Jun Min Suh

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.

Magnetically retrievable nanocomposite adorned with Pd nanocatalysts: efficient reduction of nitroaromatics in aqueous media

Herein, we describe the fabrication of a magnetically retrievable nanocomposite adorned with highly active Pd nanoparticles (NPs) (MRN-Pd), which is useful for the efficient reduction of nitroaromatics in aqueous solution. The polymerization of pyrrole as the monomer in the presence of Pd salt and iron nanopowder generates Pd nanocatalysts and localizes the resultant Pd NPs discretely and uniformly on the polypyrrole framework comprising strongly magnetic MRN-Pd catalyst without the need for any reducing agent. The nitrogen-containing polymer enhances the interaction between the decorated Pd nanocatalysts and the polymer scaffold, endowing stability to the Pd NPs and maintaining their monodispersity. This prevents the possible aggregation of the MRN-Pd catalyst and promotes its reactivity for fast reduction processes. The unique features exhibited by the MRN-Pd catalyst result in excellent catalytic activity for the expeditious reduction of nitroaromatics under green reaction conditions at room temperature. Furthermore, the pronounced magnetic characteristics of the MRN-Pd catalyst allow its convenient separation and recycling from the reaction mixture. In addition, the MRN-Pd catalyst can be completely separated and recycled using a small magnet and reused for seven consecutive cycles of high-yield reduction of nitrobenzene (99–95%) in water, thus affording a highly retrievable and sustainable magnetic nanocomposite catalyst suitable for environmentally friendly processes. The MRN-Pd catalyst also presents high catalytic activity in other typical catalytic transformations requiring Pd nanocatalysts, such as the Suzuki and Heck cross-coupling reactions.

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.

Substantially enhanced front illumination photocurrent in porous SnO2 nanorods/networked BiVO4 heterojunction photoanodes

BiVO4 is a promising photoanode for photoelectrochemical applications owing to its suitable band edge position for oxygen evolving reactions. High photocurrent under front illumination is very much essential to design tandem structures with a wireless configuration. However, the performance of BiVO4 under front illumination is limited due to poor charge transport properties. Here, we show that network-like BiVO4 coupled with porous SnO2 nanorods (NRs) is a promising model to enhance the front illumination performance. A very high photocurrent density of 5.6 mA cm−2 and 5.5 mA cm−2 has been obtained from the front and back illumination at 1.23 V vs. the reversible hydrogen electrode, respectively. We demonstrate that the appropriate nanostructuring of SnO2 NRs/BiVO4 is the underlying technology to tune the performance under directional illumination. The SnO2 NRs/BiVO4 exhibits a maximum incident photon to current efficiency of ∼80% under front and back illumination. A systematic study reveals that the optimized network like BiVO4 coated on porous SnO2 NRs synergistically boosts both the charge separation and transfer efficiencies of the photoanode resulting in a significantly high photocurrent for illumination on either side. This work provides a direction to achieve enhanced photocurrent during front and back side illumination in order to realize a wireless tandem configuration.

Facile synthesis of monodispersed Pd nanocatalysts decorated on graphene oxide for reduction of nitroaromatics in aqueous solution

We synthesized the reproducible heterogeneous catalyst of graphene oxide (GO)-supported palladium nanoparticles (NPs) via a simple and green process. The structure, morphology and physicochemical properties of the synthesized heterogeneous catalyst were characterized by the latest techniques such as high-resolution transmission electron microscopy (TEM), scanning TEM, energy-dispersive X-ray spectroscopy, X-ray diffraction analysis, and X-ray photoelectron spectroscopy. The GO-supported Pd NPs (Pd/GO nanocatalyst) exhibited excellent catalytic activity for the reduction of nitroaromatics to aminoaromatics in aqueous sodium borohydride. The nitroaromatics were converted to corresponding aminoaromatics with high yields (up to 99%) using Pd/GO nanocatalyst in aqueous solution. The hybrid heterogeneous catalyst showed 83% of conversion after six cycles in the reduction of nitrobenzene to aminobenzene. These features ensured the high catalytic activity of the introduced graphene oxide supported Pd nanocatalysts.Graphical abstract

Synthesis of Numerous Edge Sites in MoS2 via SiO2 Nanorods Platform for Highly Sensitive Gas Sensor

The utilization of edge sites in two-dimensional materials including transition-metal dichalcogenides (TMDs) is an effective strategy to realize high-performance gas sensors because of their high catalytic activity. Herein, we demonstrate a facile strategy to synthesize the numerous edge sites of vertically aligned MoS2 and larger surface area via SiO2 nanorod (NRs) platforms for highly sensitive NO2 gas sensor. The SiO2 NRs encapsulated by MoS2 film with numerous edge sites and partially vertical-aligned regions synthesized using simple thermolysis process of [(NH4)2MoS4]. Especially, the vertically aligned MoS2 prepared on 500 nm thick SiO2 NRs (500MoS2) shows approximately 90 times higher gas-sensing response to 50 ppm NO2 at room temperature than the MoS2 film prepared on flat SiO2, and the theoretical detection limit is as low as ∼2.3 ppb. Additionally, it shows reliable operation with reversible response to NO2 gas without degradation at an operating temperature of 100 °C. The use of the proposed facile approach to synthesize vertically aligned TMDs using nanostructured platform can be extended for various TMD-based devices including sensors, water splitting catalysts, and batteries.