The aerobic oxidation of glycerol provides an economically viable route to glyceraldehyde, dihydroxyacetone and glyceric acid with versatile applications, for which monometallic Pt, Au and Pd and bimetallic Au-Pt, Au- Pd and Pt-Pd catalysts on TiO2 were examined under base-free conditions. Pt exhibited a superior activity relative to Pd, and Au-Pd and Pt-Pd while Au was essentially inactive. The presence of Au on the Au-Pt/TiO2 catalysts led to their higher activities （normalized per Pt atom） in a wide range of Au/Pt atomic ratios （i.e. 1/3-7/1 ）, and the one with the Au/Pt ratio of 3/1 exhibited the highest activity. Such promoting effect is ascribed to the increased electron density on Pt via the electron transfer from Au to Pt, as characterized by the temperature-programmed desorption of CO and infra-red spectroscopy for CO adsorption. Meanwhile, the presence of Au on Au-Pt/TiO2, most like due to the observed electron transfer, changed the product selectivity, and facilitated the oxidation of the secondary hydroxyl groups in glycerol, leading to the favorable formation of dihydroxyacetone over glyceraldehyde and glyceric acid that were derived from the oxidation of the primary hydroxyl groups. The synergetic effect between Au and Pt demonstrates the feasibility in the efficient oxidation of glycerol to the targeted products, for example, by rational tuning of the electronic properties of metal catalysts.
The kesterite Cu2ZnSn(S,Se)4(CZTSSe) is an ideal candidate for light harvesting materials in earth-abundant low-cost thinfilm solar cells(TFSC). Although the solution-based processing is a most promising approach to achieve low-cost solar cells with high power conversion efficiency, the issues of poor crystallinity and carbon residue in CZTSSe thin films are still challenging. Herein, a non-hydrazine solution-based method was reported to fabricate highly crystallized and carbon-free kesterite CZTSSe thin films. Interestingly, it was found that the synthetic atmosphere of metal organic precursors have a dramatic impact on the morphology and crystallinity of CZTSSe films. By optimizing the processing parameters, we were able to obtain a kesterite CZTSSe film composed of compact large crystal grains with trace carbon residues. Also, a viable reactive ion etching(RIE) processing with optimized etching conditions was then developed to successfully eliminate trace carbon residues on the surface of the CZTSSe film.
ZOU YuGangLIU JieZHANG XingJIANG YanHU JinSongWAN Li-Jun
Tip-enhanced Raman spectrum(TERS) is a scanning probe technique for acquiring chemical information at high spatial resolution and with high chemical sensitivity. The sensitivity of TERS with atomic force microscopy(AFM) system is mainly determined by the metalized tips. Here, we report a fabrication protocol for AFM-TERS tips that incorporate a copper(Cu) primer film between a gold(Au) layer and a Si AFM tip. They were fabricated by coating the Si tip with a 2 nm Cu layer prior to adding a 20 nm Au layer. For top illumination TERS experiments, these tips exhibited superior TERS performance relative to that observed for tips coated with Au only. Samples included graphene, thiophenol and brilliant cresyl blue. The results may derive from the surface roughness of the tip apex and a Cu/Au synergism of local surface plasmon resonances.
We have fabricated hybrid molecular chain structures formed by electron acceptor compound 1 and electron donor molecules 2 and 3 at the liquid/solid interface of graphite surface.The structural details of the mono-component and the binary assemblies are revealed by high resolution scanning tunneling microscopy (STM).Compound 1 can form two well-ordered lamellar patterns at different concentrations.In the co-adsorption structures,compounds 2 and 3 can insert into the space between molecular chains of compound 1 and form large area well-ordered nanoscale phase separated lamellar structures.The unit cell parameters for the coassemblies can be "flexibly" adjusted to make the electron donors and acceptors perfectly match along the molecular chains.Scanning tunneling spectroscopy (STS) results indicate that the electronic properties of individual molecular donors and acceptors are preserved in the binary self-assembly.These results provide molecular insight into the nanoscale phase separation of organic electron acceptors and donors on surfaces and are helpful for the fabrication of surface supramolecular structures and molecular devices.
