Je Hyun Bae

Ion flow crossing over a polyelectrolyte diode on a microfluidic chip.

Key evidences are reported for the rectification mechanism of an aqueous ion diode based on polyelectrolytic plugs on a microfluidic chip by monitoring the ion flow crossing over the junction. The ion flow penetrating the polyelectrolyte junction is visualized by employing a fluorescent chemodosimeter, rhodamine B hydrazide and the pH-dependent dye, carboxy-fluorescein. How hysteresis phenomena, exhibited through the nonlinear behavior of the polyelectrolyte diode, are affected by a variety of parameters (e.g., switching potential, scan rate, and electrolyte concentration) is also investigated. The insights and knowledge from this study provide a crucial foundation for ion control at the iontronic diode in the aqueous phase, leading to more advanced aqueous organic computing devices and more diverse applications for microfluidic logic devices.

Effects of adsorption and confinement on nanoporous electrochemistry.

Characteristic molecular dynamics of reactant molecules confined in the space of the nanometer scale augments the frequency of collisions with the electrified surface so that a given faradaic reaction can be enhanced at nanoporous electrodes, the so-called nano-confinement effect. Since this effect is grounded on diffusion inside nanopores, it is predicted that adsorption onto the surface will seriously affect the enhancement by nano-confinement. We experimentally explored the correlation between adsorption and the confinement effect by examining the oxidation of butanol isomers at platinum and gold nanoporous electrodes. The results showed that electrooxidation of 2-butanol, which is a non-adsorption reaction, was enhanced more than that of 1-butanol, which is an adsorption reaction, at nanoporous platinum in acidic media. In contrast, the nanoporous gold electrode, on which 1-butanol is less adsorptive than it is on platinum, enhanced the electrooxidation of 1-butanol greatly. Furthermore, the electrocatalytic activity of nanoporous gold for oxygen reduction reaction was improved so much as to be comparable with that of flat Pt. These findings show that the nano-confinement effect can be appreciable for electrocatalytic oxygen reduction as well as alcohol oxidation unless the adsorption is extensive, and suggests a new strategy in terms of material design for innovative non-noble metal electrocatalysts.

Enhanced electrochemical reactions of 1,4-benzoquinone at nanoporous electrodes

We report that the proton-coupled electron transfer kinetics of 1,4-benzoquinone was significantly enhanced in electrified nanopores in aqueous media. At nanoporous Pt and Au electrodes, the voltammetric behaviour of 1,4-benzoquinone at nanoporous electrodes was clearly distinct from that at flat surfaces. Proton transfer as well as electron transfer kinetics were facilitated in the nanopores by the confinement effect, which indicates all factors originated from the geometric features of nano-scale concave space surrounded by inner walls, suggesting how to utilize nanoporous electrodes for electrocatalysis.

Light-guided electrodeposition of non-noble catalyst patterns for photoelectrochemical hydrogen evolution

Hydrogen is in the lime light as a carbon-free alternative energy source due to its high energy conversion efficiency. Solar-driven water splitting is one of the most promising methods for renewable hydrogen production. However, commercialization of a photoelectrochemical hydrogen production system remains a great challenge. One of the emerging concerns is the development of an inexpensive and transparent catalyst, which does not obstruct the light pathways to the semiconductor electrode. Here we report a non-noble metal electrocatalyst for hydrogen evolution, Ni-Mo, which is directly patterned on amorphous Si (a-Si) by light-guided spatially selective electrodeposition without consecutive photolithography processes. A light pattern is illuminated onto the a-Si using a digital micromirror device to commence the photoelectrochemical deposition. The catalyst patterned by the proposed method not only admits sufficient light to a-Si but also enables long distance carrier transport along the inversion layer, as previously observed in crystalline Si (c-Si) photocathodes. This new electrodeposition method enables mask-free patterning on a-Si and is expected to expedite a lower cost, more efficient, and self-biasing integrated photoelectrochemical water-splitting device.

Nonfaradaic Nanoporous Electrochemistry for Conductometry at High Electrolyte Concentration

Nanoporous electrified surfaces create a unique nonfaradaic electrochemical behavior that is sensitively influenced by pore size, morphology, ionic strength, and electric field modulation. Here, we report the contributions of ion concentration and applied ac frequency to the electrode impedance through an electrical double layer overlap and ion transport along the nanopores. Nanoporous Pt with uniform pore size and geometry (L2-ePt) responded more sensitively to conductivity changes in aqueous solutions than Pt black with poor uniformity despite similar real surface areas and enabled the previously difficult quantitative conductometry measurements at high electrolyte concentrations. The nanopores of L2-ePt were more effective in reducing the electrode impedance and exhibited superior linear responses to not only flat Pt but also Pt black, leading to successful conductometric detection in ion chromatography without ion suppressors and at high ionic strengths.

Gold Microshell Tip for In Situ Electrochemical Raman Spectroscopy

Tip fabrication by a new strategy is proposed for simultaneous acquisition of electrochemical (EC) signals from an ultramicroelectrode and spectroscopic information from surface-enhanced Raman scattering (SERS). The EC-SERS tip is prepared by carefully tuning a SERS-active gold microshell to maximize Raman scattering, mechanically attaching it to the end of a micropipet, and electrically connecting it to a ruthenium inner layer through electroless deposition.