Dominance of Plasmonic Resonant Energy Transfer over Direct Electron Transfer in Substantially Enhanced Water Oxidation Activity of BiVO4 by Shape‐Controlled Au Nanoparticles

The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape‐controlled Au NPs on bismuth vanadate (BiVO₄) are studied, and a largely enhanced photoactivity of BiVO₄ is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO₄ achieves 2.4 mA cm^?2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO₄. It is the highest value among the previously reported plasmonic Au NPs/BiVO₄. Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape‐controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells.     

Au NPs@MoS2 Sub‐Micrometer Sphere‐ZnO Nanorod Hybrid Structures for Efficient Photocatalytic Hydrogen Evolution with Excellent Stability

MoS₂ shows promising applications in photocatalytic water splitting, owing to its uniquely optical and electric properties. However, the insufficient light absorption and lack of performance stability are two crucial issues for efficient application of MoS₂ nanomaterials. Here, Au nanoparticles (NPs)@MoS₂ sub‐micrometer sphere‐ZnO nanorod (Au NPs@MoS₂‐ZnO) hybrid photocatalysts have been successfully synthesized by a facile process combining the hydrothermal method and seed‐growth method. Such photocatalysts exhibit high efficiency and excellent stability for hydrogen production via multiple optical‐electrical effects. The introduction of Au NPs to MoS₂ sub‐micrometer spheres forming a core–shell structure demonstrates strong plasmonic absorption enhancement and facilitates exciton separation. The incorporation of ZnO nanorods to the Au NPs@MoS₂ hybrids further extends the light absorption to a broader wavelength region and enhances the exciton dissociation. In addition, mutual contacts between Au NPs (or ZnO nanorods) and the MoS₂ spheres effectively protect the MoS₂ nanosheets from peeling off from the spheres. More importantly, efficiently multiple exciton separations help to restrain the MoS₂ nanomaterials from photocorrosion. As a result, the Au@MoS₂‐ZnO hybrid structures exhibit an excellent hydrogen gas evolution (3737.4 μmol g^?1) with improved stability (91.9% of activity remaining) after a long‐time test (32 h), which is one of the highest photocatalytic activities to date among the MoS₂ based photocatalysts.     

Partial conversion reaction of ZnO nanowires to ZnSe by a simple selenization method and their photocatalytic activities

A simple novel synthetic method for preparing ZnSe/ZnO heterostructured nanowire (NW) arrays via the selenization of ZnO NWs is reported. A hydrothermally grown ZnO NWs array on a glass substrate was reacted with selenium vapor to generate a 20–30 nm of zincblend ZnSe nanoparticles (NPs) on wurtzite ZnO NWs. A growth mechanism was proposed based on SEM, XRD, and TEM analysis to explain the partial chemical conversion of ZnO NW surfaces into ZnSe NPs. This mechanism is applicable to the synthesis of other chalcogenide compounds. The as-synthesized ZnSe/ZnO heterojunctions showed enhanced UV–visible light absorption properties. The materials exhibited excellent photocatalytic activity toward the decomposition of an organic dye compared to the bare ZnO due to enhanced light absorption and the type-II cascade band structure.     

Periodical 2D Photonic–Plasmonic Au/TiOx Nanocavity Resonators for Photoelectrochemical Applications

Effective light trapping at the nanoscale is vital for efficient photoelectrochemical (PEC) applications. Photonic and plasmonic resonators are the two most promising approaches for this purpose, and the synergetic combination of these two resonators will tail the propagation lengths of incident light along with field enhancements, and thus presents further enhanced light‐trapping activity. Herein, a new hybrid photonic–plasmonic resonator is proposed through sputtering plasmonic Au nanoparticles (NPs) into the 2D photonic TiO_x nanocavity. Through facile control of the size of Au NPs, the matching of resonant wavelength of plasmonic Au NPs and photonic nanocavities maximize the light‐trapping intensity and thus further improve the PEC performance. Furthermore, for expanding the PEC applications, after functionalization of Au NPs with aptamer as a biomolecular recognition unit, a PEC aptasensor is also proposed and presents the highest sensitivity for antibiotic detection.     

Effect of Gold Nanoparticles on the Photocatalytic and Photoelectrochemical Performance of Au Modified BiVO4

Nano-Micro Letters - An efficient visible light driven photocatalyst, gold nanoparticles (NPs) modified BiVO4 (Au/BiVO4), has been synthesized by deposition-precipitation with urea method. Au/BiVO4...     

Highly efficient visible light photocatalysis of novel CuS/ZnO heterostructure nanowire arrays

Here, a facile approach for the fabrication of CuS nanoparticle (NP)/ZnO nanowire (NW) heterostructures on a mesh substrate through a simple two-step solution method is demonstrated. Successive ionic layer adsorption and reaction (SILAR) was employed to uniformly deposit CuS NPs on the hydrothermally grown ZnO NW array. The synthesized CuS/ZnO heterostructure NWs exhibited superior photocatalytic activity under visible light compared to bare ZnO NWs. This strong photocatalytic activity under visible light is due to the interfacial charge transfer (IFCT) from the valence band of the ZnO NW to the CuS NP, which reduces CuS to Cu(2)S. After repeated cycles of photodecolorization of Acid Orange 7 (AO7), the photocatalytic behavior of CuS/ZnO heterostructure NWs exhibited no significant loss of activity. Furthermore, our CuS/ZnO NWs/mesh photocatalyst floats in solution via partial superhydrophobic modification of the NWs.     

From UV to Near‐Infrared Light‐Responsive Metal–Organic Framework Composites: Plasmon and Upconversion Enhanced Photocatalysis

The exploitation of photocatalysts that harvest solar spectrum as broad as possible remains a high‐priority target yet grand challenge. In this work, for the first time, metal–organic framework (MOF) composites are rationally fabricated to achieve broadband spectral response from UV to near‐infrared (NIR) region. In the core–shell structured upconversion nanoparticles (UCNPs)‐Pt@MOF/Au composites, the MOF is responsive to UV and a bit visible light, the plasmonic Au nanoparticles (NPs) accept visible light, whereas the UCNPs absorb NIR light to emit UV and visible light that are harvested by the MOF and Au once again. Moreover, the MOF not only facilitates the generation of “bare and clean” Au NPs on its surface and realizes the spatial separation for the Au and Pt NPs, but also provides necessary access for catalytic substrates/products to Pt active sites. As a result, the optimized composite exhibits excellent photocatalytic hydrogen production activity (280 µmol g^?1 h^?1) under simulated solar light, and the involved mechanism of photocatalytic H₂ production under UV, visible, and NIR irradiation is elucidated. Reportedly, this is an extremely rare study on photocatalytic H₂ production by light harvesting in all UV, visible, and NIR regions.     

Self‐Assembled Ordered Three‐Phase Au–BaTiO3–ZnO Vertically Aligned Nanocomposites Achieved by a Templating Method

Complex multiphase nanocomposite designs present enormous opportunities for developing next‐generation integrated photonic and electronic devices. Here, a unique three‐phase nanostructure combining a ferroelectric BaTiO₃, a wide‐bandgap semiconductor of ZnO, and a plasmonic metal of Au toward multifunctionalities is demonstrated. By a novel two‐step templated growth, a highly ordered Au–BaTiO₃–ZnO nanocomposite in a unique “nanoman”‐like form, i.e., self‐assembled ZnO nanopillars and Au nanopillars in a BaTiO₃ matrix, is realized, and is very different from the random three‐phase ones with randomly arranged Au nanoparticles and ZnO nanopillars in the BaTiO₃ matrix. The ordered three‐phase “nanoman”‐like structure provides unique functionalities such as obvious hyperbolic dispersion in the visible and near‐infrared regime enabled by the highly anisotropic nanostructures compared to other random structures. Such a self‐assembled and ordered three‐phase nanocomposite is obtained through a combination of vapor–liquid–solid (VLS) and two‐phase epitaxy growth mechanisms. The study opens up new possibilities in the design, growth, and application of multiphase structures and provides a new approach to engineer the ordering of complex nanocomposite systems with unprecedented control over electron–light–matter interactions at the nanoscale.     

Extension of optical properties of ZnO/SiO2 materials induced by incorporation of Au or NiO nanoparticles

Incorporating noble metal nanoparticles (NPs) and oxides has been proved to be an effective method to tune the optical properties of silica based materials. In this paper the optical and photocatalytic properties have been studied for ZnO/SiO₂ modified with Au or NiO nanoparticles. Changes in the optical properties of semiconductor ZnO particles have been observed due to the deposition of coloured Au and NiO nanoparticles by reducing the band gap energy and thus extending light absorption to visible domain. The excellent surface characteristics of NiO/ZnO/SiO₂ and Au/ZnO/SiO₂ favour the adsorption behaviour of these materials and limit the recombination of electron–holes pairs. Crystal Violet degradation under VIS light proved to have higher efficiency in the presence of Au/ZnO/SiO₂ (97%) than for NiO/ZnO/SiO₂ (60%).     

Fabrication of conducting polymer micro/nanostructures coated with Au nanoparticles for electrochemical sensors

Polypyrrole (PPy) micro/nanostructures coated with Au nanoparticles were prepared by electropolymerization and electro-deposition. Two types of PPy structures, micro-embossed and nanowire forest, were synthesized on patterned gold electrodes using different aqueous solutions, and Au nanoparticles were coated onto the PPy micro/nanostructure surface. The size of the Au nanoparticles ranged from 10 to 100 nm, and the maximum density of the nanoparticles was 73 particles/microm2. The small size and high density of the Au nanoparticles were achieved by optimizing the deposition time and chloroauric acid (HAuCl4) concentration. Cyclic voltammograms of ferrocyanide oxidation showed that the PPy micro/nanostructures coated with Au nanoparticles exhibit good electrochemical activity. These high-performance electrodes can be used in electrochemical sensors because the Au nanoparticles enhance electron transfer and provide a binding site for biomarker molecules, such as DNA, protein, and aptamers.     

ZnO nanowire/TiO2 nanoparticle photoanodes prepared by the ultrasonic irradiation assisted dip-coating method

Hybrid ZnO/TiO₂ photoanodes for dye-sensitized solar cells were prepared by combining ZnO nanowire (NW) arrays and TiO₂ nanoparticles (NPs) with the assistance of the ultrasonic irradiation assisted dip-coating method. Results show that the ultrasonic irradiation was an efficient way to promote the gap filling of TiO₂ NPs in the interstices of ZnO NWs. Hybrid ZnO NW/TiO₂ NP electrodes prepared with ultrasonic treatment exhibited better gap filling efficiency and higher visible absorptance. The overall conversion efficiency of the hybrid electrode was 0.79%, representing 35% improvement compared with that of the traditional one (0.58%). The enlarged surface area and improved attachments of TiO₂ NPs onto the walls of ZnO NWs induced by the application of ultrasonic irradiation may be the underlying reason. Electrochemical impedance spectroscopy measurements indicated that hybrid electrodes combined the advantages of improved electron transport along the ZnO NWs and increased surface area provided by infiltrated TiO₂ NPs, both of which are responsible for the improved cell efficiency.     

A Joint Experimental and Computational Search for Authentic Nano‐electrocatalytic Effects: Electrooxidation of Nitrite and L‐Ascorbate on Gold Nanoparticle‐Modified Glassy Carbon Electrodes

The investigation of electrocatalytic nanoeffects is tackled via joint electrochemical measurements and computational simulations. The cyclic voltammetry of electrodes modified with metal nanoparticles is modeled considering the kinetics of the electrochemical process on the bulk materials of the different regions of the electrode, that is, the substrate (glassy carbon) and the nanoparticles (gold). Comparison of experimental and theoretical results enables the detection of changes in the electrode kinetics at the nanoscale due to structural and/or electronic effects. This approach is applied to the experimental assessment of electrocatalytic effects by gold nanoparticles (Au NPs) in the electrooxidation of nitrite and L‐ascorbate. Glassy carbon electrode is modified with Au NPs via seed‐mediated growth method. Divergence between the kinetics of these processes on gold macroelectrodes and gold nanoparticles is examined. Whereas claimed catalytic effects are not observed in the electrooxidation of nitrite, electrocatalytic nanoeffects are verified in the case of L‐ascorbate. This is probably due to that the electron transfer process follows an adsorptive mechanism. The combination of simulation with experiments is commended as a general strategy of authentification, or not, of nanoelectrocatalytic effects.     

Synthesis and characterization of plasmonic visible active Ag/ZnO photocatalyst

Ag deposited ZnO nanoparticles (NPs) have been synthesized by simple sol–gel method for visible light active photocatalytic application. X-ray diffraction (XRD), TEM, UV–DRS and PL studies have been used to characterize the photocatalyst. The results show that Ag/ZnO NPs are wurtzite phase (WZ) of ZnO with Ag NPs in the surface region forming a hetero-interface of Ag–WZ (ZnO). Visible light activity of the material has been studied using photocatalytic degradation kinetics of methylene blue as a probe pollutant. Ag/ZnO NPs exhibit five times higher visible-light driven photocatalytic activity than pristine ZnO and four times than the reference Degussa P-25, under identical conditions. The high visible activity of Ag/ZnO may be attributed to the surface plasmon effect complemented sensitization in the presence of metallic Ag and effective charge separation through Ag–WZ hetero-interfaces.     

Au/ZnO nanocomposites: Facile fabrication and enhanced photocatalytic activity for degradation of benzene

Au nanoparticles supported on highly uniform one-dimensional ZnO nanowires (Au/ZnO hybrids) have been successfully fabricated through a simple wet chemical method, which were first used for photodegradation of gas-phase benzene. Compared with bare ZnO nanowires, the as-prepared Au/ZnO hybrids were found to possess higher photocatalytic activity for degradation of benzene under UV and visible light (degradation efficiencies reach about 56.0% and 33.7% after 24 h under UV and visible light irradiation, respectively). Depending on excitation happening on ZnO semiconductor or on the surface plasmon band of Au, the efficiency and operating mechanism are different. Under UV light irradiation, Au nanoparticles serve as an electron buffer and ZnO nanowires act as the reactive sites for benzene degradation. When visible light is used as the light irradiation source, Au nanoparticles act as the light harvesters and photocatalytic sites alongside of charge-transfer process, simultaneously.     

Effect of surface plasmon resonance on the photocatalytic activity of Au/TiO2 under UV/visible illumination

In this study, gold-loaded titanium dioxide was prepared by an impregnation method to investigate the effect of surface plasmon resonance (SPR) on photoactivity. The deposited gold nanoparticles (NPs) absorb visible light because of SPR. The effects of both the gold content and the TiO2 size of Au/TiO2 on SPR and the photocatalytic efficiency were investigated. The morphology, crystal structure, light absorption, emission from the recombination of a photoexcited electron and hole, and the degree of aggregation were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-visible-diffuse reflectance spectra (UV-VIS-DRS), photoluminescence (PL) spectroscopy, and turbidimetry, respectively. Photocatalytic activity was evaluated by the decolorization of methyl orange solution over modified titania under UV and UV/GLED (green light emitting diode) illumination. Au/TiO2 NPs exhibited an absorption peak (530-570 nm) because of SPR. The results of our photocatalytic experiments indicated that the UV-inducedly photocatalytic reaction rate was improved by simultaneously using UV and green light illumination; this corresponds to the adsorption region of SPR. Au/TiO2 could use the enhanced electric field amplitude on the surface of the Au particle in the spectral vicinity of its plasmon resonance and thus improve the photoactivity. Experimental results show that the synergistic effect between UV and green light for the improvement of photoactivity increases with increasing the SPR absorption, which in turn is affected by the Au content and TiO2 size.     

Enhanced absorptive characteristics of metal nanoparticle-coated silicon nanowires for solar cell applications

The optical properties of metal nanoparticle (NP)-coated silicon nanowires (Si NWs) are theoretically investigated using COMSOL Multiphysics commercial software. A geometrical array of periodic Si NWs coated with metal NPs is proposed. The simulation demonstrates that light absorption could be enhanced significantly in a long wavelength region of the solar spectrum, based upon the localized surface plasmons generated around metal NPs. Various metal NPs, such as Au, Ag, and Al, are all found to increase their light absorption while in contact with Si NWs, in which the Au NPs show the best result in light enhancement. This theoretical work might prove useful in providing a fundamental understanding toward improving further the efficiency of Si wired solar cells.     

Light‐Driven Shape Morphing,Assembly, and Motion of Nanocomposite Gel Surfers

Patterning of nanoparticles (NPs) via photochemical reduction within thermally responsive hydrogel films is demonstrated as a versatile platform for programming light‐driven shape morphing and materials assembly. Responsive hydrogel disks, containing patterned metal NPs, form characteristic wrinkled structures when illuminated at an air/water interface. The resulting distortion of the three‐phase (air/water/hydrogel) contact lines induces capillary interactions between two or more disks, which are either attractive or repulsive depending on the selected pattern of light. By programming the shapes of the NP‐rich regions, as well as of the hydrogel objects themselves, the number and location of attractive interactions are specified, and the assembly geometry is controlled. Remarkably, appropriately patterned illumination enables sustained rotation and motion of the hydrogel disks. Overall, these results offer insight into a wide variety of shape‐programmable materials and capillary assemblies, simply by controlling the NP patterns and illumination of these soft materials.     

Directed self-assembly of nanogold using a chemically modified nanopatterned surface

Electron-beam lithography (EBL) was used to define an aminosilane nanopatterned surface in order to electrostatically self-assemble gold nanoparticles (Au NPs). The chemically modified nanopatterned surfaces were immersed into a Au NP solution to allow the Au NPs to self-assemble. Equilibrium self-assembly was achieved in only 20 min. The number of Au NPs that self-assembled on an aminosilane dot was controlled by manipulating the diameters of both the Au NPs and the dots. Adding salt to the Au NP solution enabled the Au NPs to self-assemble in greater numbers on the same sized dot. However, the preparation of the Au NP solution containing salt was sensitive to spikes in the salt concentration. These spikes led to aggregation of the Au NPs and non-specific deposition of Au NPs on the substrate. The Au NP patterned surfaces were immersed in a sodium hydroxide solution in order to lift-off the patterned Au NPs, but no lift-off was observed without adequate physical agitation. The van der Waals forces are too strong to allow for lift-off despite the absence of electrostatic forces.     

CdSe quantum dot-sensitized Au/TiO2 hybrid mesoporous films and their enhanced photoelectrochemical performance

Novel CdSe quantum dot (QD)-sensitized Au/TiO₂ hybrid mesoporous films have been designed, fabricated, and evaluated for photoelectrochemical (PEC) applications. The Au/TiO₂ hybrid structures were made by assembly of Au and TiO₂ nanoparticles (NPs). A chemical bath deposition method was applied to deposit CdSe QDs on TiO₂ NP films with and without Au NPs embedded. We observed significant enhancements in photocurrent for the film with Au NPs, in the entire spectral region we studied (350–600 nm). Incident-photon-to-current efficiency (IPCE) data revealed an average enhancement of 50%, and the enhancement was more significant at short wavelength. This substantially improved PEC performance is tentatively attributed to the increased light absorption of CdSe QDs due to light scattering by Au NPs. Interestingly, without QD sensitization, the Au NPs quenched the photocurrent of TiO₂ films, due to the dominance of electron trapping over light scattering by Au NPs. The results suggest that metal NPs are potentially useful for improving the photoresponse in PEC cells and possibly in other devices such as solar cells based on QD-sensitized metal oxide nanostructured films. This work demonstrates that metal NPs can serve as light scattering centers, besides functioning as photo-sensitizers and electron traps. The function of metal NPs in a particular nanocomposite film is strongly dependent on their structure and morphology.      

Growth of two-dimensional arrays of uncapped gold nanoparticles on silicon substrates

A method of preparing large area patterned 2D arrays of uncapped gold (Au) nanoparticles has been developed. The pattern has been formed using self-assembly of uncapped Au nanoparticles. The Au nanoparticles were synthesized via toluene/water two phase systems using a reducing agent and colloidal solution of Au nanoparticles was produced. These nanoparticles have been prepared without using any kind of capping agent. Analysis by TEM showed discrete Au nanoparticles of 4 nm average diameter. AFM analysis also showed similar result. The TEM studies showed that these nanoparticles formed self-assembled coherent patterns with dimensions exceeding 500 nm. Spin coating on silicon substrate by suitably adjusting the speed can self-assemble these nanoparticles to lengths exceeding 1 μm.