Electrodeposited Mo3S13 Films from (NH4)2Mo3S13·2H2O for Electrocatalysis of Hydrogen Evolution Reaction.

Molybdenum sulfides are considered to be one kind of the promising candidates as cheap and efficient electrocatalysts for hydrogen evolution reaction (HER). But this is still a gap on electrocatalytic performance toward Pt. To further enhance electrocatalytic activity of molybdenum sulfides, in this work, we prepared Mo3S13 films with high ratio of sulfur to molybdenum by electrodeposition. The Mo3S13 films exhibit highly efficient electrocatalytic activity for HER and achieve a current density of 10 mA/cm2 at an overpotential of 200 mV with an onset potential of 130 mV vs RHE and a Tafel slope of 37 mV/dec, which is superior to other reported MoS2 films. The highly electrocatalytic activity is attributed to high percentage of bridging S22- and apical S2- as well as good conductivity. This study provides an avenue for designing new molybdenum sulfides electrocatalysts.

Layer-Controlled Chemical Vapor Deposition Growth of MoS2 Vertical Heterostructures via van der Waals Epitaxy.

The fascinating semiconducting and optical properties of monolayer and few-layer transition metal dichalcogenides, as exemplified by MoS2, have made them promising candidates for optoelectronic applications. Controllable growth of heterostructures based on these layered materials is critical for their successful device applications. Here, we report a direct low temperature chemical vapor deposition (CVD) synthesis of MoS2 monolayer/multilayer vertical heterostructures with layer-controlled growth on a variety of layered materials (SnS2, TaS2, and graphene) via van der Waals epitaxy. Through precise control of the partial pressures of the MoCl5 and elemental sulfur precursors, reaction temperatures, and careful tracking of the ambient humidity, we have successfully and reproducibly grown MoS2 vertical heterostructures from 1 to 6 layers over a large area. The monolayer MoS2 heterostructure was verified using cross-sectional high resolution transmission electron microscopy (HRTEM) while Raman and photoluminescence spectroscopy confirmed the layer-controlled MoS2 growth and heterostructure electronic interactions. Raman, photoluminescence, and energy dispersive X-ray spectroscopy (EDS) mappings verified the uniform coverage of the MoS2 layers. This reaction provides an ideal method for the scalable layer-controlled growth of transition metal dichalcogenide heterostructures via van der Waals epitaxy for a variety of optoelectronic applications.

Direct detection of DNA below ppb level based on thionin-functionalized layered MoS2 electrochemical sensors.

A layered MoS2-thionin composite was prepared by sonicating their mixture in an ionic liquid and gradient centrifugation. Because DNA is rarely present in single-stranded form, either naturally or after PCR amplification, the composite was used for fabrication of a double-stranded DNA (dsDNA) electrochemical biosensor due to stable electrochemical response, intercalation, and electrostatic interaction of thionin with DNA. The linear range over dsDNA concentration from 0.09 ng mL(-1) to 1.9 ng mL(-1) is obtained, and moreover, it is suitable for the detection of single-stranded DNA (ssDNA). The biosensor has been applied to the detection of circulating DNA from healthy human serum, and satisfactory results have been obtained. The constructed DNA electrochemical biosensor shows potential application in the fields of bioanalysis and clinic diagnosis. Furthermore, this work proposes a new method to construct electrochemical biosensors based on MoS2 sheets.

Biosensor based on ultrasmall MoS2 nanoparticles for electrochemical detection of H2O2 released by cells at the nanomolar level.

Monodispersed surfactant-free MoS2 nanoparticles with sizes of less than 2 nm were prepared from bulk MoS2 by simple ultrasonication and gradient centrifugation. The ultrasmall MoS2 nanoparticles expose a large fraction of edge sites, along with their high surface area, which lead to attractive electrocatalytic activity for reduction of H2O2. An extremely sensitive H2O2 biosensor based on MoS2 nanoparticles with a real determination limit as low as 2.5 nM and wide linear range of 5 orders of magnitude was constructed. On the basis of this biosensor, the trace amount of H2O2 released from Raw 264.7 cells was successfully recorded, and an efficient glucose biosensor was also fabricated. Since H2O2 is a byproduct of many oxidative biological reactions, this work serves as a pathway for the application of MoS2 in the fields of electrochemical sensing and bioanalysis.

Size-Dependent Enhancement of Electrocatalytic Oxygen-Reduction and Hydrogen-Evolution Performance of MoS2 Particles.

MoS2 particles with different size distributions were prepared by simple ultrasonication of bulk MoS2 followed by gradient centrifugation. Relative to the inert microscale MoS2, nanoscale MoS2 showed significantly improved catalytic activity toward the oxygen-reduction reaction (ORR) and hydrogen-evolution reaction (HER). The decrease in particle size was accompanied by an increase in catalytic activity. Particles with a size of around 2 nm exhibited the best dual ORR and HER performance with a four-electron ORR process and an HER onset potential of -0.16 V versus the standard hydrogen electrode (SHE). This is the first investigation on the size-dependent effect of the ORR activity of MoS2, and a four-electron transfer route was found. The exposed abundant Mo edges of the MoS2 nanoparticles were proven to be responsible for the high ORR catalytic activity, whereas the origin of the improved HER activity of the nanoparticles was attributed to the plentiful exposed S edges. This newly discovered process provides a simple protocol to produce inexpensive highly active MoS2 catalysts that could easily be scaled up. Hence, it opens up possibilities for wide applications of MoS2 nanoparticles in the fields of energy conversion and storage.

A simple and rapid competitive enzyme-linked immunosorbent assay (cELISA) for high-throughput measurement of secretory immunoglobulin A (sIgA) in saliva.

A simple competitive enzyme-linked immunosorbent assay (cELISA) was established for rapid measurement of secretory immunoglobulin A (sIgA) in saliva. The method was based on competitive reaction between the immobilized IgA and free IgA in the solution for the limited amount of horseradish peroxidase-conjugated rabbit anti-human IgA. In comparison with the conventionally used Sandwich ELISA, the cELISA is simpler, low-cost, and shows better reproducibility since it is not affected by the variation of capture antibodies from different batches. The assay time was also significantly reduced from more than 5h to less than 3h. Different curve-fitting models were compared, among which the fully specified logit-log model gave the best results. The linear working range and limit of detection were found to be 0.1-100 microg mL(-1) and 0.05 microg mL(-1), respectively. Matrix effects of saliva samples were investigated and a reasonable range of dilution factors were proposed. The developed method offers a very practical approach for high-throughput measurement of sIgA in saliva samples.