Lawrence Yoon Suk Lee

Significant enhancement in photocatalytic reduction of water to hydrogen by Au/Cu2ZnSnS4 nanostructure

Enhanced photocatalytic activities by Au core Novel Au/Cu2 ZnSnS4 core/shell nanoparticles (NPs) are synthesized for the first time via wet chemistry approach. The insertion of Au core into CZTS NPs dramatically enhances light absorption due to surface plasmon resonance effect, especially in the Vis-NIR region. Au/CZTS core/shell NPs show much higher photocatalytic activities for hydrogen evolution compared with other CZTS nanostructures.

Morphology-Controlled Synthesis of Au/Cu2FeSnS4 Core–Shell Nanostructures for Plasmon-Enhanced Photocatalytic Hydrogen Generation

Copper-based chalcogenides of earth-abundant elements have recently arisen as an alternate material for solar energy conversion. Cu2FeSnS4 (CITS), a quaternary chalcogenide that has received relatively little attention, has the potential to be developed into a low-cost and environmentlly friendly material for photovoltaics and photocatalysis. Herein, we report, for the first time, the synthesis, characterization, and growth mechanism of novel Au/CITS core-shell nanostructures with controllable morphology. Precise manipulations in the core-shell dimensions are demonstrated to yield two distinct heterostructures with spherical and multipod gold nanoparticle (NP) cores (Au(sp)/CITS and Au(mp)/CITS). In photocatalytic hydrogen generation with as-synthesized Au/CITS NPs, the presence of Au cores inside the CITS shell resulted in higher hydrogen generation rates, which can be attributed to the surface plasmon resonance (SPR) effect. The Au(sp)/CITS and Au(mp)/CITS core-shell NPs enhanced the photocatalytic hydrogen generation by about 125% and 240%, respectively, compared to bare CITS NPs.

Ferrocenylalkylthiolate labeling of defects in alkylthiol self-assembled monolayers on gold

Coverage defects in alkylthiol self-assembled monolayers (SAMs) are critically important to function related to electron transfer from soluble redox probes. There is therefore a need for an accurate and direct measurement of the number and type of coverage defect in a range of SAMs. Ferrocenyldodecanethiol (FcC12SH) has been assessed as an electrochemically-addressable label of coverage defects. It is shown that short time exposure of a SAM to FcC12SH leads to a quantifiable Fc coverage (ΓFc), with ΓFc < 1% readily measurable. The voltammetric signature of FcC12SH label is also able to differentiate types of defect in a given SAM. A number of SAM preparation conditions are assessed for the density and type of coverage defect. This labeling method therefore will be a useful tool for research into SAM property–function relationships.

Cu 2 ZnSnS 4 /MoS 2 -Reduced Graphene Oxide Heterostructure: Nanoscale Interfacial Contact and Enhanced Photocatalytic Hydrogen Generation

Hydrogen generation from water using noble metal-free photocatalysts presents a promising platform for renewable and sustainable energy. Copper-based chalcogenides of earth-abundant elements, especially Cu2ZnSnS4 (CZTS), have recently arisen as a low-cost and environment-friendly material for photovoltaics and photocatalysis. Herein, we report a new heterostructure consisting of CZTS nanoparticles anchored onto a MoS2-reduced graphene oxide (rGO) hybrid. Using a facile two-step method, CZTS nanoparticles were in situ grown on the surface of MoS2-rGO hybrid, which generated high density of nanoscale interfacial contact between CZTS and MoS2-rGO hybrid. The photoexcited electrons of CZTS can be readily transported to MoS2 through rGO backbone, reducing the electron-hole pair recombination. In photocatalytic hydrogen generation under visible light irradiation, the presence of MoS2-rGO hybrids enhanced the hydrogen production rate of CZTS by 320%, which can be attributed to the synergetic effect of increased charge separation by rGO and more catalytically active sites from MoS2. Furthermore, this CZTS/MoS2-rGO heterostructure showed much higher photocatalytic activity than both Au and Pt nanoparticle-decorated CZTS (Au/CZTS and Pt/CZTS) photocatalysts, indicating the MoS2-rGO hybrid is a better co-catalyst for photocatalytic hydrogen generation than the precious metal. The CZTS/MoS2-rGO system also demonstrated stable photocatalytic activity for a continuous 20 h reaction.

Dominant Factors Governing the Electron Transfer Kinetics and Electrochemical Biosensing Properties of Carbon Nanofiber Arrays

Carbon-based electrodes have been widely used in electroanalysis for more than half a century, but the factors governing the heterogeneous electron-transfer (HET) rate are still unclear. The effects of the exposed edge plane site density, inherent resistance of the carbon electrode, and adjustable resistors on the HET kinetics of several outer- and inner-sphere redox couples including [Fe(CN)6]3-/4-, Ru(NH3)63+/2+, Fe3+/2+, dopamine, ascorbic acid, and uric acid are investigated using three kinds of carbon electrodes composed of core-shell quasi-aligned nanofiber arrays (QANFAs). The internal resistance is found to be a key factor affecting the HET kinetics and electrochemical biosensing properties. The electrodes exhibit high selectivity and sensitivity in dopamine detection in the presence of ascorbic acid and uric acid. In addition to the promising application to electrochemical biosensing, the core-shell TiC/C QANFAs encompassing a highly electroactive carbon shell and conductive TiC core provide insights into the design and construction of the ideal carbon electrode.

Tailored transition metal-doped nickel phosphide nanoparticles for the electrochemical oxygen evolution reaction (OER)

Foreign transition metals are doped into the hexagonal nickel phosphide structure through a simple and facile bottom-up wet-chemical synthesis process via stabilization with oleylamine, trioctylphosphine (TOP), and trioctylphosphine oxide (TOPO): the as-prepared transition metal-doped nickel phosphide nanoparticles show a high level of doping but create no significant distortion of the crystal structure and morphology against pristine nickel phosphide nanoparticles, which exhibit excellent activity in the electrochemical oxygen evolution reaction (OER), having overpotential as small as 330 mV at 20 mA cm-2 with a low Tafel slope value of 39 mV dec-1.

Recent Development in Water Oxidation Catalysts Based on Manganese and Cobalt Complexes

Energy directly harvested from sunlight offers an ultimate method of meeting the needs for clean energy with minimal impact on our environment. Intensive research efforts are currently being put on the development of efficient conversion system that can transform solar energy into fuel via light-driven water splitting to generate H2 and O2, learning from Nature’s photosynthesis to collect and store solar energy in chemical bonds. Especially, the development of efficient water oxidation catalysts is one of the key issues for achieving artificial photosynthetic devices. From a practical point of view, it is highly desirable to replace noble metal catalysts, which have been quite successful so far, by earth-abundant metal catalysts. In recent years, there has been noticeable progress in the development of water oxidation catalysts (WOCs) based on earth-abundant metals. This review chapter covers the most significant achievements in WOCs based on manganese and cobalt complexes, with emphasis on recent developments in the last three years.