Kuei-Hsien Chen

Bi doped Mg2Si0.4Sn0.6 had been synthesised in a high energy ball mill followed by compaction using a sintering hot press. The structural and compositional characterization of sintered mass indicated the formation of a highly densified single-phase product. The microstructure of the hot-pressed samples had been critically assessed. Thermoelectric properties were measured between room temperature and 723 K. A decrease in electrical conductivity was found with the increase in temperature but the Seebeck coefficient showed a reverse trend justifying the attainment of degenerate semiconducting behaviour. Meanwhile, the lattice thermal conductivity was subdued to 1.5 W/mK at 623 K. However, the highest zT value of 0.8 was achieved at 723 K. Moreover, the detailed X-ray photoelectron spectroscopic analysis was carried for the determination of binding energy of the constituent elements in the experimental alloy; it also provided the correct estimation of atomic percentage of the concerned elements. The Raman spectrum revealed a shift in F2g peak with respect to that of Mg2Sn and Mg2Si in correspondence with the composition of the synthesised alloy. The synthesised alloy showed micro and nano hardness of 3.7 and 4.03 GPa respectively, which implies that good mechanical strength could be achieved in the synthesised alloy.

Abstract Electrochemical reduction of oxygen into hydrogen peroxide in an acidic medium offers an energy-efficient and green H2O2 synthesis as an alternative to the energy-intensive anthraquinone process. Unfortunately, high overpotential, low production rates, and fierce competition from traditional four-electron reduction limit it. In this study, a metalloenzyme-like active structure is mimicked in carbon-based single-atom electrocatalysts for oxygen reduction to H2O2. Using a carbonization strategy, the primary electronic structure of the metal center with nitrogen and oxygen coordination is modulated, followed by epoxy oxygen functionalities close to the metal active sites. In an acidic medium, CoNOC active structures proceed with greater than 98% H2O2 selectivity (2e?/2H+) rather than CoNC active sites that are selective to H2O (4e?/4H+). Among all MNOC (M = Fe, Co, Mn, and Ni) single-atom electrocatalysts, the CoNOC is the most selective (> 98%) for H2O2 production, with a mass activity of 10 A g?1 at 0.60 V vs. RHE. X-ray absorption spectroscopy is used to identify the formation of unsymmetrical MNOC active structures. Experimental results are also compared to density functional theory calculations, which revealed that the structure-activity relationship of the epoxy-surrounded CoNOC active structure reaches optimum (?G*OOH) binding energies for high selectivity.

Abstract Earth-abundant commercial conductive carbon materials are ideal electrocatalyst supports but cannot be directly utilized for single-atom catalysts owing to the lack of anchoring sites. Therefore, we employed crosslink polymerization to modify the conductive carbon surface with Fe?Co dual-site electrocatalysts for oxygen reduction reaction (ORR). First, metal-coordinated polyurea (PU) aerogels were prepared using via crosslinked polymerization at ambient temperature. Then, carbon-supported, atomically dispersed Fe?Co dual-atom sites (FeCoNC/BP) were formed by high-temperatures pyrolysis with a nitrogen source. FTIR and 13C NMR measurements showed PU linkages, while 15N NMR revealed metal?nitrogen coordination in the PU gels. Asymmetric, N-coordinated, and isolated Fe?Co active structures were found after pyrolysis using XAS and STEM. In alkaline media, FeCoNC/BP exhibited excellent ORR activity, with a E1/2 of 0.93?V vs. RHE, higher than that of Pt/C (20?%) (0.90?V), FeNC/BP (0.88?V), and CoNC/BP (0.85?V). An accelerated durability test (ADT) on FeCoNC/BP indicated good durability over 35000 cycles. FeCoNC/BP also showed moderate ORR and ADT performance in acidic media. The macro/mesoporous N-doped carbon structures enhanced the mass transport properties of the dual Fe?Co active-sites. Therefore, modifying carbon supports with nonprecious metal catalysts may be a cost-effective-strategy for sustained electrochemical energy conversion.

Abstract Application of lasers is omnipresent in modern-day technology. However, preparation of a lasing device usually requires sophisticated design of the materials and is costly, which may limit the suitable choice of materials and the lasing wavelengths. Random lasers, on the other hand, can circumvent the aforementioned shortcomings with simpler fabrication process, lower processing cost, material flexibility for any lasing wavelengths with lower lasing threshold, providing a roadmap for the design of super-bright lighting, displays, Li-Fi, etc. In this work, ultralow-threshold random laser action from semiconductor nanoparticles assisted by a highly porous vertical-graphene-nanowalls (GNWs) network is demonstrated. The GNWs embedded by the nanomaterials produce a suitable cavity for trapping the optical photons with semiconductor nanomaterials acting as the gain medium. The observed laser action shows ultralow values of threshold energy density ≈10 nJ cm?2 due to the strong photon trapping within the GNWs. The threshold pump fluence can be further lowered to ≈1 nJ cm?2 by coating Ag/SiO2 upon the GNWs due to the combined effect of photon trapping and strong plasmonic enhancement. In view of the growing demand of functional materials and novel technologies, this work provides an important step toward realization of high-performance optoelectronic devices.

Layered MoS2 is considered as one of the most promising two-dimensional photocatalytic materials for hydrogen evolution and water splitting; however, the electronic structure at the MoS2-liquid interface is so far insufficiently resolved. Measuring and understanding the band offset at the surfaces of MoS2 are crucial for understanding catalytic reactions and to achieve further improvements in performance. Herein, the heterogeneous charge transfer behavior of MoS2 flakes of various layer numbers and sizes is addressed with high spatial resolution in organic solutions using the ferrocene/ferrocenium (Fc/Fc+) redox pair as a probe in near-field scanning electrochemical microscopy, i.e. in close nm probe-sample proximity. Redox mapping reveals an area and layer dependent reactivity for MoS2 with a detailed insight into the local processes as band offset and confinement of the faradaic current obtained. In combination with additional characterization methods, we deduce a band alignment occurring at the liquid-solid interface.

One of the key challenges in artificial photosynthesis is to design a photocatalyst that can bind and activate the CO2 molecule with the smallest possible activation energy and produce selective hydrocarbon products. In this contribution, a combined experimental and computational study on Ni-nanocluster loaded black TiO2 (Ni/TiO2[Vo]) with built-in dual active sites for selective photocatalytic CO2 conversion is reported. The findings reveal that the synergistic effects of deliberately induced Ni nanoclusters and oxygen vacancies provide (1) energetically stable CO2 binding sites with the lowest activation energy (0.08 eV), (2) highly reactive sites, (3) a fast electron transfer pathway, and (4) enhanced light harvesting by lowering the bandgap. The Ni/TiO2[Vo] photocatalyst has demonstrated highly selective and enhanced photocatalytic activity of more than 18 times higher solar fuel production than the commercial TiO2 (P-25). An insight into the mechanisms of interfacial charge transfer and product formation is explored.