（摩尔分数xSb5＋)为（2.9～5.8)×10－6时,（Sn、Sb)O2 x纳米晶粒表面的电子缺陷浓度增大,增强了对气体的吸附能力,从而提高了对可燃性气体的灵敏度.同时可使晶粒保持短柱状的形态特征,对其灵敏度有一定的控制作用.     

Nanoplasmonic Photoluminescence Spectroscopy at Single‐Particle Level: Sensing for Ethanol Oxidation

Surface plasmon resonances of metal nanoparticles have shown significant promise for the use of solar energy to drive catalytic chemical reactions. More importantly, understanding and monitoring such catalytic reactions at single‐nanoparticle level is crucial for the study of local reaction processes. Herein, using plasmonic photoluminescence (PL) spectroscopy, we describe a novel sensing method for catalytic ethanol oxidation reactions at the single‐nanoparticle level. The Au nanorod monitors the interfacial interaction with ethanol during the catalytic reaction through the PL intensity changes in the single‐particle PL spectra. The analysis of energy relaxation of excited electron–hole pairs indicates the relationship between the PL quenching and ethanol oxidation reaction on the single Au nanorod.     

Electron spectroscopic investigation of Sn coatings on glasses

Float glasses of different thicknesses and a conducting tin oxide glass have been investigated using Photo and Auger Electron Spectroscopy induced by AlKalpha X-rays. On the basis of measured chemical XPS shifts in the binding energies the chemical state of Sn (+2 or +4) incorporated on the float glasses could not be assigned. The use of the Auger parameter allows to separate relaxation and chemical contributions. The derived true chemical shifts of Sn on float-glasses are larger than those of SnO and/or SnO(2) due to the larger ionic environment of the glass matrix. Ar(+) or HF etching reveals that the concentration of Sn decreases exponentially as a function of depth from the surface.     

Correlation between rheological,electrical, and microstructure characteristics in polyethylene/aluminum nanocomposites

Polyethylene (PE)/aluminum (Al) nanocomposites with various filler contents were prepared by a solution compounding method. We investigated the influence of the surface modification of Al nanoparticles on the microstructure and physical properties of the nanocomposites. The silane coupling agent octyl‐trimethoxysilane was shown to significantly increase interfacial compatibility between the polymer phase and Al nanoparticles. Rheological percolation threshold values were determined by analyzing the improvement in storage modulus at low frequencies depending on the Al loadings. Lower percolation threshold values were obtained for the composites prepared with the original nanoparticles than those prepared with the silane‐modified Al nanoparticles. A strong correlation between the time and concentration dependences of dc conductivity and rheological properties was observed in the different nanocomposite systems. The rheological threshold of the composites is smaller than the percolation threshold of electrical conductivity for both of the nanocomposite systems. The difference in percolation threshold is understood in terms of the smaller particle–particle distance required for electrical conduction when compared with that required to impede polymer mobility. It was directly shown by SEM characterization that the nanoparticle surface modification yielded better filler dispersion, as is consistent with our rheological and electrical analysis. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2143–2154, 2008     

Morphological and photoelectrochemical characterization of core-shell nanoparticle films for dye-sensitized solar cells: Zn-O type shell on SnO2 and TiO2 cores

Core-shell type nanoparticles with SnO2 and TiO2 cores and zinc oxide shells were prepared and characterized by surface sensitive techniques. The influence of the structure of the ZnO shell and the morphology ofnanoparticle films on the performance was evaluated. X-ray absorption near-edge structure and extended X-ray absorption fine structure studies show the presence of thin ZnO-like shells around the nanoparticles at low Zn levels. In the case of SnO2 cores, ZnO nanocrystals are formed at high Zn/Sn ratios (ca. 0.5). Scanning electron microscopy studies show that Zn modification of SnO2 nanoparticles changes the film morphology from a compact mesoporous structure to a less dense macroporous structure. In contrast, Zn modification of TiO2 nanoparticles has no apparent influence on film morphology. For SnO2 cores, adding ZnO improves the solar cell efficiency by increasing light scattering and dye uptake and decreasing recombination. In contrast, adding a ZnO shell to the TiO2 core decreases the cell efficiency, largely owing to a loss of photocurrent resulting from slow electron transport associated with the buildup of the ZnO surface layer.