Hydrogen evolution reaction (HER) from water through electrocatalysis using cost-effective materials to replace precious Pt catalysts holds great promise for clean energy technologies. In this work we developed a highly active and stable catalyst containing Co doped earth abundant iron pyrite FeS(2) nanosheets hybridized with carbon nanotubes (Fe(1-x)CoxS(2)/CNT hybrid catalysts) for HER in acidic solutions. The pyrite phase of Fe(1-x)CoxS(2)/CNT was characterized by powder X-ray diffraction and absorption spectroscopy. Electrochemical measurements showed a low overpotential of ∼0.12 V at 20 mA/cm(2), small Tafel slope of ∼46 mV/decade, and long-term durability over 40 h of HER operation using bulk quantities of Fe(0.9)Co(0.1)S(2)/CNT hybrid catalysts at high loadings (∼7 mg/cm(2)). Density functional theory calculation revealed that the origin of high catalytic activity stemmed from a large reduction of the kinetic energy barrier of H atom adsorption on FeS(2) surface upon Co doping in the iron pyrite structure. It is also found that the high HER catalytic activity of Fe(0.9)Co(0.1)S(2) hinges on the hybridization with CNTs to impart strong heteroatomic interactions between CNT and Fe(0.9)Co(0.1)S(2). This work produces the most active HER catalyst based on iron pyrite, suggesting a scalable, low cost, and highly efficient catalyst for hydrogen generation.

Raman spectroscopy, which is based on the inelastic scattering of photons by chemical entities, has been successfully utilized for the investigation of adsorbed molecules on surfaces, [1][2][3] although the low cross section limits its applications.Surface-enhanced Raman scattering (SERS) has drawn a lot of attention since its discovery in 1974, [4] primarily because it can greatly enhance the normally weak Raman signal and thereby facilitate the convenient identification of the vibrational signatures of molecules in chemical and biological systems. [5] Recently, the observation of single-molecule Raman scattering has further enhanced the Raman detection sensitivity limit and widened the scope of SERS for sensor applications. [6,7] Although SERS effects can be achieved simply by exploiting the electromagnetic resonance properties of roughened surfaces or nanoparticles of Au or Ag, the fabrication of reliable SERS substrates with uniformly high enhancement factors remains the focus of much research. Spraying Au or Ag colloids on a substrate leads to an extremely high SERS signal at some local 'hot-junctions'; [6][7][8] however, it is not easy to achieve a reliable, stable, and uniform SERS signal spanning a wide dynamical range using this method. Van Duyne and coworkers have used nanosphere lithography, [9] while Liu andLee exploited soft lithography, [10] in order to fabricate Ag nanoparticle arrays with high SERS activity and improved uniformity. Käll and co-workers have shown theoretically that the effective Raman cross section of a molecule placed between two metal nanoparticles can be enhanced by more than 12 orders of magnitude.[11] Such enhancement is likely to be related to the 'hot-junctions' observed in some SERS experiments. Several theoretical groups have also investigated field enhancement for SERS from metal nanoparticle arrays. [12][13][14] Specifically, García-Vidal and Pendry proposed that very localized plasmon modes, created by strong electromagnetic coupling between two adjacent metallic objects, dominate the SERS response in an array of nanostructures.[12] The interparticle-coupling-induced enhancement was attributed to the broadening of the plasmon resonance peak because the probability of the resonance covering both the excitation wavelength and the Raman peak increases with its width. They calculated the average enhancement factor over the surfaces of an array of infinitely long Ag nanorods with semicircular cross sections, and showed that significant near-field interaction occurs between adjacent nanorods when the gap between the nanorods reaches half the value of their diameter. Other groups have studied the dependence of the enhancement factor on the gap between adjacent nanoparticles on a SERS active substrate. For example, Gunnarsson et al. investigated SERS on ordered Ag nanoparticle arrays with an interparticle gap above 75 nm. [15] Lee and co-workers were able to achieve the temperature-controlled variation of interparticle gaps between Ag nanoparticles embedded in a polymer membra...

Detecting bacteria in clinical samples without using time-consuming culture processes would allow rapid diagnoses. such a culture-free detection method requires the capture and analysis of bacteria from a body fluid, which are usually of complicated composition. Here we show that coating Ag-nanoparticle arrays with vancomycin (Van) can provide label-free analysis of bacteria via surface-enhanced Raman spectroscopy (sERs), leading to a ~1,000-fold increase in bacteria capture, without introducing significant spectral interference. Bacteria from human blood can be concentrated onto a microscopic Van-coated area while blood cells are excluded. Furthermore, a Van-coated substrate provides distinctly different sERs spectra of Van-susceptible and Van-resistant Enterococcus, indicating its potential use for drug-resistance tests. our results represent a critical step towards the creation of sERs-based multifunctional biochips for rapid culture-and label-free detection and drug-resistant testing of microorganisms in clinical samples.

Rapid and accurate diagnosis for pathogens and their antibiotic susceptibility is critical for controlling bacterial infections. Conventional methods for determining bacterium's sensitivity to antibiotic depend mostly on measuring the change of microbial proliferation in response to the drug. Such “biological assay” inevitably takes time, ranging from days for fast-growing bacteria to weeks for slow-growers. Here, a novel tool has been developed to detect the “chemical features” of bacterial cell wall that enables rapid identification of drug resistant bacteria within hours. The surface-enhanced Raman scattering (SERS) technique based on our newly developed SERS-active substrate was applied to assess the fine structures of the bacterial cell wall. The SERS profiles recorded by such a platform are sensitive and stable, that could readily reflect different bacterial cell walls found in Gram-positive, Gram-negative, or mycobacteria groups. Moreover, characteristic changes in SERS profile were noticed in the drug-sensitive bacteria at the early period (i.e., ∼1 hr) of antibiotic exposure, which could be used to differentiate them from the drug-resistant ones. The SERS-based diagnosis could be applied to a single bacterium. The high-speed SERS detection represents a novel approach for microbial diagnostics. The single-bacterium detection capability of SERS makes possible analyses directly on clinical specimen instead of pure cultured bacteria.

This study describes a strategy for developing ultra-high-responsivity broadband Si-based photodetectors (PDs) using ZnO nanorod arrays (NRAs). The ZnO NRAs grown by a low-temperature hydrothermal method with large growth area and high growth rate absorb the photons effectively in the UV region and provide refractive index matching between Si and air for the long-wavelength region, leading to 3 and 2 orders of magnitude increase in the responsivity of Si metal-semiconductor-metal PDs in the UV and visible/NIR regions, respectively. Significantly enhanced performances agree with the theoretical analysis based on the finite-difference time-domain method. These results clearly demonstrate that Si PDs combined with ZnO NRAs hold high potential in next-generation broadband PDs.

A combined process of electropolishing, focused-ion-beam lithography, and controlled anodization is used to fabricate anodic alumina films with ordered nanochannels. The ion beam is used to create a hexagonally close-packed lattice of concaves on a polished aluminum surface and the concaves act as pinning points for guiding the growth of nanochannels in the following anodization step. By carefully matching the lattice constant (100 nm) with the anodization voltage, ordered nanochannels with aspect ratio of ∼100 are fabricated. The effects of the ion dose and its corresponding depth of the concaves on the ordering of the nanochannel array are investigated and a minimum depth of 3 nm is found to be necessary for effective guidance of the growth of ordered nanochannels.

Rapid bacterial antibiotic susceptibility test (AST) and minimum inhibitory concentration (MIC) measurement are important to help reduce the widespread misuse of antibiotics and alleviate the growing drug-resistance problem. We discovered that, when a susceptible strain of Staphylococcus aureus or Escherichia coli is exposed to an antibiotic, the intensity of specific biomarkers in its surface-enhanced Raman scattering (SERS) spectra drops evidently in two hours. The discovery has been exploited for rapid AST and MIC determination of methicillin-susceptible S. aureus and wild-type E. coli as well as clinical isolates. The results obtained by this SERS-AST method were consistent with that by the standard incubation-based method, indicating its high potential to supplement or replace existing time-consuming methods and help mitigate the challenge of drug resistance in clinical microbiology.

Two dimensional magic clusters have been directly observed on the p 3 3p 3 R30 ± reconstructed Ga͞Si(111) surface using scanning tunneling microscopy. The magic numbers are n͑n 1 1͒͞2, where n (2, 3, 4, or 5) is the number of atoms on each side of these triangular clusters with preferred orientation with respect to the substrate. The p 3 3p 3 R30 ± adatom lattice surrounding the magic clusters exhibits characteristic vacancies. A structural model is proposed to account for the cluster orientation and lattice vacancies as well as the extraordinary abundance and stability of the decamers ͑n 4͒. [S0031-9007(98)06520-X] PACS numbers: 68.35.Bs, 61.16.ChMagic clusters, i.e., clusters with enhanced stability at certain sizes, have been intensively studied over the last decade. For magic clusters in free space, many interesting results about their electronic and atomic shell structures are found in the literature [1][2][3][4][5][6]. In contrast, magic clusters supported by a substrate (henceforth referred to as 2D magic clusters) are rarely discussed. Only recently have researchers found indirect evidence of such clusters in a molecular beam scattering experiment [7] and issues related to the stability of clusters on various substrates caught researchers' attention [8,9]. The main difference between free and supported clusters lies in the presence of the supporting substrate for the latter. The geometric constraint and electronic effect exerted by the substrate may or may not destroy the stability of an approaching magic cluster. For example, according to a calculation [8], Na 8 (a magic cluster in free space) retains its intrinsic structure after landing on the insulating NaCl(100) surface, but it spontaneously collapses on the Na(110) surface. Therefore, it is of fundamental interest to search for direct evidence of 2D magic clusters and study the cluster-surroundings interaction that needs not to be considered for magic clusters in free space. The recent interests in 2D magic clusters are also related to emerging attempts to coat surfaces with size-selected clusters [10]. Since the formation of 2D magic clusters is a plausible approach to the creation of this type of novel material, it is important to experimentally demonstrate the existence of 2D magic clusters and understand the conditions and mechanism for their formation.