Noh Soo Han

Defect states of ZnO nanoparticles: Discrimination by time-resolved photoluminescence spectroscopy

ZnO nanoparticles with different shapes and sizes were prepared by changing coordinating ligands. Hexagonal cones presented UV and green (∼500 nm) emissions, which originated from excitons and defects, respectively. Oxygen vacancies were found to be major defects in the hexagonal cones. Blue emission at ∼440 nm was observed for hexagonal plates, and analyses of time-resolved photoluminescence spectra showed that two transitions were responsible for this blue emission, because transitions from Zni to the valence band (430 nm) and from Zni to VZn (480 nm) were distinguished by emission wavelengths and lifetimes. The visible emissions from defects were related to the roles of coordinating ligands.

An oxygen-vacancy rich 3D novel hierarchical MoS2/BiOI/AgI ternary nanocomposite: enhanced photocatalytic activity through photogenerated electron shuttling in a Z-scheme manner

An oxygen-vacancy rich, bismuth oxyiodide-based Z-scheme 3D hierarchical MoS2/BiOI/AgI ternary nanocomposite photocatalyst was fabricated using a simple precipitation process in ethylene glycol and water. The presence of oxygen-vacancies in BiOI and the two-dimensional nature of molybdenum disulfides in the composite prolongs the charge carrier lifetime through a Z-scheme system and enhances the performance of the photocatalyst for the degradation of rhodamine B. On the basis of efficient separation of photoexcited electron-hole pairs, a mechanism is proposed whereby MoS2 and oxygen vacancy states increase charge carrier lifetimes and improve the photocatalytic activity. The Z-scheme mechanism of the photocatalysis is consistent with the results of static and time-resolved photoluminescence, scavenging, and terephthalic acid photoluminescence experiments. Among the as-synthesized photocatalysts, the one containing 2 wt% of MoS2 in a composite of MoS2/BiOI/AgI exhibited the highest photocatalytic activity towards rhodamine B degradation, and its activity was 7 and 16 times higher than that of BiOI/AgI and BiOI, respectively. Degradation of phenol, the colorless model pollutant, was studied to confirm the visible-light photocatalytic performance of the MoS2/BiOI/AgI composite. This easily fabricated Z-scheme based MoS2/BiOI/AgI composite exhibits promising photocatalytic activity and will be useful for potential applications in energy and environmental areas.

Light–Matter Interactions in Cesium Lead Halide Perovskite Nanowire Lasers

Light-matter interactions in inorganic perovskite nanolasers are investigated using single-crystalline cesium lead halide (CsPbX3, X = Cl, Br, and I) nanowires synthesized by the chemical vapor transport method. The perovskite nanowires exhibit a uniform growth direction, smooth surfaces, straight end facets, and homogeneous composition distributions. Lasing occurs in the perovskite nanowires at low thresholds (3 μJ/cm(2)) with high quality factors (Q = 1200-1400) under ambient atmospheric environments. The wavelengths of the nanowire lasers are tunable by controlling the stoichiometry of the halide, allowing the lasing of the inorganic perovskite nanowires from blue to red. The unusual spacing of the Fabry-Pérot modes suggests strong light-matter interactions in the reduced mode volume of the nanowires, while the polarization of the lasing indicates that the Fabry-Pérot modes belong to the same fundamental transverse mode. The dispersion curve of the exciton-polariton model suggests that the group refractive index of the polariton is significantly enhanced.

Modulation of charge carrier pathways in CdS nanospheres by integrating MoS2 and Ni2P for improved migration and separation toward enhanced photocatalytic hydrogen evolution

The photocatalytic hydrogen evolution reaction using semiconductor nanostructures has received considerable attention in tackling energy and pollution problems. Although several semiconductor photocatalysts have been developed, materials satisfactory in all aspects (e.g., economical and eco-friendly with high efficiency) are still to be developed. Herein, a new and efficient noble-metal-free CdS/MoS2@Ni2P ternary nanohybrid photocatalyst is prepared using a combined hydrothermal and metal–organic framework template strategy. The designed nanostructures show an appealing hydrogen evolution rate, which is 69.29-fold higher than the bare CdS nanostructures and almost 6-fold higher than the CdS–Pt nanocomposites, with an apparent quantum efficiency of 24.4%. Furthermore, the rate enhancement factor of photocatalytic hydrogen evolution in the presence of MoS2 and Ni2P on CdS is much larger than that of several cocatalyst-modified CdS nanostructures reported earlier. The enhanced photocatalytic hydrogen evolution rate is attributed to better migration and separation efficiency in CdS/MoS2@Ni2P than bare CdS, which is supported by photoluminescence, dynamics, photocurrent, and impedance studies. We anticipate that the work presented here may open up new insights for the utilization of low-cost CdS/MoS2@Ni2P hybrid nanostructures as a substitute for noble metals for effective photocatalytic hydrogen evolution.

Unexpected Size Effect Observed in ZnO-Au Composite Photocatalysts

Semiconductor-metal nanocomposites prepared with well-defined gold nanoclusters, such as Au25, Au144, and Au807, showed size-dependent photocatalytic activities for the reduction of nile blue and azobenzene. Whereas the photoreduction of nile blue was directly related with the charge separation and transfer rate from the photoexcited ZnO to gold nanoclusters, the photoreaction of azobenzene showed unexpected size effect with a clear threshold. Mechanistic investigations revealed that the photoreduction of azobenzene proceeded via a proton-coupled electron transfer process. The photocatalytic activity of the ZnO-Au nanocomposites was also dependent on the excitation intensity, demonstrating that the multielectron/multiproton process was controlled by the charge separation and transfer in the nanocomposites.

Blue luminescence of dendrimer-encapsulated gold nanoclusters.

Direct evidence for the blue luminescence of gold nanoclusters encapsulated inside hydroxyl-terminated polyamidoamine (PAMAM) dendrimers was provided by spectroscopic studies as well as by theoretical calculations. Steady-state and time-resolved spectroscopic studies showed that the luminescence of the gold nanoclusters consisted largely of two electronic transitions. Theoretical calculations indicate that the two transitions are attributed to the different sizes of the gold nanoclusters (Au8 and Au13). The luminescence of the gold nanoclusters was clearly distinguished from that of the dendrimers.

Self-Assembled Tb3+ Complex Probe for Quantitative Analysis of ATP during Its Enzymatic Hydrolysis via Time-Resolved Luminescence in Vitro and in Vivo

To more accurately assess the pathways of biological systems, a probe is needed that may respond selectively to adenosine triphosphate (ATP) for both in vitro and in vivo detection modes. We have developed a luminescence probe that can provide real-time information on the extent of ATP, ADP, and AMP by virtue of the luminescence and luminescence lifetime observed from a supramolecular polymer based on a C3 symmetrical terpyridine complex with Tb3+ (S1-Tb). The probe shows remarkable selective luminescence enhancement in the presence of ATP compared to other phosphate-displaying nucleotides including adenosine diphosphate (ADP), adenosine monophosphate (AMP), guanosine triphosphate (GTP), thymidine triphosphate (TTP), H2PO4- (Pi), and pyrophosphate (PPi). In addition, the time-resolved luminescence lifetime and luminescence spectrum of S1-Tb could facilitate the quantitative measurement of the exact amount of ATP and similarly ADP and AMP within living cells. The time-resolved luminescence lifetime of S1-Tb could also be used to quantitatively monitor the amount of ATP, ADP, and AMP in vitro following the enzymatic hydrolysis of ATP. The long luminescence lifetime, which was observed into the millisecond range, makes this S1-Tb-based probe particularly attractive for monitoring biological ATP levels in vivo, because any short lifetime background fluorescence arising from the complex molecular environment may be easily eliminated.