Fe-POM/attapulgite composite materials: Efficient catalysts for plastic pyrolysis.

This article describes the catalytic cracking of low-density polyethylene over attapulgite clay and iron substituted tungstophosphate/attapulgite clay (Fe-POM/attapulgite) composite materials to evaluate their suitability and performance for recycling of plastic waste into liquid fuel. The prepared catalysts enhanced the yield of liquid fuel (hydrocarbons) produced in cracking process. A maximum yield of 82% liquid oil fraction with a negligible amount of coke was obtained for 50% Fe-POM/attapulgite composite. Whereas, only 68% liquid oil fractions with a large amount of solid black residue was produced in case of non-catalytic pyrolysis. Moreover, Fe-POM/attapulgite clay composites showed higher selectivity towards lower hydrocarbons (C5-C12) with aliphatic hydrocarbons as major fractions. These synthesised composite catalysts significantly lowered the pyrolysis temperature from 375°C to 310°C. Hence, recovery of valuable fuel oil from polyethylene using these synthesised catalysts suggested their applicability for energy production from plastic waste at industrial level as well as for effective environment pollution control.

Solution/Ammonolysis Syntheses of Unsupported and Silica-Supported Copper(I) Nitride Nanostructures from Oxidic Precursors.

Herein we describe an alternative strategy to achieve the preparation of nanoscale Cu3N. Copper(II) oxide/hydroxide nanopowder precursors were successfully fabricated by solution methods. Ammonolysis of the oxidic precursors can be achieved essentially pseudomorphically to produce either unsupported or supported nanoparticles of the nitride. Hence, Cu3N particles with diverse morphologies were synthesized from oxygen-containing precursors in two-step processes combining solvothermal and solid-gas ammonolysis stages. The single-phase hydroxochloride precursor, Cu2(OH)3Cl was prepared by solution-state synthesis from CuCl2·2H2O and urea, crystallising with the atacamite structure. Alternative precursors, CuO and Cu(OH)2, were obtained after subsequent treatment of Cu2(OH)3Cl with NaOH solution. Cu3N, in the form of micro- and nanorods, was the sole product formed from ammonolysis using either CuO or Cu(OH)2. Conversely, the ammonolysis of dicopper trihydroxide chloride resulted in two-phase mixtures of Cu3N and the monoamine, Cu(NH3)Cl under similar experimental conditions. Importantly, this pathway is applicable to afford composite materials by incorporating substrates or matrices that are resistant to ammoniation at relatively low temperatures (ca. 300 °C). We present preliminary evidence that Cu3N/SiO2 nanocomposites (up to ca. 5 wt.% Cu3N supported on SiO2) could be prepared from CuCl2·2H2O and urea starting materials following similar reaction steps. Evidence suggests that in this case Cu3N nanoparticles are confined within the porous SiO2 matrix.

Microwave-Assisted Synthesis of ZnO-rGO Core-Shell Nanorod Hybrids with Photo- and Electro-Catalytic Activity.

The unique two-dimensional structure and surface chemistry of reduced graphene oxide (rGO) along with its high electrical conductivity can be exploited to modify the electrochemical properties of ZnO nanoparticles (NPs). ZnO-rGO nanohybrids can be engineered in a simple new two-step synthesis, which is both fast and energy-efficient. The resulting hybrid materials show excellent electrocatalytic and photocatalytic activity. The structure and composition of the as-prepared bare ZnO nanorods (NRs) and the ZnO-rGO hybrids have been extensively characterised and the optical properties subsequently studied by UV/Vis spectroscopy and photoluminescence (PL) spectroscopy (including decay lifetime measurements). The photocatalytic degradation of Rhodamine B (RhB) dye is enhanced using the ZnO-rGO hybrids as compared to bare ZnO NRs. Furthermore, potentiometry comparing ZnO and ZnO-rGO electrodes reveals a featureless capacitive background for an Ar-saturated solution whereas for an O2 -saturated solution a well-defined redox peak was observed using both electrodes. The change in reduction potential and significant increase in current density demonstrates that the hybrid core-shell NRs possess remarkable electrocatalytic activity for the oxygen reduction reaction (ORR) as compared to NRs of ZnO alone.

Highly efficient catalytic pyrolysis of polyethylene waste to derive fuel products by novel polyoxometalate/kaolin composites.

We report here alumina-substituted Keggin tungstoborate/kaolin clay composite materials (KAB/kaolin) as polyethylene cracking catalysts. KAB/kaolin composites with varying concentrations of KAB (10-50 wt.%) were synthesized by the wet impregnation method and successfully characterized by Fourier-transform infrared spectroscopy, powder X-ray diffraction, thermo-gravimetric analysis and scanning electron microscopy with energy dispersive X-ray spectroscopy analytical techniques. Use of KAB loaded kaolin composites as the catalyst for low-density polyethylene (LDPE) cracking exhibited a higher percentage of polymer conversion (99%), producing 84 wt.% of fuel oil and negligible amount (˂ 1 wt.%) of solid residue while thermal cracking produced ~22 wt.% residue. Furthermore, gas chromatography-mass spectrometry analysis of oil obtained by non-catalytic cracking exhibited a high selectivity to high molecular weight hydrocarbons (C13-C23) compared to the catalytic cracking where 70 mol.% of gasoline range hydrocarbons (C5-C12) were produced. We propose that higher cracking ability of our prepared catalysts might ensue from both Brønsted and Lewis acid sites (from KAB and kaolin respectively), which enhanced the yield of liquid fuel products and reduced the cracking temperature of LDPE. These findings suggest that the prepared composites were cost-effective and excellent cracking catalysts that could be recommended for highly efficient conversion of waste plastic materials to petrochemicals at an industrial scale.

MCNTs@MnO2 Nanocomposite Cathode Integrated with Soluble O2-Carrier Co-salen in Electrolyte for High-Performance Li-Air Batteries.

Li-air batteries (LABs) are promising because of their high energy density. However, LABs are troubled by large electrochemical polarization during discharge and charge, side reactions from both carbon cathode surface/peroxide product and electrolyte/superoxide intermediate, as well as the requirement for pure O2. Here we report the solution using multiwall carbon nanotubes (MCNTs)@MnO2 nanocomposite cathode integrated with N,N'-bis(salicylidene)ethylenediaminocobalt(II) (CoII-salen) in electrolyte for LABs. The advantage of such a combination is that on one hand, the coating layer of δ-MnO2 with about 2-3 nm on MCNTs@MnO2 nanocomposite catalyzes Li2O2 decomposition during charge and suppresses side reactions between product Li2O2 and MCNT surface. On the other hand, CoII-salen works as a mobile O2-carrier and accelerates Li2O2 formation through the reaciton of (CoIII-salen)2-O22- + 2Li+ + 2e- → 2CoII-salen + Li2O2. This reaction route overcomes the pure O2 limitation and avoids the formation of aggressive superoxide intermediate (O2- or LiO2), which easily attacks organic electrolyte. By using this double-catalyst system of Co-salen/MCNTs@MnO2, the lifetime of LABs is prolonged to 300 cycles at 500 mA g-1 (0.15 mA cm-2) with fixed capacity of 1000 mAh g-1 (0.30 mAh cm-2) in dry air (21% O2). Furthermore, we up-scale the capacity to 500 mAh (5.2 mAh cm-2) in pouch-type batteries (∼4 g, 325 Wh kg-1). This study should pave a new way for the design and construction of practical LABs.

Facile preparation of ß-/γ-MgH2 nanocomposites under mild conditions and pathways to rapid dehydrogenation.

A magnesium hydride composite with enhanced hydrogen desorption kinetics can be synthesized via a simple wet chemical route by ball milling MgH2 with LiCl as an additive at room temperature followed by tetrahydrofuran (THF) treatment under an Ar atmosphere. The as-synthesized composite comprises ca. 18 mass% orthorhombic γ-MgH2 and 80 mass% tetragonal ß-MgH2 as submicron-sized particles. The ß-/γ-MgH2 nanocomposite exhibits a dehydrogenation capacity of 6.6 wt% and starts to release hydrogen at ∼260 °C; ca. 140 °C lower than that of commercial MgH2. The apparent activation energy for dehydrogenation is 115 ± 3 kJ mol(-1), which is ca. 46% lower than that of commercial MgH2. Analysis suggests that the meta-stable γ-MgH2 component either directly dehydrogenates exothermically or first transforms into stable ß-MgH2 very close to the dehydrogenation onset. The improved hydrogen release performance can be attributed both to the existence of the MgH2 nanostructure and to the presence of γ-MgH2.

Facile Surfactant-Free Synthesis of p-Type SnSe Nanoplates with Exceptional Thermoelectric Power Factors.

A surfactant-free solution methodology, simply using water as a solvent, has been developed for the straightforward synthesis of single-phase orthorhombic SnSe nanoplates in gram quantities. Individual nanoplates are composed of {100} surfaces with {011} edge facets. Hot-pressed nanostructured compacts (Eg ≈0.85 eV) exhibit excellent electrical conductivity and thermoelectric power factors (S(2) σ) at 550 K. S(2) σ values are 8-fold higher than equivalent materials prepared using citric acid as a structure-directing agent, and electrical properties are comparable to the best-performing, extrinsically doped p-type polycrystalline tin selenides. The method offers an energy-efficient, rapid route to p-type SnSe nanostructures.

Insight into lithium transport in lithium nitridometallate battery materials from muon spin relaxation.

Muon spin relaxation and powder neutron diffraction have been combined to study three lithium cobalt nitride battery materials. Neutron diffraction shows that these retain the P6/mmm space group of Li(3)N with Co located only on Li(1) sites. The lattice parameters vary smoothly with the degree of metal substitution, such that the [Li(2)N] layers expand while the layer separation contracts, as observed previously for similar series of Cu- and Ni-substituted materials. However, in contrast to the latter, the Li(3-x-y)Co(x)N phases exhibit Curie-Weiss paramagnetism and this prevents the use of nuclear magnetic resonance to measure Li(+) transport parameters. Therefore, muon spin relaxation has been employed here as an alternative technique to obtain quantitative information about Li(+) diffusion. Muon spin relaxation shows that Li(+) diffusion in Li(3-x-y)Co(x)N is anisotropic with transport confined to the [Li(2)N] plane at low temperature and exchange between Li(1) and Li(2) sites dominant at high temperature. By a comparison with previous studies some general trends have been established across a range of Cu-, Ni- and Co-substituted materials. For intra-layer diffusion E(a) decreases as metal substitution increases and the corresponding expansion of the layers results in a more open pathway for Li(+) diffusion. However, an optimal value of x is found with a ≈ 3.69 Å after which the concomitant contraction in layer spacing reduces the polarizability of the lattice framework.

From doping to composites: zirconia (ZrO2) modified hematite photoanodes for water splitting.

Herein, a ZrO2 added α-Fe2O3 photoanode that can split water at low applied potential is reported. First, the pristine hematite α-Fe2O3 photoanode was synthesized using an aerosol-assisted chemical vapour deposition (AACVD) method followed by modification with various amounts of ZrO2 (2 to 40%) in the form of thin films on conducting glass substrate. The XRD, Raman spectroscopy and scanning electron microscopy (SEM) analyses confirmed the presence of the monoclinic phase of ZrO2 in the composites with multifaceted particles of compact morphology. The optical analysis showed an increase in the absorbance and variation in band gap of the composites ascribed to the heterogeneity of the material. The photoelectrochemical studies gave a photocurrent density of 1.23 mA cm-2 at 1.23 V vs. RHE for the pristine hematite and remarkably higher value of 3.06 mA cm-2 for the optimized amount of ZrO2 in the modified α-Fe2O3 photoanode. To the best of our knowledge, this is the highest photocurrent reported for a ZrO2 containing photoanode. The optimized composite electrode produced nine times more oxygen than that produced by pristine hematite.

Pillared Vanadium Molybdenum Disulfide Nanosheets: Toward High-Performance Cathodes for Magnesium-Ion Batteries.

If magnesium-ion batteries (MIBs) are to be seriously considered for next-generation energy storage, then a number of major obstacles need to be overcome. The lack of reversible cathode materials with sufficient capacity and cycle life is one of these challenges. Here, we report a new MIB cathode constructed of vertically stacked vanadium molybdenum sulfide (VMS) nanosheets toward addressing this challenge. The integration of vanadium within molybdenum sulfide nanostructures acts so as to improve the total conductivity, enhancing charge transfer, and to produce abundant lattice defects, improving both the accommodation and transport of Mg2+. Additionally, electrolyte additive-induced interlayer expansion provides a means to admit Mg2+ cations into the electrode structure and thus enhance their diffusion. The VMS nanosheets are capable of exhibiting capacities of 211.3 and 128.2 mA h g-1 at current densities of 100 and 1000 mA g-1, respectively. The VMS nanosheets also demonstrate long-term cycling stability, retaining 82.7% of the maximum capacity after 500 cycles at a current density of 1000 mA h g-1. These results suggest that VMS nanosheets could be promising candidates for high-performance cathodes in MIBs.

Crystallography at non-ambient conditions and physical properties of the synthesized double perovskites, Sr2(Co1-xFex)TeO6.

Polycrystalline double perovskite-type Sr2(Co1-xFex)TeO6 with various stoichiometric compositions (x = 0, 0.25, 0.5, 0.75, and 1) were synthesized by solid-state reactions in air. The crystal structures and phase transitions of this series at different temperature intervals were determined by X-ray powder diffraction, and from the obtained data the crystal structures were refined. It has been proven that for the compositions x = 0.25, 0.50, and 0.75, the phases crystallize at room temperature in the monoclinic space group I2/m. Down to 100 K, depending on the composition, these structures experience a phase transition from I2/m to P21/n. At high temperatures up to 1100 K their crystal structures show two further phase transitions. The first one is a first-order phase transition, from monoclinic I2/m to tetragonal I4/m, followed by a second-order phase transition to cubic Fm3̄m. Therefore, the phase transition sequence of this series detected at temperatures ranging from 100 K to 1100 K is P21/n → I2/m → I4/m → Fm3̄m. The temperature-dependent vibrational features of the octahedral sites were investigated by Raman spectroscopy, which furthermore complements the XRD results. A decrease in the phase-transition temperature with increasing iron content has been observed for these compounds. This fact is explained by the progressive diminishing of the distortion of the double-perovskite structure in this series. Using room-temperature Mössbauer spectroscopy, the presence of two iron sites is confirmed. The two different transition metal cations Co and Fe at the B sites allow exploring their effect on the optical band-gap.

Carbon-Free Conversion of SiO2 to Si via Ultra-Rapid Alloy Formation: Toward the Sustainable Fabrication of Nanoporous Si for Lithium-Ion Batteries.

Silicon has the potential to improve lithium-ion battery (LIB) performance substantially by replacing graphite as an anode. The sustainability of such a transformation, however, depends on the source of silicon and the nature of the manufacturing process. Today's silicon industry still overwhelmingly depends on the energy-intensive, high-temperature carbothermal reduction of silica─a process that adversely impacts the environment. Rather than use conventional thermoreduction alone to break Si-O bonds, we report the efficient conversion of SiO2 directly to Mg2Si by a microwave-induced Mg plasma within 2.5 min at merely 200 W under vacuum. The underlying mechanism is proposed, wherein electrons with enhanced kinetics function readily as the reductant while the "bombardment" from Mg cations and electrons promotes the fast nucleation of Mg2Si. The 3D nanoporous (NP) Si is then fabricated by a facile thermal dealloying step. The resulting hierarchical NP Si anodes deliver stable, extended cycling with excellent rate capability in Li-ion half-cells, with capacities several times greater than graphite. The microwave-induced metal plasma (MIMP) concept can be applied just as efficiently to the synthesis of Mg2Si from Si, and the chemistry should be extendable to the reduction of multiple metal(loid) oxides via their respective Mg alloys.

Ternary and higher pnictides; prospects for new materials and applications.

Discoveries of complex solid compounds of the group 15 elements have risen dramatically over the past 2 decades and within the last 10 years the potential offered by unusual and unexpected physical and chemical properties and phenomena are beginning to be realised in a materials context. This critical review highlights just some of the many areas in which ternary and higher pnictides are making an impact. A growing understanding of synthesis-structure-property relationships in nitrides, phosphides, arsenides and antimonides in particular has led to amazing progress over a very short space of time and provided insight that has proved to be transferrable to other areas of solid state and materials chemistry (254 references).

Energy-Saving Pathways for Thermoelectric Nanomaterial Synthesis: Hydrothermal/Solvothermal, Microwave-Assisted, Solution-Based, and Powder Processing.

The pillars of Green Chemistry necessitate the development of new chemical methodologies and processes that can benefit chemical synthesis in terms of energy efficiency, conservation of resources, product selectivity, operational simplicity and, crucially, health, safety, and environmental impact. Implementation of green principles whenever possible can spur the growth of benign scientific technologies by considering environmental, economical, and societal sustainability in parallel. These principles seem especially important in the context of the manufacture of materials for sustainable energy and environmental applications. In this review, the production of energy conversion materials is taken as an exemplar, by examining the recent growth in the energy-efficient synthesis of thermoelectric nanomaterials for use in devices for thermal energy harvesting. Specifically, "soft chemistry" techniques such as solution-based, solvothermal, microwave-assisted, and mechanochemical (ball-milling) methods as viable and sustainable alternatives to processes performed at high temperature and/or pressure are focused. How some of these new approaches are also considered to thermoelectric materials fabrication can influence the properties and performance of the nanomaterials so-produced and the prospects of developing such techniques further.

Effects of iron substitution and anti-site disorder on crystal structures, vibrational, optical and magnetic properties of double perovskites Sr2(Fe1-xNix)TeO6.

The double-perovskite series, Sr2(Fe1-xNix)TeO6 (x = 0, 0.25, 0.50, 0.75, and 1) has been synthesized in polycrystalline form by solid-state reaction at 1300 K in air. Their crystal structures were probed by powder X-ray diffraction at room temperature. Rietveld analysis revealed that all samples crystallize in the monoclinic space group I2/m. The double-perovskite structures ideally contain two alternating types of octahedra (Fe/Ni)2dO6 and (Te)2aO6, tilted in the system (a-a-c0). However, the refinements have shown a complex distribution of all three cations over the two available octahedral sites; 2d (½, ½, 0) and 2a (0, 0, 0). Raman spectroscopy further complements the obtained results, by revealing a tiny increase of the wavenumber of some Raman modes when Fe is substituted by Ni. The optical characteristics of the series were determined by fitting diffuse reflectance UV/Vis spectra enabling the optical band gaps to be derived from Tauc method and derivation of absorption spectra fitting (DASF) techniques. Analyses of the obtained 57Fe Mössbauer hyperfine parameters at room temperature of samples with compositions x = 0, 0.25, 0.50 and 0.75 reveal the presence of Fe3+ in high-spin state with an anti-site disorder of Fe-Ni-Te cations in distorted octahedral environments (site 2d and 2a). The results show that significant correlations exist between the crystal structures and physical properties of double perovskites containing B site transition elements of different charge and size. Temperature-dependent magnetic susceptibility data show magnetic transitions below 40(1) K (38(1) K, 31(1) K, 25(1) K, 20(1) K, and 35(1) K for x = 0, 0.25, 0.50, 0.75, and 1, respectively. A divergence between FC and ZFC curves for all compositions has been observed. The results show that the ground states of the doped materials might be spin glasses or magnetically ordered.

New ternary and quaternary barium nitride halides; synthesis and crystal chemistry.

New ternary and quaternary nitride halides, Ba(2)N(X,X') (X = F, Cl, Br; X' = Br, I), have been synthesized from the high temperature reactions of barium subnitride with the respective barium halides under an inert atmosphere. The former include the first fully characterized barium nitride halides for X other than F, and the latter are the first examples of barium nitride mixed halides. The variation in structure with composition has been investigated by powder X-ray and powder neutron diffraction techniques. The heavier ternary and quaternary nitride halides (X, X' = Cl, Br, I) crystallize in the hexagonal space group R3m, with the anti-α-NaFeO(2) structure. Ba(2)NF forms with both an anti-α-NaFeO(2) structure, in which N(3-) and F(-) are ordered and an anion-disordered simple rock salt structure. The hexagonal polymorph of Ba(2)NF is the only example to date of a nitride fluoride adopting this layered structure. Both the ternary and the quaternary compounds display very weak, temperature independent paramagnetism.

Structure, stoichiometry and transport properties of lithium copper nitride battery materials: combined NMR and powder neutron diffraction studies.

A combined NMR and neutron diffraction study has been carried out on three Li(3-x-y)Cu(x)N materials with x=0.17, x=0.29 and x=0.36. Neutron diffraction indicates that the samples retain the P6/mmm space group of the parent Li(3)N with Cu located only on Li(1) sites. The lattice parameters vary smoothly with x in a similar fashion to Li(3-x-y)Ni(x)N, but the Li(2) vacancy concentration for the Cu-substituted materials is negligible. This structural model is confirmed by wideline (7)Li NMR spectra at 193 K which show three different local environments for the Li(1) site, resulting from the substitution of neighbouring Li atoms in the Li(1) layer by Cu. Since the Cu-substituted materials are only very weakly paramagnetic, variable temperature (7)Li wideline NMR spectra can be used to measure diffusion coefficients and activation energies. These indicate anisotropic Li(+) diffusion similar to the parent Li(3)N with transport confined to the [Li(2)N] plane at low temperature and exchange between Li(1) and Li(2) sites dominant at high temperature. For the intra-layer process the diffusion coefficients at room temperature are comparable to Li(3)N and Li(3-x-y) Ni(x)N, while E(a) decreases as x increases in contrast to the opposite trend in Ni-substituted materials. For the inter-layer process E(a) decreases only slightly as x increases, but the diffusion coefficients at room temperature increase rapidly with x.

Mechanochemical Synthesis and Structure of Lithium Tetrahaloaluminates, LiAlX4 (X = Cl, Br, I): A Family of Li-Ion Conducting Ternary Halides.

State-of-the-art oxides and sulfides with high Li-ion conductivity and good electrochemical stability are among the most promising candidates for solid-state electrolytes in secondary batteries. Yet emerging halides offer promising alternatives because of their intrinsic low Li+ migration energy barriers, high electrochemical oxidative stability, and beneficial mechanical properties. Mechanochemical synthesis has enabled the characterization of LiAlX4 compounds to be extended and the iodide, LiAlI4, to be synthesized for the first time (monoclinic P21/c, Z = 4; a = 8.0846(1) Å; b = 7.4369(1) Å; c = 14.8890(2) Å; ß = 93.0457(8)°). Of the tetrahaloaluminates, LiAlBr4 exhibited the highest ionic conductivity at room temperature (0.033 mS cm-1), while LiAlCl4 showed a conductivity of 0.17 mS cm-1 at 333 K, coupled with the highest thermal and oxidative stability. Modeling of the diffusion pathways suggests that the Li-ion transport mechanism in each tetrahaloaluminate is closely related and mediated by both halide polarizability and concerted complex anion motions.

Multiple Roles of Unconventional Heteroatom Dopants in Chalcogenide Thermoelectrics: The Influence of Nb on Transport and Defects in Bi2Te3.

Improvements in the thermoelectric performance of n-type Bi2Te3 materials to more closely match their p-type counterparts are critical to promote the continued development of bismuth telluride thermoelectric devices. Here the unconventional heteroatom dopant, niobium, has been employed as a donor in Bi2Te3. Nb substitutes for Bi in the rhombohedral Bi2Te3 structure and exhibits multiple roles in its modulation of electrical transport and defect-induced phonon scattering. The carrier concentration is significantly increased as electrons are afforded by aliovalent doping and formation of vacancies on the Te sites. In addition, incorporation of Nb in the pseudoternary Bi2-xNbxTe3-δ system increases the effective mass, m*, which is consistent with cases of "conventional" elemental doping in Bi2Te3. Lastly, inclusion of Nb induces both point and extended defects (tellurium vacancies and dislocations, respectively), enhancing phonon scattering and reducing the thermal conductivity. As a result, an optimum zT of 0.94 was achieved in n-type Bi0.92Nb0.08Te3 at 505 K, which is dramatically higher than an equivalent undoped Bi2Te3 sample. This study suggests not only that is Nb an exciting and novel electron dopant for the Bi2Te3 system but also that unconventional dopants might be utilized with similar effects in other chalcogenide thermoelectrics.