Optimizing interfacial electronic coupling with metal oxide to activate inert polyaniline for superior electrocatalytic hydrogen generation
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Magneto-optical (MO) coupling incorporates photon-induced change of magnetic polarization that can be adopted in ultrafast switching, optical isolators, mode convertors, and optical data storage components for advanced optical integrated circuits. However, integrating plasmonic, magnetic, and dielectric properties in one single material system poses challenges since one natural material can hardly possess all these functionalities. Here, co-deposition of a three-phase heterostructure composed of a durable conductive nitride matrix with embedded core–shell vertically aligned nanopillars, is demonstrated. Additionally, the unique coupling between ferromagnetic NiO core and atomically sharp plasmonic Au shell enables strong MO activity out-of-plane at room temperature. Further, a template growth process is applied, which significantly enhances the ordering of the nanopillar array. The ordered nanostructure offers two schemes of spin polarization which result in stronger antisymmetry of Kerr rotation. The presented complex hybrid metamaterial platform with strong magnetic and optical anisotropies is promising for tunable and modulated all-optical-based nanodevices.
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Propylene is an important chemical feedstock that is largely produced via cracking of oil-derived naphtha. Direct conversion of propane into propylene may be a more attractive alternative. Specifically, propane dehydrogenation (DH) and oxidative dehydrogenation (ODH) are promising for this transformation, albeit only DH has been industrially implemented. However, even the best DH catalysts (Pt-based) still suffer from deactivation. VO x - and BO x -based ODH catalysts result in significant over-oxidation and lack a mechanistic understanding. A common challenge in developing these catalysts is the broad distribution of surface species caused by the use of non-ordered catalyst supports. This hampers clear structure-performance correlations. Recent progress in the preparation of well-defined active sites on ordered supports has brought about improved catalysts, as well as fundamental insight into the working mechanism. This review will highlight recent advancements in the development of these catalysts and provide direction on the use of ordered supports for propane upgrading.
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Literature shows that adding Fe as a separate phase to MoO 3 /ZSM-5 catalysts can improve benzene selectivity in methane dehydroaromatization (MDA), but only when added in small quantities, making it difficult to characterize the state of Fe in the catalyst and understand the role of Fe-Mo interactions on the catalytic properties. We explore how the nature of the Mo-Fe interactions in the catalyst precursor can influence the stability and product selectivity in MDA, by employing for the first time Fe 2 (MoO 4 ) 3 /ZSM-5 as a catalyst precursor in MDA. We have compared the activity of Fe 2 (MoO 4 ) 3 /ZSM-5 with monometallic MoO 3 /ZSM-5 and mixed MoO 3 + Fe 2 O 3 /ZSM-5 containing equivalent Mo and Fe loadings and found that Fe 2 (MoO 4 ) 3 /ZSM-5 shows higher benzene selectivity than the mixed MoO 3 + Fe 2 O 3 /ZSM-5 catalyst and exhibits higher stability in reaction compared to the monometallic MoO3/ZSM-5 catalyst. Structural characterization suggests that Fe 2 (MoO 4 ) 3 partially segregates to Fe 2 O 3 and amorphous MoO x during thermal pretreatment. The MoO x species migrate into the zeolite channels during pretreatment, while Fe oxides remain on the external surface of the zeolite. Gas adsorption/desorption techniques and density functional theory calculations demonstrate that the preexisting Fe 2 O 3 phases on the external surface of the zeolite in the mixed MoO 3 + Fe 2 O 3 /ZSM-5 precursor trap (MoO 3 ) 3 clusters preventing them from migrating into the zeolite channels during pretreatment, whereas gradual formation of amorphous MoOx together with the segregation of the Fe 2 O 3 phase when using the Fe 2 (MoO 4 ) 3 precursor diminishes trapping of (MoO 3 ) 3 and consequently enhances migration and anchoring of the MoO x species in the zeolite channels, boosting selectivity to benzene. Characterization of used catalysts suggests that the presence of Fe promotes formation of structured carbon nanofibers which reduce the rate of catalyst deactivation.
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ZrO 2 and CeO 2 films were grown in SBA-15 by Atomic Layer Deposition (ALD) to loadings of 0.92 g oxide/g SBA-15. Scanning Transmission Electron Microscopy (STEM) with Energy Dispersive Spectra (EDS) showed that the oxides grew uniformly inside the mesopores. Film thicknesses were then analyzed as a function of the number of ALD cycles using three methods: 1) mass changes assuming bulk densities for the films; 2) changes in pore size from Barret-Joyner-Halenda (BJH) analysis with N 2 adsorption isotherms; and 3) small-angle X-ray scattering (SAXS). Film thicknesses assuming bulk densities were between 6 and 8 times smaller than those obtained from BJH analysis. SAXS analysis gave film thicknesses that were approximately twice that obtained from bulk densities. Here, possible explanations of the discrepancies between these methods are discussed.
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