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Nanoengineering Carbon Spheres as Nanoreactors for Sustainable Energy Applications
Colloidal carbon sphere nanoreactors have been explored extensively as a class of versatile materials for various applications in energy storage, electrochemical conversion, and catalysis, due to their unique properties such as excellent electrical conductivity, high specific surface area, controlled porosity and permeability, and surface functionality. Here, the latest updated research on colloidal carbon sphere nanoreactor, in terms of both their synthesis and applications, is summarized. Various synthetic strategies are first discussed, including the hard template method, the soft template method, hydrothermal carbonization, the microemulsion polymerization method, and extension of the Stober method. Then, the functionalization of colloidal carbon sphere nanoreactors, including the nanoengineering of compositions and the surface features, is discussed. Afterward, recent progress in the major applications of colloidal carbon sphere nanoreactors, in the areas of energy storage, electrochemical conversion, and catalysis, is presented. Finally, the perspectives and challenges for future developments are discussed in terms of controlled synthesis and functionalization of the colloidal carbon sphere nanoreactors with tunable structure, and the composition and properties that are desirable for practical applications
Influence of Anchoring Groups on the Charge Transfer and Performance of p-Si/TiO2/Cobaloxime Hybrid Photocathodes for Photoelectrochemical H-2 Production
Although hybrid photocathodes built by immobilizing molecular catalysts to the surface of semiconductors through chemical linkages have been reported in recent years, systematic and comparative studies remain scarce about the impact of various anchoring groups on the performance, stability, and charge-transfer kinetics of molecular catalyst-decorated hybrid photocathodes for photoelectrochemical (PEC) H-2 production. In this study, the molecular cobaloxime catalysts, CoPy-4-X (Py = pyridine, X = PO3H2, COOH, and CONH(OH)), bearing different anchoring groups were synthesized and covalently immobilized to the surface of the porous TiO2 layer coated on a p-Si plate or a fluorine-doped tin oxide glass. The influence of the anchoring groups on the performance of p-Si/TiO2/CoPy-4-X photocathodes was comparatively studied for PEC H-2 evolution. Among the tested hybrid photocathodes, the one with a hydroxamate as an anchoring group displayed higher activity and lower charge-transfer resistance than that observed for the electrode with a carboxylate or a phosphonate as the anchoring group. Notably, the catalytic current of p-Si/Ti-2/CoPy-4-CONH(OH) was attenuated only by 2.9% in the controlled potential photoelectrolysis tests in borate buffer solution at pH 9 at 0 V versus a reversible hydrogen electrode over 6 h. Moreover, the influence of anchoring groups on the interfacial electron transfer from the TiO2 layer to the immobilized cobaloxime catalyst and electron-hole recombination was studied by transient absorption spectroscopy. These results revealed that the hydroxamate as an anchoring group is superior to the carboxylate and phosphonate groups for speeding up the interfacial electron transfer and firmly immobilizing the molecular catalysts to the metal oxide semiconductors to build efficient and stable hybrid photoelectrodes
Interfacial Enhancement by gamma-Al2O3 of Electrochemical Oxidative Dehydrogenation of Ethane to Ethylene in Solid Oxide Electrolysis Cells
Oxidative dehydrogenation of ethane (ODE) is limited by the facile deep oxidation and potential safety hazards. Now, electrochemical ODE reaction is incorporated into the anode of a solid oxide electrolysis cell, utilizing the oxygen species generated at anode to catalytically convert ethane. By infiltrating gamma-Al2O3 onto the surface of La0.6Sr0.4Co0.2Fe0.8O3-delta-Sm0.2Ce0.8O2-delta (LSCF-SDC) anode, the ethylene selectivity reaches as high as 92.5 %, while the highest ethane conversion is up to 29.1 % at 600 degrees C with optimized current and ethane flow rate. Density functional theory calculations and in situ X-ray photoelectron spectroscopy characterizations reveal that the Al2O3/LSCF interfaces effectively reduce the amount of adsorbed oxygen species, leading to improved ethylene selectivity and stability, and that the formation of Al-O-Fe alters the electronic structure of interfacial Fe center with increased density of state around Fermi level and downshift of the empty band, which enhances ethane adsorption and conversion