Woonbae Sohn

Wafer-scale transferable molybdenum disulfide thin-film catalysts for photoelectrochemical hydrogen production

We demonstrate that wafer-scale, transferable, and transparent thin-film catalysts based on MoS2, which consists of cheap and earth abundant elements, can provide a low onset potential of 1 mA cm−2 at 0.17 V versus a reversible hydrogen electrode and the high photocurrent density of 24.6 mA cm−2 at 0 V for a p-type Si photocathode. c-Domains with vertically stacked (100) planes in the transferable 2H-MoS2 thin films, which are grown via a thermolysis method, act as active sites for the hydrogen evolution reaction, and photogenerated electrons are efficiently transported through the n-MoS2/p-Si heterojunction.

Dominance of Plasmonic Resonant Energy Transfer over Direct Electron Transfer in Substantially Enhanced Water Oxidation Activity of BiVO4 by Shape-Controlled Au Nanoparticles

The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape-controlled Au NPs on bismuth vanadate (BiVO4 ) are studied, and a largely enhanced photoactivity of BiVO4 is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO4 achieves 2.4 mA cm-2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO4 . It is the highest value among the previously reported plasmonic Au NPs/BiVO4 . Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape-controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells.

Drastically enhanced hydrogen evolution activity by 2D to 3D structural transition in anion-engineered molybdenum disulfide thin films for efficient Si-based water splitting photocathodes

We synthesized transferrable and transparent anion-engineered molybdenum disulfide thin-film catalysts through a simple thermolysis method by using [(NH4)2MoS4] solution and powder precursors with different sulphur/phosphorus weight ratios. The synthesized sulphur-doped molybdenum phosphide (S:MoP) thin film changed from a two-dimensional van der Waals structure to a three-dimensional hexagonal structure by introduction of phosphorus atoms in the MoS2 thin film. The S:MoP thin film catalyst, which is composed of cheap and earth abundant elements, could provide the lowest onset potential and the highest photocurrent density for planar p-type Si photocathodes. The density functional theory calculations indicate that the surface of S:MoP thin films absorb hydrogen better than that of MoS2 thin films. The structurally engineered thin film catalyst facilitates the easy transfer of photogenerated electrons from the p-Si light absorber to the electrolyte. Anion-engineering of the MoS2 thin film catalyst would be an efficient way to enhance the catalytic activity for photoelectrochemical water splitting.

Chemically fluorinated graphene oxide for room temperature ammonia detection at ppb levels

Chemoresistive gas sensors based on two-dimensional (2D) materials including graphene-based materials have attracted significant research interest owing to their potential use in next-generation technologies including the Internet of Things (IoT). The functionalization of 2D materials is considered as a key strategy to achieve superior gas sensing properties such as high selectivity, high sensitivity, and reversible response and recovery, because it can modulate the chemical and electrical properties of 2D materials for more efficient gas sensing. Herein, we present a facile solution process and the room temperature gas sensing properties of chemically fluorinated graphene oxide (CFGO). The CFGO sensors exhibit improved sensitivity, selectivity, and reversibility upon exposure to NH3 with a significantly low theoretical detection limit of ∼6 ppb at room temperature in comparison to NO2 sensing properties. The effect of fluorine doping on the sensing mechanism is examined by first-principles calculations based on density functional theory. The calculations reveal that the fluorine dopant changes the charge distribution on the oxygen containing functional groups in graphene oxide, resulting in the preferred selective adsorption and desorption of NH3 molecules. We believe that the remarkable NH3 sensing properties of CFGO and investigation by first-principles calculations would enlarge the possibility of functionalized 2D materials for practical gas sensing applications such as the IoT.

Toward High-Performance Hematite Nanotube Photoanodes: Charge-Transfer Engineering at Heterointerfaces

Vertically ordered hematite nanotubes are considered to be promising photoactive materials for high-performance water-splitting photoanodes. However, the synthesis of hematite nanotubes directly on conducting substrates such as fluorine-doped tin oxide (FTO)/glass is difficult to be achieved because of the poor adhesion between hematite nanotubes and FTO/glass. Here, we report the synthesis of hematite nanotubes directly on FTO/glass substrate and high-performance photoelectrochemical properties of the nanotubes with NiFe cocatalysts. The hematite nanotubes are synthesized by a simple electrochemical anodization method. The adhesion of the hematite nanotubes to the FTO/glass substrate is drastically improved by dipping them in nonpolar cyclohexane prior to postannealing. Bare hematite nanotubes show a photocurrent density of 1.3 mA/cm(2) at 1.23 V vs a reversible hydrogen electrode, while hematite nanotubes with electrodeposited NiFe cocatalysts exhibit 2.1 mA/cm(2) at 1.23 V which is the highest photocurrent density reported for hematite nanotubes-based photoanodes for solar water splitting. Our work provides an efficient platform to obtain high-performance water-splitting photoanodes utilizing earth-abundant hematite and noble-metal-free cocatalysts.

Growth mechanism of Si3N4 nanowires from amorphous Si3N4 powders synthesized by low-temperature vapor-phase reaction

A novel synthesis method to prepare Si3N4 nanowires from amorphous silicon nitride (a-Si3N4) powder synthesized by a low-temperature vapor-phase reaction method was investigated. Highly crystalline α-Si3N4 nanowires were synthesized by heat treatment of the a-Si3N4 powder under ammonia atmosphere. The surface of the nanowires was smooth and clean without any attached particles. The thickness of the nanowires was in the range of ∼200–300 nm with lengths of tens of micrometers. The nucleation of nanowires from the reaction between SiO and N2 occurs on the surface of the a-Si3N4 powder, which is covered by a thin layer of SiO2, and the nanowires grow from the rearrangement of Si and N atoms of the a-Si3N4 powder. The reduction of SiO2 to SiO by ammonia was promoted in the presence of a Ni catalyst; therefore, the growth was observed at a lower temperature when Ni was added to the a-Si3N4 powder than in the presence of added Fe. The growth of α-Si3N4 nanowires occurs along the [100, 101] direction and follows the vapor–solid–solid mechanism.

p–p Heterojunction of Nickel Oxide-Decorated Cobalt Oxide Nanorods for Enhanced Sensitivity and Selectivity toward Volatile Organic Compounds

The utilization of p-p isotype heterojunctions is an effective strategy to enhance the gas sensing properties of metal-oxide semiconductors, but most previous studies focused on p-n heterojunctions owing to their simple mechanism of formation of depletion layers. However, a proper choice of isotype semiconductors with appropriate energy bands can also contribute to the enhancement of the gas sensing performance. Herein, we report nickel oxide (NiO)-decorated cobalt oxide (Co3O4) nanorods (NRs) fabricated using the multiple-step glancing angle deposition method. The effective decoration of NiO on the entire surface of Co3O4 NRs enabled the formation of numerous p-p heterojunctions, and they exhibited a 16.78 times higher gas response to 50 ppm of C6H6 at 350 °C compared to that of bare Co3O4 NRs with the calculated detection limit of approximately 13.91 ppb. Apart from the p-p heterojunctions, increased active sites owing to the changes in the orientation of the exposed lattice surface and the catalytic effects of NiO also contributed to the enhanced gas sensing properties. The advantages of p-p heterojunctions for gas sensing applications demonstrated in this work will provide a new perspective of heterostructured metal-oxide nanostructures for sensitive and selective gas sensing.

Facile synthesis of CsPbBr3/PbSe composite clusters

Abstract In this work, CsPbBr3 and PbSe nanocomposites were synthesized to protect perovskite material from self-enlargement during reaction. UV absorption and photoluminescence (PL) spectra indicate that the addition of Se into CsPbBr3 quantum dots modified the electronic structure of CsPbBr3, increasing the band gap from 2.38 to 2.48 eV as the Cs:Se ratio increased to 1:3. Thus, the emission color of CsPbBr3 perovskite quantum dots was modified from green to blue by increasing the Se ratio in composites. According to X-ray diffraction patterns, the structure of CsPbBr3 quantum dots changed from cubic to orthorhombic due to the introduction of PbSe at the surface. Transmission electron microscopy and X-ray photoemission spectroscopy confirmed that the atomic distribution in CsPbBr3/PbSe composite clusters is uniform and the composite materials were well formed. The PL intensity of a CsPbBr3/PbSe sample with a 1:1 Cs:Se ratio maintained 50% of its initial intensity after keeping the sample for 81 h in air, while the PL intensity of CsPbBr3 reduced to 20% of its initial intensity. Therefore, it is considered that low amounts of Se could improve the stability of CsPbBr3 quantum dots.

Decoration of metal oxide surface with {111} form Au nanoparticles using PEGylation

The benefit of introducing gold nanoparticles is due to the plasmon relaxation process. The plasmon decay induces various phenomena such as near-field enhancement, hot electron injection, and resonance energy transfer. Shape-controlled octahedral gold nanoparticles can maximize the efficiency of these processes. For practical purposes, a high-coverage decoration method, comparable to physical vapor deposition on a metal oxide semiconductor nanostructure, is indispensable. However, the ligand exchange reaction to attach octahedral gold nanoparticles is limited in aqueous solution due to the inactivity of the gold (111) surface as a result of a densely-packed cetyltrimethylammonium bilayer structure. Herein, we report a controllable high-coverage surface decoration method of octahedral gold nanoparticles on the targeted semiconductor nanostructures via phase transfer by an organic medium with thiolated-polyethylene glycol. Our results deliver an innovative platform for future plasmonic gold nanoparticle applications.

Efficient Water Splitting Cascade Photoanodes with Ligand-Engineered MnO Cocatalysts

Abstract The band edge positions of semiconductors determine functionality in solar water splitting. While ligand exchange is known to enable modification of the band structure, its crucial role in water splitting efficiency is not yet fully understood. Here, ligand‐engineered manganese oxide cocatalyst nanoparticles (MnO NPs) on bismuth vanadate (BiVO4) anodes are first demonstrated, and a remarkably enhanced photocurrent density of 6.25 mA cm−2 is achieved. It is close to 85% of the theoretical photocurrent density (≈7.5 mA cm−2) of BiVO4. Improved photoactivity is closely related to the substantial shifts in band edge energies that originate from both the induced dipole at the ligand/MnO interface and the intrinsic dipole of the ligand. Combined spectroscopic analysis and electrochemical study reveal the clear relationship between the surface modification and the band edge positions for water oxidation. The proposed concept has considerable potential to explore new, efficient solar water splitting systems.