Duck Hyun Youn

Single-crystalline, wormlike hematite photoanodes for efficient solar water splitting

A hematite photoanode showing a stable, record-breaking performance of 4.32 mA/cm2 photoelectrochemical water oxidation current at 1.23 V vs. RHE under simulated 1-sun (100 mW/cm2) irradiation is reported. This photocurrent corresponds to ca. 34% of the maximum theoretical limit expected for hematite with a band gap of 2.1 V. The photoanode produced stoichiometric hydrogen and oxygen gases in amounts close to the expected values from the photocurrent. The hematitle has a unique single-crystalline “wormlike” morphology produced by in-situ two-step annealing at 550°C and 800°C of β-FeOOH nanorods grown directly on a transparent conducting oxide glass via an all-solution method. In addition, it is modified by platinum doping to improve the charge transfer characteristics of hematite and an oxygen-evolving co-catalyst on the surface.

Highly active and stable hydrogen evolution electrocatalysts based on molybdenum compounds on carbon nanotube-graphene hybrid support.

Highly active and stable electrocatalysts for hydrogen evolution have been developed on the basis of molybdenum compounds (Mo2C, Mo2N, and MoS2) on carbon nanotube (CNT)-graphene hybrid support via a modified urea-glass route. By a simple modification of synthetic variables, the final phases are easily controlled from carbide, nitride to sulfide with homogeneous dispersion of nanocrystals on the CNT-graphene support. Among the prepared catalysts, Mo2C/CNT-graphene shows the highest activity for hydrogen evolution reaction with a small onset overpotential of 62 mV and Tafel slope of 58 mV/dec as well as an excellent stability in acid media. Such enhanced catalytic activity may originate from its low hydrogen binding energy and high conductivity. Moreover, the CNT-graphene hybrid support plays crucial roles to enhance the activity of molybdenum compounds by alleviating aggregation of the nanocrystals, providing a large area to contact with electrolyte, and facilitating the electron transfer.

Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries.

Graphene–carbon nanotube composite as an effective conducting scaffold to enhance the photoelectrochemical water oxidation activity of a hematite film

The iron oxide photoanode was modified with a graphene–carbon nanotube (CNT) composite conducting scaffold for efficient charge transfer from Fe2O3 particles to transparent conducting oxide substrate in photoelectrochemical water splitting cells. The Fe2O3–composite photoanode showed a photocurrent increase of 530% compared with to the bare Fe2O3 photoanode at 1.23 V vs. RHE, while the increase was only 200 and 240% for Fe2O3–CNT and Fe2O3–graphene photoanodes, respectively. This remarkable performance enhancement by the composite scaffold was attributed to synergistic effects induced by the formation of a 3D-like architecture from 1D CNT and 2D graphene. They become a spacer for each other forming a more open and highly exposed structure, in which both 2D graphene and 1D CNT can exist in the forms with much less self-agglomeration, thus not only enlarging the contact area between the conducting scaffold and Fe2O3 particles but also recovering in part the intrinsic conducting ability of graphene and CNT.

Highly Conformal Deposition of an Ultrathin FeOOH Layer on a Hematite Nanostructure for Efficient Solar Water Splitting

An ultrathin (ca. 2 nm) amorphous FeOOH overlayer was deposited conformally on a hematite nanostructure by a simple solution-based precipitation method, to generate an oxygen evolution cocatalyst for efficient solar water splitting. This uniform and highly conformal coating of the ultrathin metal oxyhydroxide is rare and is distinguished from the layers prepared by other conventional methods. With the FeOOH overlayer as the cocatalyst, the water oxidation photocurrent of hematite increased by a factor of approximately two and the onset potential shifted in the cathodic direction by 0.12 V under 1 sun illumination. The enhanced performance was attributed to the improved water oxidation kinetics and the passivation of the surface states of the hematite.

Self-assembled foam-like graphene networks formed through nucleate boiling

Self-assembled foam-like graphene (SFG) structures were formed using a simple nucleate boiling method, which is governed by the dynamics of bubble generation and departure in the graphene colloid solution. The conductivity and sheet resistance of the calcined (400°C) SFG film were 11.8 S·cm–1 and 91.2 Ω□−1, respectively, and were comparable to those of graphene obtained by chemical vapor deposition (CVD) (~10 S·cm–1). The SFG structures can be directly formed on any substrate, including transparent conductive oxide (TCO) glasses, metals, bare glasses, and flexible polymers. As a potential application, SFG formed on fluorine-doped tin oxide (FTO) exhibited a slightly better overall efficiency (3.6%) than a conventional gold electrode (3.4%) as a cathode of quantum dot sensitized solar cells (QDSSCs).

A highly efficient transition metal nitride-based electrocatalyst for oxygen reduction reaction: TiN on a CNT–graphene hybrid support

Transition metal nitrides of group 4–6 (Mo2N, W2N, NbN, Ta3N5, and TiN) were synthesized by the urea-glass route and screened for oxygen reduction reaction (ORR) electrodes in PEMFCs. In terms of electrochemical stability and activity, TiN was selected as the most promising candidate as a catalyst for ORR. To further enhance the activity for ORR, TiN was modified with nanostructured carbon supports including CNTs, graphene (GR), and CNT–GR hybrid. The obtained nanocarbon-supported TiN catalysts exhibited small particle sizes of TiN (<7 nm) and a good TiN–support interaction with reduced aggregation and no free-standing TiN particles away from the supports compared to bare TiN. In particular, TiN supported on the CNT–GR hybrid (TiN/CNT–GR) showed greatly enhanced ORR activity than bare TiN and other supported TiN catalysts. It exhibited a high onset potential (0.83 V) and the highest current density among the reported nitride-based electrocatalysts. The enhancement was ascribed to a synergistic effect between TiN nanoparticles (NPs) and CNT–GR hybird support, roles of which were to provide active sites for ORR and a facile electron pathway to NPs, respectively. Besides, TiN/CNT–GR exhibited large mesopores that could allow easy access of the electrolyte due to the formation of a 3-D CNT–GR structure assembled between 2-D graphene and 1-D CNTs. Further, it showed an excellent methanol tolerance compared to the commercial Pt/C catalyst. Thus, our TiN/CNT–GR could be a promising ORR electrocatalyst for PEMFCs and DMFCs.

Simple Synthesis of Nanocrystalline Tin Sulfide/N-Doped Reduced Graphene Oxide Composites as Lithium Ion Battery Anodes

Composites of nitrogen-doped reduced graphene oxide (NRGO) and nanocrystalline tin sulfides were synthesized, and their performance as lithium ion battery anodes was evaluated. Following the first cycle the composite consisted of Li2S/LixSn/NRGO. The conductive NRGO cushions the stress associated with the expansion of lithiation of Sn, and the noncycling Li2S increases the residual Coulombic capacity of the cycled anode because (a) Sn domains in the composite formed of unsupported SnS2 expand only by 63% while those in the composite formed of unsupported SnS expand by 91% and (b) Li percolates rapidly at the boundary between the Li2S and LixSn nanodomains. The best cycling SnS2/NRGO-derived composite retained a specific capacity of 562 mAh g-1 at the 200th cycle at 0.2 A g-1 rate.

Fabrication of graphene-based electrode in less than a minute through hybrid microwave annealing.

Highly efficient and stable MoS2 nanocrystals on graphene sheets (MoS2/GR) are synthesized via a hybrid microwave annealing process. Through only 45 second-irradiation using a household microwave oven equipped with a graphite susceptor, crystallization of MoS2 and thermal reduction of graphene oxide into graphene are achieved, indicating that our synthetic method is ultrafast and energy-economic. Graphene plays a crucial role as an excellent microwave absorber as well as an ideal support material that mediates the growth of MoS2 nanocrystals. The formed MoS2/GR electrocatalyst exhibits high activity of hydrogen evolution reaction with small onset overpotential of 0.1 V and Tafel slope of 50 mV per decade together with an excellent stability in acid media. Thus our hybrid microwave annealing could be an efficient generic method to fabricate various graphene-based hybrid electric materials for broad applications.

TiN Nanoparticles on CNT–Graphene Hybrid Support as Noble‐Metal‐Free Counter Electrode for Quantum‐Dot‐Sensitized Solar Cells

The development of an efficient noble-metal-free counter electrode is crucial for possible applications of quantum-dot-sensitized solar cells (QDSSCs). Herein, we present TiN nanoparticles on a carbon nanotube (CNT)-graphene hybrid support as a noble-metal-free counter electrode for QDSSCs employing a polysulfide electrolyte. The resulting TiN/CNT-graphene possesses an extremely high surface roughness, a good metal-support interaction, and less aggregation relative to unsupported TiN; it also has superior solar power conversion efficiency (4.13 %) when applying a metal mask, which is much higher than that of the state-of-the-art Au electrode (3.35 %). Based on electrochemical impedance spectroscopy measurements, the enhancement is ascribed to a synergistic effect between TiN nanoparticles and the CNT-graphene hybrid, the roles of which are to provide active sites for the reduction of polysulfide ions and electron pathways to TiN nanoparticles, respectively. The combination of graphene and CNTs leads to a favorable morphology that prevents stacking of graphene or bundling of CNTs, which maximizes the contact of the support with TiN nanoparticles and improves electron-transfer capability relative to either carbon material alone.