TiO mesoporous crystal has been prepared by one-step corroding process via an oriented attachment (OA) mechanism with SrTiO as precursor. High resolution transmission electron microscopy (HRTEM) and nitrogen adsorption-desorption isotherms confirm its mesoporous crystal structure. Well-dispersed ruthenium (Ru) in the mesoporous nanocrystal TiO can be attained by the same process using Ru-doped precursor SrTiRu O. Ru is doped into lattice of TiO, which is identified by HRTEM and super energy dispersive spectrometer (super-EDS) elemental mapping. X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance spectroscopy (EPR) suggest the pentavalent Ru but not tetravalent, while partial Ti in TiO accept an electron from Ru and become Ti, which is observed for the first time. This Ru-doped TiO performs high activity for electrocatalytic hydrogen evolution reaction (HER) in alkaline solution. First-principles calculations simulate the HER process and prove TiO:Ru with Ru and Ti holds high HER activity with appropriate hydrogen-adsorption Gibbs free energies (Δ G).
Core-satellite is one of the most powerful superstructures since it leads to enhanced or completely new properties through compatible combination of each component. Here we create a novel ceria-based core-shell-satellite supersandwich structure with near-infrared (NIR) light manipulated catalytic activity by integrating the upconversion luminescent and catalytic functionality of CeO2 nanoparticles. Specifically, lanthanide-doped octahedral CeO2 nanoparticles (o-CeO2) are coated with silica layer (o-CeO2@SiO2) to enhance their luminescence intensity. The pH-dependent catalytic active cubic CeO2 nanoparticles (c-CeO2) are then assembled on the surface of o-CeO2@SiO2 to form the supersandwich structure (o-CeO2@SiO2@c-CeO2) following a classic chemical reaction. The upconversion quantum yield of o-CeO2 in this nanostructure can be nearly doubled. Furthermore, under NIR light irradiation, the o-CeO2@SiO2@c-CeO2 supersandwich structure based composite catalyst displays superior catalytic activity in selective reduction of aromatic nitro compounds to corresponding azo compounds, and the composite photocatalyst can be easily recycled for several times without significant loss of catalytic activity. This strategy may serve as a universal method for the construction of multifunctional nanostructures and shed light on the green chemistry for chemical synthesis.
Co@CoS nanochains with core-shell structures are prepared by a direct-current arc-discharge technique and followed sulfurization at 200 °C. The nanochains, which consist of uniform nanospheres connecting each other, can range up to several micrometers. The thickness of CoS shell can be changed by regulating the sulfurization time. In this heterostructure of Co@CoS, Co nanochains function as a conductive network and can inject electrons into CoS, which manipulates the work function of CoS and makes it more apposite for catalysis. The density functional theory calculation also reveals that coupling with Co can significantly reduce the overpotential needed to drive the oxygen evolution process. On the basis of the exclusive structure, Co@CoS nanochains have shown high catalytic activity in the oxygen evolution reaction. Co@CoS reaches an overpotential of 285 mv at 10 mA cm, which is much lower than that of Co nanochains (408 mV) and CoS (418 mV). Co@CoS also shows higher catalytic activity and robustness compared to state-of-the-art noble-metal catalyst RuO.
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