Kuei-Hsien Chen

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 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.

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.

Graphitic carbon nitride (CN) has emerged as a highly promising material in the photocatalysis field. However, its bulk structure suffers from a lack of active sites, limiting its practical application. Herein, a boron-doped CN (BCN) was prepared by a green gas-blowing-assisted thermal polymerization and then subjected to different exfoliation processes in order to delaminate the layered structure and tune the surface-active sites. A thorough comparative study shows that thermal exfoliation creates unsaturated nitrogen sites and induces the formation of interconnected layers that act as an electron diffusion channel for better charge transport. Furthermore, the thermally exfoliated BCN is rich in structural disorders that serve as dissociation defects for photoinduced charge carriers with a low exciton binding energy of 27 meV. Experimental results supported by theoretical calculations show that the nitrogen adjacent to boron is activated by the surrounding surface amino groups and the perforated texture to serve as an active adsorption site towards CO2 and H2O. Consequently, the exfoliated BCN acts as an outstanding bifunctional photocatalyst towards CO2 reduction into CO (40.41 μmol g−1 h−1) and prominent hydrogen evolution (4740 μmol g−1 h−1, 12.2% apparent quantum yield (AQY)).

Abstract Double-atom site catalysts (DASs) have emerged as a recent trend in the oxygen reduction reaction (ORR), thereby modifying the intermediate adsorption energies and increasing the activity. However, the lack of an efficient dual atom site to improve activity and durability has limited these catalysts from widespread application. Herein, the nitrogen-coordinated iron and tin-based DASs (Fe-Sn-N/C) catalyst are synthesized for ORR. This catalyst has a high activity with ORR half-wave potentials (E1/2) of 0.92 V in alkaline, which is higher than those of the state-of-the-art Pt/C (E1/2 = 0.83 V), Fe-N/C (E1/2 = 0.83 V), and Sn-N/C (E1/2 = 0.77 V). Scanning electron transmission microscopy analysis confirmed the atomically distributed Fe and Sn sites on the N-doped carbon network. X-ray absorption spectroscopy analysis revealed the charge transfer between Fe and Sn. Both experimental and theoretical results indicate that the Sn with Fe-NC (Fe-Sn-N/C) induces charge redistribution, weakening the binding strength of oxygenated intermediates and leading to improved ORR activity. This study provides the synergistic effects of DASs catalysts and addresses the impacts of P-block elements on d-block transition metals in ORR.

Cr substituted tetrahedrites with the chemical formula Cu12−xCrxSb4S13 (x = 0.15, 0.25, 0.35, 0.5, 0.75, 1.0) have been synthesised for thermoelectric study. Cr substitutes at the Cu site to optimize the thermoelectric properties and achieve a higher figure of merit (zT). X-Ray diffraction (XRD) analysis revealed that the tetrahedrite is the major phase with minor impurity phases. Electron probe microanalysis (EPMA) shows the formation of tetrahedrite main phase with near stoichiometry and the presence of Cu3SbS4, CuSbS2 and Sb as secondary phases. X-ray photoelectron spectroscopy (XPS) shows the oxidation state of Cu, Sb and S as +1, +3 and −2, respectively, whereas for Cr, it could not be identified. Temperature-dependent magnetic susceptibility of sample x = 0.75 shows antiferromagnetic correlation originating from the Cr ion. The calculated effective magnetic moment of 2.83 μB per Cr atom indicates the presence of Cr+4 in this sample. The decrease in the electrical resistivity upon doping indicates the compensation of holes due to the substitution of Cr at the Cu site. But the x = 0.35 sample is not following the trend due to larger compensation of holes with an activation energy of 124.6 meV. The temperature-dependent behaviour of electrical resistivity shows the shift in the Fermi level from the valance band towards the band gap. The absolute Seebeck coefficient is positive throughout the temperature range and follows a similar trend as that of electrical resistivity, with the exception of the x = 0.35 sample. The electronic thermal conductivity reduces due to hole compensation caused by Cr substitution. Moreover, the substitution of Cr effectively reduces the lattice thermal conductivity due to point defect scattering of phonons. A maximum zT of 1.0 is achieved for sample x = 0.35 at 700 K.

The quest of earth-abundant bifunctional electrocatalysts for highly efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is essential for clean and renewable energy systems. Herein, directed by the experimental analysis, we demonstrate layered nickel lithium phosphosulfide (NiLiP2S6) crystal as a highly efficient water-splitting catalyst in alkaline media. With strained lattice due to stacked layers as observed by TEM and electronic structure analysis performed by XPS showed mixed Ni2+,3+ oxidation states induced by addition of Li as a cation, NiLiP2S6 displays excellent OER (current density of 10 mA cm–2 showed an overpotential of 303 mV vs. RHE and a Tafel slope of 114 mV dec–1) and HER activity (current density of −10 mA cm–2 showed an overpotential of 184 mV vs. RHE and a Tafel slope of 94.5 mV dec–1). Finally, an alkaline media was employed to demonstrate the overall water splitting using NiLiP2S6 as both the anode and the cathode, which attained a 50 mA cm−2 current density at 1.68 V. This bimetallic phosphosulfide, together with long-term stability and enhanced intrinsic activity, shows enormous potential in water splitting applications.