Solvent-Free Depolymerization of Plastic Waste Enabled by Plastic-Catalyst Interfacial Engineering.

Depolymerization of condensation polymers by chemolysis often suffers from the large usage of solvents and homogeneous catalysts such as acids, bases, and metal salts. The catalytic efficiency of heterogeneous catalysts is largely constrained by the poor interfacial contact between solid catalysts and solid plastics below melting points. We report here our discovery of autogenous heterogeneous catalyst layer on polyethylene terephthalate surfaces during the generally believed homogeneous catalytic depolymerization process. Inspired by the "contact mass" concept in industrial chlorosilane production, we further demonstrate that the construction of plastic-catalyst solid-solid interfaces enables solvent-free depolymerization of polyethylene terephthalate by vapor phase methanolysis at relatively low temperatures. Trace amounts of earth-abundant element (zinc) introduced by electrostatic adsorption is sufficient for catalyzing the depolymerization. The concept of plastic-catalyst contact mass interfacial catalysis might inspire new pathways for tackling plastic waste problems.

Elucidating the Roles of Amorphous Alumina Overcoat in Palladium-Catalyzed Selective Hydrogenation.

Amorphous alumina overcoats generated by atomic layer deposition (ALD) have been shown to improve the selectivity and durability of supported metal catalysts in many reactions. Several mechanisms have been proposed to explain the enhanced catalytic performance, but the accessibilities of reactants through the amorphous overcoats remain elusive, which is crucial for understanding reaction mechanisms. Here, we show that an AlOx ALD overcoat is able to improve the alkene product selectivity of a supported Pd catalyst in acetylene (C2H2) hydrogenation. We further demonstrate that the AlOx ALD overcoat blocks the access of C2H2 (kinetic diameter of 0.33 nm), O2 (0.35 nm), and CO (0.38 nm) but allows H2 (0.29 nm) to access Pd surfaces. A H-D exchange experiment suggests that H2 might dissociate heterolytically at the Pd-AlOx interface. These findings are in favor of a hydrogen spillover mechanism.

Construction of Inverse Metal-Zeolite Interfaces via Area-Selective Atomic Layer Deposition.

The spatial confinement at metal-zeolite interfaces offers a powerful knob to steer the selectivity of chemical reactions on metal catalysts. However, encapsulating metal catalysts into small-pore zeolites remains a challenging task. Here, we demonstrate an inverse design of metal-zeolite interfaces, "metal-on-zeolite," constructed by area-selective atomic layer deposition. This inverse design bypasses the intrinsic synthetic issues associated with metal encapsulation, offering a potential solution for the fabrication of task-specific metal-zeolite interfaces for desired catalytic applications. Infrared spectroscopy and several probe reactions confirmed the spatial confinement effects at the inverse metal-zeolite interfaces.

Transmission electron microscopy studies and modeling of 3D reciprocal space of ω forming alloy.

Initial stage of ω phase formation and associated anomalous features that appear in diffraction patterns of a metastable ß transition metal alloy have been investigated in this study with the aid of transmission electron microscopy, simulation and modeling. The paper explores discrete features that emerge in selected area diffraction patterns of quenched Ti-15wt%Mo alloy and analyzes the correlation between ω reflections and diffuse arcs by considering all variants of ω phase as per the formation kinetics of ω phase in ß matrix while quenching. Superimposed simulated diffraction patterns have been compared with experimental counterparts and it is deduced that there is lack of congruence between ω reflections and diffuse arcs even after considering trigonal ω with varying degrees of displacement. Direct lattice imaging of trigonal ω in ß matrix has been demonstrated by phase contrast microscopy coupled with Fourier filtering techniques. By investigating the nature of ω reflections and diffuse arcs with the aid of electron diffraction pattern calculations and phase contrast microscopy, it is shown that, existing model of three-dimensional (3D) reciprocal space of ω forming alloy at quenched stage is not complete. A new model incorporating a patterned intensity distribution is fitted at the octahedral sites of an fcc reciprocal lattice whose planar intersections with Ewald's sphere show a better fit with the observed experimental diffraction patterns.

Synthesis of novel Ru2C under high pressure-high temperature conditions.

We report here, for the first time, synthesis of the Fe(2)N type hexagonal phase of ruthenium carbide by a high pressure-high temperature technique using a laser heated diamond anvil cell (LHDAC). The synthesis is carried out by laser heating a mixture of pure elements, Ru and C, at very low 'pressure' of 5 GPa and T ~ 2000 K. The structure of the temperature quenched high pressure phase is characterized by in situ high pressure x-ray diffraction (HPXRD) and is corroborated by ex situ TEM imaging and diffraction, carried out for the first time on the retrieved sample synthesized by LHDAC. The lattice parameters of Ru(2)C at ambient pressure are found to be a = 2.534 Å and c = 4.147 Å. In situ HPXRD studies up to 14.2 GPa yield a bulk modulus of 178(4) GPa. Electronic structure calculations reveal the system to be metallic in nature with a degree of covalence along the Ru-C bond. As ruthenium is isoelectronic to osmium, this result for Ru(2)C has significant implications in the synthesis and study of osmium carbides.

Microstructural studies of nanocomposite thin films of Ni/CrN prepared by reactive magnetron sputtering.

Synthesis and characterization of nanocomposites of Ni/CrN thin films prepared by DC magnetron sputtering from a target of 50 wt.%Ni-50 wt.%Cr is investigated. The films prepared as a function of nitrogen flow rate and substrate temperature showed that the films contained Ni and CrN phases with crystallite sizes in the nanometer range. Measurement of nanomechanical properties of the composite films exhibited a significant decrease in the values of hardness and Young's modulus than those of pure CrN films.

Eu(3+) doped gadolinium oxysulfide (Gd(2)O(2)S) nanostructures-synthesis and optical and electronic properties.

One-dimensional Eu(3+) doped gadolinium oxysulfide (Gd(2)O(2)S:Eu(3+)) nanotubes/nanorods have been synthesized via precursors of Gd(OH)(3) nanostructures using a hydrothermal technique. The blue-shifts in the optical spectra for the Gd(2)O(2)S:Eu(3+) system corresponding to the fundamental absorption and Eu(3+)-X(2-) ligand (X =  O/S) charge transfer bands (CTBs) are significant (∼0.22-0.36 eV) with respect to the bulk counterpart. The nanotubes are good candidates for investigating the size-induced electrical and optical properties of functional oxysulfides. In order to identify the origin and nature of the electronic transitions observed in the visible region, optical and photo-induced impedance measurements have been extended to the nanotubes in this report.

Synthesis of nanoparticles of barium lanthanum hafnium oxide by a modified combustion process.

Barium lanthanum hafnium oxide, a complex perovskite ceramic, has been synthesized as nanoparticles by a modified combustion process for the first time. The Ba, La, and Hf ions required for the formation of Ba2LaHfO5.5 were obtained in solution by dissolving in boiling nitric acid a stoichiometric mixture of BaCO3, La2O3, and HfO2 that had been heated at 1200 degrees C for 4 h. By complexing the ions with citric acid and using ammonia as fuel, it was possible to get Ba2LaHfO5.5 as nanoparticles in a single-step combustion process. The powder obtained by the present combustion process was characterized by X-ray diffraction, BET surface area analysis, differential thermal analysis, thermogravimetric analysis, infrared spectroscopy, and scanning and high-resolution transmission electron microscopy. According to the results of X-ray and electron diffraction, the powder synthesized through the combustion process showed single-phase barium lanthanum hafnium oxide. The transmission electron microscopic investigations showed a grain size of 42 nm, with a standard deviation of 8 nm. The nanoparticles of Ba2LaHfO5.5 synthesized by the present combustion technique could be sintered to > 97% of the theoretical density at a relatively low temperature of 1425 degrees C. Scanning electron microscopic studies on the sintered Ba2LaHfO5.5 samples showed that the final grain size of the sintered specimen was < 500 nm.