Can Xue

Designing, fabricating, and imaging Raman hot spots

We have developed a probe of the electromagnetic mechanism of surface-enhanced Raman scattering via Au nanodisk arrays generated by using on-wire lithography. In this approach, disk thickness and interparticle gap are precisely controlled from 5 nm to many micrometers. Confocal Raman microscopy demonstrates that disk thickness and gap play a crucial role in determining surface-enhanced Raman scattering intensities. Theoretical calculations also demonstrate that these results are consistent with the electromagnetic mechanism, including the surprising result that the largest enhancement does not occur for the smallest gaps.

One‐pot Synthesis of CdS Nanocrystals Hybridized with Single‐Layer Transition‐Metal Dichalcogenide Nanosheets for Efficient Photocatalytic Hydrogen Evolution

Exploration of low-cost and earth-abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition-metal dichalcogenides (TMDs) showed outstanding performance as co-catalysts for the hydrogen evolution reaction (HER), designing TMD-hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one-pot wet-chemical method is developed to prepare MS2-CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single-layer MS2 nanosheets with lateral size of 4-10 nm selectively grow on the Cd-rich (0001) surface of wurtzite CdS nanocrystals. These MS2-CdS nanohybrids possess a large number of edge sites in the MS2 layers, which are active sites for the HER. The photocatalytic performances of WS2-CdS and MoS2-CdS nanohybrids towards the HER under visible light irradiation (>420 nm) are about 16 and 12 times that of pure CdS, respectively. Importantly, the MS2-CdS nanohybrids showed enhanced stability after a long-time test (16 h), and 70% of catalytic activity still remained.

Mechanistic Study of Photomediated Triangular Silver Nanoprism Growth

This article presents a mechanistic study of the photomediated growth of silver nanoprisms. The data show that the photochemical process is driven by silver redox cycles involving reduction of silver cations by citrate on the silver particle surface and oxidative dissolution of small silver particles by O2. Bis(p-sulfonatophenyl)phenylphosphine increases the solubility of the Ag(+) by complexing it and acts as a buffer to keep the concentration of Ag(+) at 20 microM. The silver particles serve as photocatalysts and, under plasmon excitation, facilitate Ag(+) reduction by citrate. Higher Ag(+) concentrations favor a competitive thermal process, which results in increased prism thickness.

Hetero-nanostructured suspended photocatalysts for solar-to-fuel conversion

Converting solar energy into valuable hydrogen and hydrocarbon fuels through photocatalytic water splitting and CO2 photo-reduction is highly promising in addressing the growing demand for renewable and clean energy resources. Developing efficient photocatalysts for solar-driven H2 production and CO2 reduction is the most essential part in achieving this goal. For the purpose of attaining high photocatalytic efficiency, hetero-nanostructures formed by multiple material components have been demonstrated as an effective strategy. Within this heterostructure, its interface is a critical consideration, whereby it determines the principle of charge transfer across the heterojunctions and consequent surface reactions. This article reviews the recent developments of hetero-nanostructures for photocatalytic H2 production and CO2 reduction based on material compositions that form heterojunctions.

Preparation of Au-BiVO4 heterogeneous nanostructures as highly efficient visible-light photocatalysts

Au-BiVO(4) heterogeneous nanostructures have been successfully prepared through in situ growth of gold nanoparticles on BiVO(4) microtubes and nanosheets via a cysteine-linking strategy. The experimental results reveal that these Au-BiVO(4) heterogeneous nanostructures exhibit much higher visible-light photocatalytic activities than the individual BiVO(4) microtubes and nanosheets for both dye degradation and water oxidation. The enhanced photocatalytic efficiencies are attributed to the charge transfer from BiVO(4) to the attached gold nanoparticles as well as their surface plasmon resonance (SPR) absorption. These new heteronanostructures are expected to show considerable potential applications in solar-driven wastewater treatment and water splitting.

Full solution-processed synthesis of all metal oxide-based tree-like heterostructures on fluorine-doped tin oxide for water splitting

Well-ordered tree-like functional heterostructures, composed of the environmentally friendly oxides ZnO, TiO(2) , and CuO, on a fluorine-doped tin oxide substrate are realized by a practical, cost-effective, solution-processable strategy. The heterostructures are demonstrated to be an efficient light-harvesting medium in a photo-electrochemical cell to split water for hydrogen-gas generation, and the developed strategy provides a highly promising, cheap, green way to fabricate multifunctional hierarchically branched structures for many potential applications.

Programmable photo-electrochemical hydrogen evolution based on multi-segmented CdS-Au nanorod arrays.

Programmable photocatalysts for hydrogen evolution have been fabricated based on multi-segmented CdS-Au nanorod arrays, which exhibited high-efficiency and programmability in hydrogen evolution as the photoanodes in the photoelectrochemical cell. Multiple different components each possess unique physical and chemical properties that provide these cascade nanostructures with multiformity, programmability, and adaptability. These advantages allow these nanostructures as promising candidates for high efficient harvesting and conversion of solar energy.

Chemical Fabrication of Heterometallic Nanogaps for Molecular Transport Junctions

We report a simple and reproducible method for fabricating heterometallic nanogaps, which are made of two different metal nanorods separated by a nanometer-sized gap. The method is based upon on-wire lithography, which is a chemically enabled technique used to synthesize a wide variety of nanowire-based structures (e.g., nanogaps and disk arrays). This method can be used to fabricate pairs of metallic electrodes, which exhibit distinct work functions and are separated by gaps as small as 2 nm. Furthermore, we demonstrate that a symmetric thiol-terminated molecule can be assembled into such heterometallic nanogaps to form molecular transport junctions (MTJs) that exhibit molecular diode behavior. Theoretical calculations demonstrate that the coupling strength between gold and sulfur (Au-S) is 2.5 times stronger than that of Pt-S. In addition, the structures form Raman hot spots in the gap, allowing the spectroscopic characterization of the molecules that make up the MTJs.

Direct evidence of plasmon enhancement on photocatalytic hydrogen generation over Au/Pt-decorated TiO2 nanofibers.

Direct evidence of plasmon-enhanced H2 generation is observed in photocatalytic water reduction by using TiO2 electrospun nanofibers co-decorated with Au and Pt nanoparticles through dual-beam irradiation. The Au/Pt/TiO2 nanofibers exhibit certain activity for H2 generation under single irradiation at 420 nm that excites the defect/impurity states of TiO2. Significantly, when secondary irradiation at 550 nm is introduced to simultaneously excite Au SPR, we observed 2.5 times higher activity for H2 generation. Further investigation by finely controlling the irradiation wavelengths reveals that the enhancement factor on the photocatalytic activity for H2 generation is directly correlated with the plasmon absorption band of the Au nanoparticles in the Au/Pt/TiO2 nanofibers. The control experiments with different sacrificial agents suggest that the hot plasmonic electrons of Au are responsible for the enhanced photocatalytic activity that can be magnified when TiO2 is simultaneously excited.

Enhanced visible-light-driven photocatalytic hydrogen generation over g-C3N4 through loading the noble metal-free NiS2 cocatalyst

Nickel sulfide nanoparticles were successfully grown as a cocatalyst on the surface of polymeric g-C3N4 photocatalysts through a hydrothermal method. The NiS2 composition is confirmed by various spectroscopic techniques and electron microscopy. It was found that the presence of NiS2 nanoparticles on the g-C3N4 surface could greatly enhance the photocatalytic activity of g-C3N4 for hydrogen generation under visible-light irradiation. Significantly, the NiS2-loaded g-C3N4 was capable of showing an even higher photocatalytic H2 generation rate than that of Pt-loaded g-C3N4. Such enhanced photocatalytic activities by NiS2-loading could be attributed to the effective charge transfer between g-C3N4 and the attached NiS2 nanoparticles which might also serve as active sites for proton reduction into H2. Our studies demonstrate a promising strategy to develop economic noble-metal-free composites as photocatalysts for efficient solar-to-hydrogen conversion.