Suppressing Non-Radiative Relaxation through Single-Atom Metal Modification for Enhanced Fluorescence Efficiency in Molybdenum Disulfide Quantum Dots.

To enhance the fluorescence efficiency of semiconductor nanocrystal quantum dots (QDs), strategies via enhancing photo-absorption and eliminating non-radiative relaxation have been proposed. In this study, we demonstrate that fluorescence efficiency of molybdenum disulfide quantum dots (MoS2 QDs) can be enhanced by single-atom metal (Au, Ag, Pt, Cu) modification. Four-fold enhancement of the fluorescence emission of MoS2 QDs is observed with single-atom Au modification. The underlying mechanism is ascribed to the passivation of non-radiative surface states owing to the new defect energy level of Au in the forbidden band that can trap excess electrons in n-type MoS2 , increasing the recombination probability of conduction band electrons with valence band holes of MoS2 . Our results open an avenue for enhancing the fluorescence efficiency of QDs via the modification of atomically dispersed metals, and extend their scopes and potentials in a fundamental way for economic efficiency and stability of single-atom metals.

Synthesis of Pure Thiophene-Sulfur-Doped Graphene for an Oxygen Reduction Reaction with High Performance.

Various S-bonding configurations existing in sulfur-doped reduced graphene oxide (S-rGO) show different electronic structures and physiochemical properties. Thus, understanding the properties of unique S-bonding configurations requires the construction of S-rGO with only single configuration. Here, we synthesized S-rGO with a pure thiophene-sulfur configuration through a simple and low-cost hydrothermal method by simply controlling the oxidation degree of the graphene oxide (GO) precursor. Through the use of a GO precursor with a high content of C-O groups, pure doping of the thiophene-sulfur configuration in the rGO can be achieved. Further electrochemical characterization reveals an increased electrocatalytic activity of the pure thiophene-sulfur-doped S-rGO in the oxygen reduction reaction, indicating the important role of thiophene-sulfur. The present work deepens the understanding of the functions of doped nonmetal elements in carbon materials in electrocatalysis and helps in the design of high performance electrocatalysts.

A Novel Reformed Reduced Kernel Extreme Learning Machine with RELIEF-F for Classification.

With the exponential growth of the Internet population, scientists and researchers face the large-scale data for processing. However, the traditional algorithms, due to their complex computation, are not suitable for the large-scale data, although they play a vital role in dealing with large-scale data for classification and regression. One of these variants, which is called Reduced Kernel Extreme Learning Machine (Reduced-KELM), is widely used in the classification task and attracts attention from researchers due to its superior performance. However, it still has limitations, such as instability of prediction because of the random selection and the redundant training samples and features because of large-scaled input data. This study proposes a novel model called Reformed Reduced Kernel Extreme Learning Machine with RELIEF-F (R-RKELM) for human activity recognition. RELIEF-F is applied to discard the attributes of samples with the negative values in the weights. A new sample selection approach, which is used to further reduce training samples and to replace the random selection part of Reduced-KELM, solves the unstable classification problem in the conventional Reduced-KELM and computation complexity problem. According to experimental results and statistical analysis, our proposed model obtains the best classification performances for human activity data sets than those of the baseline model, with an accuracy of 92.87 % for HAPT, 92.81 % for HARUS, and 86.92 % for Smartphone, respectively.

Self-supporting Atmosphere-Assisted Synthesis of 1D Mo2 C-based Catalyst for Efficient Hydrogen Evolution.

One-dimensional materials exhibit fascinating properties in electrocatalytic applications but their fabrication faces the challenge of tedious and complicated operations. We have developed a bottom-up strategy to construct a 1D metal carbide catalyst (Mo2 C@NC) consisting of ultrafine Mo2 C nanoparticles embedded within nitrogen-doped carbon layers by simply calcining a mixture of ammonium molybdate, urea and melamine. Experimental results and thermodynamic calculations demonstrate that the retainable pyrolysis-generated self-supporting atmosphere plays a crucial role in the crystalline phase and morphology of materials. When functioned as an electrocatalyst for the hydrogen evolution reaction (HER), the achieved Mo2 C@NC presents an excellent catalytic activity as well as outstanding stability. This work could shed fresh light onto the facile synthesis of effective HER catalysts with 1D nanostructure.

SERS Detection of Nucleobases in Single Silver Plasmonic Nanopores.

Conventional ion current-based nanopore techniques that identify single molecules are hampered by limitations of providing only the ionic current information. Here, we introduce a silver nanotriangle-based nanopore (diameter < 50 nm) system for detecting molecule translocation using surface-enhanced Raman scattering. Rhodamine 6G is used as a model molecule to study the effect of an electric field (-1 V) on the mass transport. The four DNA bases also show significantly different SERS signals when they are transported into the plasmonic nanopore. The observations suggest that in the electric field, analyte molecules are driven into the nanopipette through the hot spot of the silver nanopore. The plasmonic nanopore shows great potential as a highly sensitive SERS platform for detecting molecule transport and paves the way for single molecule probing.

Importance of Au nanostructures in CO2 electrochemical reduction reaction.

Electrochemical conversion of CO2 into fuels is a promising means to solve greenhouse effect and recycle chemical energy. However, the CO2 reduction reaction (CO2RR) is limited by the high overpotential, slow kinetics and the accompanied side reaction of hydrogen evolution reaction. Au nanocatalysts exhibit high activity and selectivity toward the reduction of CO2 into CO. Here, we explore the Faradaic efficiency (FE) of CO2RR catalyzed by 50 nm gold colloid and trisoctahedron. It is found that the maximum FE for CO formation on Au trisoctahedron reaches 88.80% at -0.6 V, which is 1.5 times as high as that on Au colloids (59.04% at -0.7 V). The particle-size effect of Au trisoctahedron has also been investigated, showing that the FE for CO decreases almost linearly to 62.13% when the particle diameter increases to 100 nm. The X-ray diffraction characterizations together with the computational hydrogen electrode (CHE) analyses reveal that the (2 2 1) facets on Au trisoctahedron are more feasible than the (1 1 1) facets on Au colloids in stabilizing the critical intermediate COOH*, which are responsible for the higher FE and lower overpotential observed on Au trisoctahedron.

Nanochannel-Ion Channel Hybrid Device for Ultrasensitive Monitoring of Biomolecular Recognition Events.

We propose an in situ and label-free method for detection of biomolecular recognition events by use of a nanochannel-ion channel hybrid device integrated with an electrochemical detector. The aptamer is first immobilized on the outer surface of the nanochannel-ion channel hybrid. Its binding with target thrombin in solution considerably regulates the mass-transfer behavior of the device owing to the varied surface charge density and effective channel size. Via the electrochemical detector, the changed mass-transport property can be monitored in real time, which enables in situ and label-free detection of thrombin-aptamer recognition. The solution pH has a significant influence on detection sensitivity. Under optimal pH conditions, a detection limit as low as 0.22 fM thrombin can be achieved, which is much lower than most reported work. The present nanofluidic device provides a simple, ultrasensitive, and label-free platform for monitoring biomolecular recognition events, which would hold great potential in exploring the functions and reaction mechanisms of biomolecules in living systems.

Energy Level Engineering of MoS2 by Transition-Metal Doping for Accelerating Hydrogen Evolution Reaction.

Water-splitting devices for hydrogen generation through electrolysis (hydrogen evolution reaction, HER) hold great promise for clean energy. However, their practical application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. We previously reported that HER can be largely enhanced through finely tuning the energy level of molybdenum sulfide (MoS2) by hot electron injection from plasmonic gold nanoparticles. Under this inspiration, herein, we propose a strategy to improve the HER performance of MoS2 by engineering its energy level via direct transition-metal doping. We find that zinc-doped MoS2 (Zn-MoS2) exhibits superior electrochemical activity toward HER as evidenced by the positively shifted onset potential to -0.13 V vs RHE. A turnover of 15.44 s-1 at 300 mV overpotential is achieved, which by far exceeds the activity of MoS2 catalysts reported. The large enhancement can be attributed to the synergistic effect of electronic effect (energy level matching) and morphological effect (rich active sites) via thermodynamic and kinetic acceleration, respectively. This design opens up further opportunities for improving electrocatalysts by incorporating promoters, which broadens the understanding toward the optimization of electrocatalytic activity of these unique materials.