Monitoring Hydrogen Evolution Reaction Intermediates of Transition Metal Dichalcogenides via Operando Raman Spectroscopy

© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim A deeper understanding of the water-splitting hydrogen evolution reaction (HER) mechanism during photocatalytic processes is crucial for the rational design of efficient photocatalysts. In particular, the HER mechanism promoted by multielement hybrid structures remains extremely challenging and elusive. Herein, an in situ photoelectrochemical/Raman measurement system is employed to monitor the HER mechanism of hybrid nanostructures under realistic working conditions via operando Raman spectra and linear-sweep voltammetry curves. As a proof of concept, tunable composition transition metal dichalcogenides MoS2xSe2(1−x) nanosheets are used as a model photocatalyst to unveil the corresponding photocatalytic mechanism. The spectroscopic studies reveal that hydrogen atoms can be adsorbed to active sulfur and selenium atoms via intermediate species formed during the photocatalytic process. More importantly, the studies demonstrate that an exponential relationship exists between the number of reactive electrons and the Raman intensity of intermediate species, which can serve as a guideline to directly evaluate the HER performance in photocatalysts by comparing the Raman intensities of the intermediate species. As a simple, intuitive, and general analytical method, the designed operando Raman measurement approach provides a new tool for elucidating catalytic reaction mechanisms in a realistic and complex environment; and strategically improving H2 production performance of multielement photocatalysts

Heat Diffusion-Induced Gradient Energy Level in Multishell Bisulfides for Highly Efficient Photocatalytic Hydrogen Production

© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Insufficient light absorption and low carrier separation/transfer efficiency constitute two key issues that hinder the development of efficient photocatalytic hydrogen production. Here, multishell ZnS/CoS2 bisulfide microspheres with gradient distribution of Zn based on the heat diffusion theory are designed. The Zn distribution can be adjusted by regulating the heating rate and manipulating the diffusion coefficients of the different elements conforming the multishell photocatalyst. Because of the unique structure, a gradient energy level is created from the core to the exterior of the multishell microspheres, which effectively facilitates the exciton separation and electron transfer. In addition, stronger light absorption and larger specific surface area have been achieved in the multishell ZnS/CoS2 photocatalysts. As a result, the multishell ZnS/CoS2 microspheres with gradient distribution of Zn exhibit a remarkable hydrogen production rate of 8001 µmol g−1 h−1, which is 3.5 times higher than that of the normal multishell ZnS/CoS2 particles with well-distributed Zn and 11.3 times higher than that of the mixed nonshell ZnS and CoS2 particles. This work demonstrates for the first time that controlling the diffusion rate of the different elements in the semiconductor is an effective route to simultaneously regulate morphology and structure to design highly efficient photocatalysts

Lignin-derived electrospun freestanding carbons as alternative electrodes for redox flow batteries

Based on information provided the embargo period/end date is 12 monthsBased on information provided the embargo period/end date is 12 month

Manipulating the Optical Properties of Carbon Dots by Fine-Tuning their Structural Features

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Synthesis and Application of Carbon–Iron Oxide Microspheres’ Black Pigments in Electrophoretic Displays

Carbon–iron oxide microspheres’ black pigments (CIOMBs) had been prepared via ultrasonic spray pyrolysis of aqueous solutions containing ferrous chloride and glucose. Due to the presence of carbon, CIOMBs not only exhibited remarkably acid resistance, but also could be well dispersed in both polar solvents and nonpolar solvent. Finally, dispersions of hollow CIOMBs in tetrachloroethylene had successfully been applied in electrophoretic displays

Microcellular Electrode Material for Microbial Bioelectrochemical Systems Synthesized by Hydrothermal Carbonization of Biomass Derived Precursors

V.F. acknowledges a UQ Postdoctoral Fellowship. This work was supported by the Australian Research Council Grant DP110100539. The authors acknowledge the facilities and the scientific and technical assistance of the Australian Microscopy & Microanalysis Research Facility at the Centre for Microscopy and Microanalysis (The University of Queensland). The Ghent University Special Research Fund (BOF) is acknowledged for the postdoctoral grant of M.N.B

Free-standing supercapacitors from Kraft lignin nanofibers with remarkable volumetric energy density

We have discovered a very simple method to address the challenge associated with the low volumetric energy density of free-standing carbon nanofiber electrodes for supercapacitors by electrospinning Kraft lignin in the presence of an oxidizing salt (NaNO₃) and subsequent carbonization in a reducing atmosphere. The presence of the oxidative salt decreases the diameter of the resulting carbon nanofibers doubling their packing density from 0.51 to 1.03 mg cm⁻² and hence doubling the volumetric energy density. At the same time, the oxidative NaNO₃ salt eletrospun and carbonized together with lignin dissolved in NaOH acts as a template to increase the microporosity, thus contributing to a good gravimetric energy density. By simply adjusting the process parameters (amount of oxidizing/reducing agent), the gravimetric and volumetric energy density of the resulting lignin free-standing carbon nanofiber electrodes can be carefully tailored to fit specific power to energy demands. The areal capacitance increased from 147 mF cm⁻² in the absence of NaNO₃ to 350 mF cm⁻² with NaNO₃ translating into a volumetric energy density increase from 949 μW h cm⁻³ without NaNO₃ to 2245 μW h cm⁻³ with NaNO₃. Meanwhile, the gravimetric capacitance also increased from 151 F g⁻¹ without to 192 F g⁻¹ with NaNO

A Two-Step Hydrothermal Synthesis Approach to Monodispersed Colloidal Carbon Spheres

This work reports a newly developed two-step hydrothermal method for the synthesis of monodispersed colloidal carbon spheres (CCS) under mild conditions. Using this approach, monodispersed CCS with diameters ranging from 160 to 400 nm were synthesized with a standard deviation around 8%. The monomer concentration ranging from 0.1 to 0.4 M is in favor of generation of narrower size distribution of CCS. The particle characteristics (e.g., shape, size, and distribution) and chemical stability were then characterized by using various techniques, including scanning electron microscopy (SEM), FT-IR spectrum analysis, and thermalgravity analysis (TGA). The possible nucleation and growth mechanism of colloidal carbon spheres were also discussed. The findings would be useful for the synthesis of more monodispersed nanoparticles and for the functional assembly

Magnetic Iron Oxide Nanoparticles: Synthesis and Surface Functionalization Strategies

Surface functionalized magnetic iron oxide nanoparticles (NPs) are a kind of novel functional materials, which have been widely used in the biotechnology and catalysis. This review focuses on the recent development and various strategies in preparation, structure, and magnetic properties of naked and surface functionalized iron oxide NPs and their corresponding application briefly. In order to implement the practical application, the particles must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of iron oxide NPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The problems and major challenges, along with the directions for the synthesis and surface functionalization of iron oxide NPs, are considered. Finally, some future trends and prospective in these research areas are also discussed