Unveiling Enhanced PEC Water Oxidation: Morphology Tuning and Interfacial Phase Change in α-Fe2O3@K-OMS-2 Branched Core-Shell Nanoarrays.

A simple fabrication method that involves two steps of hydrothermal reaction has been demonstrated for the growth of α-Fe2O3@K-OMS-2 branched core-shell nanoarrays. Different reactant concentrations in the shell-forming step led to different morphologies in the resultant composites, denoted as 0.25 OC, 0.5 OC, and 1.0 OC. Both 0.25 OC and 0.5 OC formed perfect branched core-shell structures, with 0.5 OC possessing longer branches, which were observed by SEM and TEM. The core K-OMS-2 and shell α-Fe2O3 were confirmed by grazing incidence X-ray diffraction (GIXRD), EDS mapping, and atomic alignment from high-resolution STEM images. Further investigation with high-resolution HAADF-STEM, EELS, and XPS indicated the existence of an ultrathin layer of Mn3O4 sandwiched at the interface. All composite materials offered greatly enhanced photocurrent density at 1.23 VRHE, compared to the pristine Fe2O3 photoanode (0.33 mA/cm2), and sample 0.5 OC showed the highest photocurrent density of 2.81 mA/cm2. Photoelectrochemical (PEC) performance was evaluated for the samples by conducting linear sweep voltammetry (LSV), applied bias photo-to-current efficiency (ABPE), electrochemical impedance spectroscopy (EIS), incident-photo-to-current efficiency (IPCE), transient photocurrent responses, and stability tests. The charge separation and transfer efficiencies, together with the electrochemically active surface area, were also investigated. The significant enhancement in sample 0.5 OC is ascribed to the synergetic effect brought by the longer branches in the core-shell structure, the conductive K-OMS-2 core, and the formation of the Mn3O4 thin layer formed between the core and shell.

Highly Mesoporous MoO3 Catalysts for Electrophilic Aromatic Substitution.

Herein, a straightforward synthesis method for highly mesoporous molybdenum oxide has been demonstrated via use of inverse micelles and molybdenum-oxo cluster formation. The synthesized catalyst is stable, crystalline, and MoO3 phase pure, as confirmed through thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. Further results from electron paramagnetic resonance, Raman spectroscopy, and UV-vis spectroscopy confirm the MoO3 phase purity. Chemisorption studies reveal that the synthesized material is 65 times more active than its commercial parts. The quantitative value of ammonia chemisorption for the synthesized catalyst is 1270 µmol/g, whereas the commercial catalyst only gives 22 µmol/g. These materials were tested for electrophilic substitution reactions since they are excellent solid acid. Electrophilic substitution of benzyl alcohol with toluene gives a >99% conversion with ∼80% of selectivity toward the methyl diphenylmethane product. The turnover number and turnover frequency values were calculated to be as high as 115 and 38, respectively. A substrate scope study shows that the reaction has preference toward electron-donating groups, whereas electron-withdrawing groups block the reaction. Based on the obtained results, a mechanism has been proposed.

Magnetically Doped Molybdenum Disulfide Layers for Enhanced Carbon Dioxide Capture.

Carbon capture and storage (CCS) technologies have the potential for reducing greenhouse gas emissions and creating clean energy solutions. One of the major aspects of the CCS technology is designing energy-efficient adsorbent materials for carbon dioxide capture. In this research, using a combination of first-principles theory, synthesis, and property measurements, we explore the CO2 gas adsorption capacity of MoS2 sheets via doping with iron, cobalt, and nickel. We show that substitutional dopants act as active sites for CO2 adsorption. The adsorption performance is determined to be dependent on the type of dopant species as well as its concentration. Nickel-doped MoS2 is found to be the best adsorbent for carbon capture with a relatively high gas adsorption capacity compared to pure MoS2 and iron- and cobalt-doped MoS2. Specifically, Brunauer-Emmett-Teller (BET) measurements show that 8 atom % Ni-MoS2 has the highest surface area (51 m2/g), indicating the highest CO2 uptake relative to the other concentrations and other dopants. Furthermore, we report that doping could lead to different magnetic solutions with changing electronic structures where narrow band gaps and the semimetallic tendency of the substrate are observed and can have an influence on the CO2 adsorption ability of MoS2. Our results provide a key strategy to the characteristic tendencies for designing highly active and optimized MoS2-based adsorbent materials utilizing the least volume of catalysts for CO2 capture and conversion.