Kuei-Hsien Chen

Gas bubble evolution is an important phenomenon in many electrochemical processes and it is highly sensitive to the surface properties. Here we visualize the gas bubble dynamics on the surface of different graphene substrates during hydrogen evolution reaction (HER) using atomic force microscopy combined with scanning electrochemical microscopy. The low overpotential and low surface hydrophobicity of few-layer graphene formed on C-phase SiC causes the uniform distribution of hydrogen nanobubbles, which easily depart from the surface during the reaction. Conversely, the high overpotential and more hydrophobic surface of HOPG induces hydrogen bubbles to linger on the surface for an extended duration, leading to its accumulation and the subsequent formation of microbubbles. This in-situ nanoscale electrochemical mapping of hydrogen bubble dynamics provides new insight into electrocatalytic HER that occurs on non-metal electrodes.

Designing an organic polymer photocatalyst for efficient hydrogen evolution with visible and near-infrared (NIR) light activity is still a major challenge. Unlike the common behavior of gradually increasing the charge recombination while shrinking the bandgap, we present here a series of polymer nanoparticles (Pdots) based on ITIC and BTIC units with different π-linkers between the acceptor-donor-acceptor (A-D-A) repeated moieties of the polymer. These polymers act as an efficient single polymer photocatalyst for H2 evolution under both visible and NIR light, without combining or hybridizing with other materials. Importantly, the difluorothiophene (ThF) π-linker facilitates the charge transfer between acceptors of different repeated moieties (A-D-A-(π-Linker)-A-D-A), leading to the enhancement of charge separation between D and A. As a result, the PITIC-ThF Pdots exhibit superior hydrogen evolution rates of 279 µmol/h and 20.5 µmol/h with visible (>420 nm) and NIR (>780 nm) light irradiation, respectively. Furthermore, PITIC-ThF Pdots exhibit a promising apparent quantum yield (AQY) at 700 nm (4.76%).

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Multielement alloying is an appealing approach for suppressing thermal conductivity of thermoelectric materials. In this study, we synthesized GeTe-based high-entropy alloys with notable (S, Se) substitution at Te sites and (Ag, Sb) at Ge sites. The Ge0.82Ag0.08Sb0.1S0.5Se0.1Te0.4 exhibits an extremely low thermal conductivity of ∼ 0.66 W/m⋅K and a high Seebeck coefficient (>250 μV/K) over a temperature range of 150 – 400 °C. The influence of lattice distortion on phase transformation and transport properties of Ge0.9-2xAg2xSb0.1S0.5Se0.1Te0.4 (x = 0 – 0.06) was investigated.

Abstract Effects of electronic and atomic structures of V-doped 2D layered SnS2 are studied using X-ray spectroscopy for the development of photocatalytic/photovoltaic applications. Extended X-ray absorption fine structure measurements at V K-edge reveal the presence of VO and VS bonds which form the intercalation of tetrahedral OVS sites in the van der Waals (vdW) gap of SnS2 layers. X-ray absorption near-edge structure (XANES) reveals not only valence state of V dopant in SnS2 is ≈4+ but also the charge transfer (CT) from V to ligands, supported by V Lα,β resonant inelastic X-ray scattering. These results suggest V doping produces extra interlayer covalent interactions and additional conducting channels, which increase the electronic conductivity and CT. This gives rapid transport of photo-excited electrons and effective carrier separation in layered SnS2. Additionally, valence-band photoemission spectra and S K-edge XANES indicate that the density of states near/at valence-band maximum is shifted to lower binding energy in V-doped SnS2 compare to pristine SnS2 and exhibits band gap shrinkage. These findings support first-principles density functional theory calculations of the interstitially tetrahedral OVS site intercalated in the vdW gap, highlighting the CT from V to ligands in V-doped SnS2.

Lithium metal anodes form a dendritic structure after cycling which causes an internal short circuit in flammable electrolytes and results in battery fires. Today's separators are insufficient for suppressing the formation of lithium dendrites. Herein, we report on the use of mesoporous silica thin films (MSTFs) with perpendicular nanochannels (pore size ∼5 nm) stacking on an anodic aluminum oxide (AAO) membrane as the MSTF⊥AAO separator for advancing Li metal batteries. The nanoporous MSTF⊥AAO separator with novel inorganic structures shows ultra-long term stability of Li plating/stripping in Li–Li cells at an ultra-high current density and capacity (10 mA cm−2 and 5 mA h cm−2). A significant improvement over the state-of-the-art separator is evaluated based on three performance indicators, e.g. cycle life, current density and capacity. In Li–Cu cells, the MSTF⊥AAO separator shows a coulombic efficiency of >99.9% at a current density of 10 mA cm−2 for more than 250 h of cycling. The separator gives improved rate capability in Li–LiFePO4 (LFP) batteries. The excellent performance of the MSTF⊥AAO separator is due to good wetting of electrolytes, straight nanopores with negative charges, uniform Li deposition and blocking the finest dendrite.

Most chemical vapor deposition methods for transition metal dichalcogenides use an extremely small amount of precursor to render large single-crystal flakes, which usually causes low coverage of the materials on the substrate. In this study, a self-capping vapor-liquid-solid reaction is proposed to fabricate large-grain, continuous MoS2 films. An intermediate liquid phase-Na2Mo2O7 is formed through a eutectic reaction of MoO3 and NaF, followed by being sulfurized into MoS2. The as-formed MoS2 seeds function as a capping layer that reduces the nucleation density and promotes lateral growth. By tuning the driving force of the reaction, large mono/bilayer (1.1 mm/200 μm) flakes or full-coverage films (with a record-high average grain size of 450 μm) can be grown on centimeter-scale substrates. The field-effect transistors fabricated from the full-coverage films show high mobility (33 and 49 cm2 V−1 s−1 for the mono and bilayer regions) and on/off ratio (1 ~ 5 × 108) across a 1.5 cm × 1.5 cm region.

BiCuTeO is a promising thermoelectric material owing to its intrinsically low thermal conductivity and high carrier concentration. This study investigated the influence of stoichiometric oxygen deficiencies on the thermoelectric performance of BiCuTeO. Bulk BiCuTeO1−x (0.16 ≥ x) samples were prepared by a conventional solid state reaction and pelleted by hot pressing. Synchrotron X-ray diffraction, electron probe X-ray microanalysis, scanning electron microscopy, and transmission electron microscopy characterized the samples. A maximum value of 1.06 was achieved for the dimensionless figure of merit ZT at 673 K for BiCuTeO0.88, which is approximately 49% better than the current maximal ZT value for BiCuTeO. The power factor was noticeably improved owing to increases in the electrical conductivity and Seebeck coefficient. Moreover, the optimal oxygen deficiency could introduce nanoparticles, resulting in reduced thermal conductivity. The findings will be important for the future development of metal oxide thermoelectric materials for use in practical thermoelectric devices.

Thermoelectric (TE) devices used to convert waste heat directly into electricity are highly desirable for alleviating the prevailing energy crisis and global climate-change issues. Among the various TE materials available, metal oxides exhibit high thermal and chemical stabilities in air, and are hence, preferred for use in many TE applications. However, most of them possess TE figures of merit (ZT) that are below the applicable value of 2, in the mid-temperature region (from 250 to 600 °C). In a previous work, the removal of a small amount of Bi from BiCuSeO was found to improve the ZT of BiCuSeO. In this work, we pursue another track and study the TE performance of BiCuTeO after the addition of up to 6% excess Bi. Bi1+xCuTeO (x = 0.00–0.06) samples were prepared by solid-state reactions, followed by hot-pressing to form pellets. By adding a stoichiometric excess of Bi into BiCuTeO, 16% enhancement in power factor was achieved at 450 °C. This enhancement can be attributed to the increase in the Seebeck coefficient because of the appearance of secondary phases. Detailed characterizations and discussions of the effect of the nominal excess Bi in BiCuTeO are presented in this paper. The findings of this study can be applied in the investigation of novel high-performance TE materials.

BiCuTeO is a potential thermoelectric material owing to its low thermal conductivity and high carrier concentration. However, the thermoelectric performance of BiCuTeO is still below average and has much scope for improvement. In this study, we manipulated the nominal oxygen content in BiCuTeO and synthesized BiCuTeOx (x = 0.94–1.06) bulks by a solid-state reaction and pelletized them by a cold-press method. The power factor was enhanced by varying the nominal oxygen deficiency due to the increased Seebeck coefficient. The thermal conductivity was also reduced due to the decrease in lattice thermal conductivity owing to the small grain size generated by the optimal nominal oxygen content. Consequently, the ZT value was enhanced by ∼11% at 523 K for stoichiometric BiCuTeO0.94 compared to BiCuTeO. Thus, optimal oxygen manipulation in BiCuTeO can enhance the thermoelectric performance. This study can be applied to developing oxides with high thermoelectric performances.

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Photocatalytic formation of hydrocarbons using solar energy via artificial photosynthesis is a highly desirable renewable-energy source for replacing conventional fossil fuels. Using an l-cysteine-based hydrothermal process, here we synthesize a carbon-doped SnS2 (SnS2-C) metal dichalcogenide nanostructure, which exhibits a highly active and selective photocatalytic conversion of CO2 to hydrocarbons under visible-light. The interstitial carbon doping induced microstrain in the SnS2 lattice, resulting in different photophysical properties as compared with undoped SnS2. This SnS2-C photocatalyst significantly enhances the CO2 reduction activity under visible light, attaining a photochemical quantum efficiency of above 0.7%. The SnS2-C photocatalyst represents an important contribution towards high quantum efficiency artificial photosynthesis based on gas phase photocatalytic CO2 reduction under visible light, where the in situ carbon-doped SnS2 nanostructure improves the stability and the light harvesting and charge separation efficiency, and significantly enhances the photocatalytic activity.