Heterogeneous synthesis of glycerol carbonate from glycerol and dimethyl carbonate catalyzed by LiCl/CaO

In this article, a CaO-based catalyst was prepared by impregnating chloride salts on CaO to develop a highly efficient heterogeneous catalyst for the synthesis of glycerol carbonate (GC) from glycerol and dimethyl carbonate. LiCl/CaO exhibited a high catalytic activity under moderate reaction conditions. The effects of the LiCl loadings, the amount of catalyst and the calcination temperature on the catalytic activity were investigated. The highest yield of 94.19% glycerol carbonate was obtained at 65 °C on CaO loaded with 10% LiCl after 1 h, and the catalyst had high stability in reusing work. Scanning electron microscopy (SEM), X-ray diffraction (XRD), BET, CO₂-TPD, XPS and thermalgravity (TG) were used to characterize the prepared catalyst. It was found that the high catalytic activity of CaO after modification with LiCl is associated with the structural aspects and the amount of basicity of the catalyst. The Li₂O₂ species, which is a strong basic site that is formed by the substitution of the Ca²⁺ in CaO lattice by Li⁺, has great activity for transesterification.     

Cobalt‐Doped Perovskite‐Type Oxide LaMnO3 as Bifunctional Oxygen Catalysts for Hybrid Lithium–Oxygen Batteries

Perovskite‐type oxides based on rare‐earth metals containing lanthanum manganate are promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. Perovskite‐type LaMnO₃ shows excellent ORR performance, but poor OER activity. To improve the OER performance of LaMnO₃, the element cobalt is doped into perovskite‐type LaMnO₃ through a sol–gel method followed by a calcination process. To assess electrocatalytic activities for the ORR and OER, a series of LaMn_1?xCo_xO₃ (x=0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) perovskite oxides were synthesized. The results indicate that the amount of doped cobalt has a significant effect on the catalytic performance of LaMn_1?xCo_xO₃. If x=0.3, LaMn_0.7Co_0.3O₃ not only shows a tolerable electrocatalytic activity for the ORR, but also exhibits a great improvement (>200 mV) on the catalytic activity for the OER; this indicates that the doping of cobalt is an effective approach to improve the OER performance of LaMnO₃. Furthermore, the results demonstrate that LaMn_0.7Co_0.3O₃ is a promising cost‐effective bifunctional catalyst with high performance in the ORR and OER for application in hybrid Li?O₂ batteries.     

Core shell‐structured NiFe2O4@TiO2 nanoparticle‐anchored reduced graphene oxide for rapid degradation of rhodamine B

In this work, the NiFe₂O₄@TiO₂/reduced graphene oxide (RGO) ternary nanocomposites with high saturation magnetization and catalytic efficiency have been synthesized through the following steps. First, graphene oxide was prepared using the modified Hummer's method. Second, the NiFe₂O₄ nanoparticles were successfully prepared using the hydrothermal method. Third, the core shell‐structured NiFe₂O₄@TiO₂/RGO nanocomposite precursors were easily obtained through hydrolysis reaction. The morphology of NiFe₂O₄@TiO₂/RGO nanocomposites was characterized from scanning electron microscope (SEM) and transmission electron microscope (TEM) images. Moreover, the results of X‐ray diffraction (XRD) patterns proved that the TiO₂ coating shell consisted of anatase. The vibrating sample magnetometer (VSM) measurements showed that the saturation magnetization value of NiFe₂O₄@TiO₂/RGO ternary nanocomposites was 25 emu/g. The X‐ray photoelectron spectroscopy (XPS) analysis confirmed that only part of the graphite oxide (GO) was reduced to RGO in the ternary nanocomposite. The degradation experiments proved that NiFe₂O₄@TiO₂/RGO nanocomposite exhibited the high catalytic efficiency and outstanding recyclable performance for rhodamine B (RhB).     

Synthesis of glycerol carbonate from glycerol and dimethyl carbonate catalyzed by K2CO3/MgO

A series of M/MgO (M?=?CaO, KNO₃, KOH, K₂CO₃) catalysts were prepared by a dry impregnation method and used for synthesis of glycerol carbonate from glycerol and dimethyl carbonate. It was found that K₂CO₃/MgO was the most efficient catalyst, with a glycerol carbonate yield of approximately 99% under the conditions: DMC/glycerol molar ratio 2.5:1, catalyst/raw material weight ratio 1%, reaction time 2?h, and reaction temperature 80?°C. FTIR, BET, TEM, and XRD were used for characterization of the catalyst and showed that the active sites seemed to be K₂O formed on the K₂CO₃/MgO catalyst. Finally, a recycling experiment showed that the catalyst was relatively stable and could be reused up to four times, at least, by regeneration.     

The solid state reaction between lanthanum oxide and strontium carbonate

The reaction between lanthanum oxide and strontium carbonate was studied non-isothermally between 350 and 1150 °C at different heating rates, intermediates and the final solid product were characterized by X-ray diffractometry (XRD). The reaction proceeds through formation of lanthanum oxycarbonate La₂O(CO₃)₂, lanthanum dioxycarbonate La₂O₂CO₃, and non-stoichiometric strontium lanthanum oxide La₂SrO_x (x = 4 + δ). La₄SrO₇ was found to be the final product which begins to form at ∼700 °C. Li⁺ doping enhances the formation of the final product as well as commencement of the reactions at lower temperatures.     

Fabrication and characterization of double‐shelled CeO2‐La2O3/Au/Fe3O4 hollow architecture as a recyclable and highly thermal stability nanocatalyst

A novel magnetic binary‐metal‐oxide‐coated nanocataly composing of a hollow Fe₃O₄ core and CeO₂‐La₂O₃ shells with Au nanoparticles encapsulated has been created in this work. The structural features of catalysts were characterized by several techniques, including SEM, TEM, UV‐vis, FTIR, XRD, XPS and TGA analyses. After the coating of CeO₂‐La₂O₃ layer, CeO₂‐La₂O₃/Au/C/Fe₃O₄ microspheres showed a superior thermal stability and catalytic reactivity compared with a pure CeO₂ or La₂O₃ layer. Accompanied by the burning of carbon layer, the specific surface could be increased by the formation of double‐shelled structure. Besides, the desired samples could be separated by magnet, implying the superior recycle performance. Using the reduction of 4‐nitrophenol by NaBH₄ as a model reaction, the microspheres exhibited highly reusability, superior catalytic activity, thermal stability, which are attributed to the unique double‐shelled structure of the support, uniform distribution of Au nanoparticles, the highly thermal stability of CeO₂‐La₂O₃ layer and mixed oxide synergistic effect. As a consequence, the unique nanocatalyst will open a promising way in the fabrication of the double‐shelled hollow binary‐metal‐oxide materials for future research and has great potential in other applications.     

Synthesis of La<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> by thermal treatment of mechanically activated salt mixture

A lanthanum zirconate La₂Zr₂O₇ was synthesized by soft mechanochemical method using zirconium oxynitrate ZrO(NO₃)₂·6H₂O and lanthanum carbonate La₂(CO₃)₃·8H₂O as reagents. Mechanical activation of the reagents was carried out in a centrifugal planetary ball mill. The processes occurring during calcination of the jointly and the separately mechanically activated salt mixture were studied using DSC, TG coupled with mass spectrometry, XRD analysis, and FTIR spectroscopy. It was shown that in the course of joint mechanical activation in the mill alongside with intimate mixing of the reagents and their amorphization exchange reaction occurred, producing lanthanum nitrate, basic lanthanum nitrate, basic zirconium carbonate, and hydrated zirconium oxide. The DSC curve of the jointly mechanically activated salt mixture showed a strong exothermic peak at 878 °C which was not associated with mass loss. This peak was attributed to La₂Zr₂O₇ crystallization in agreement with XRD data. Nanocrystalline lanthanum zirconate synthesized by annealing of the jointly mechanically activated salt mixture was characterized using XRD analysis, scanning, and transmission electron microscopy.     

Atom-economy Synthesis of N-Substituted Carbamate from Urea Derivative and Dimethyl Carbonate Catalyzed by La/SiO_2: Characterization and Activity

A series of silica gel immobilized lanthanum catalysts were prepared for the atom‐economy synthesis of N‐substituted carbamates from urea derivatives and dimethyl carbonate. The La/SiO₂ catalysts with lanthanum loadings varied from 1.3 wt% to 8.5 wt% were characterized by AES, BET, XRD, TEM, FT‐IR, XPS and TPD. According to the characterization, lanthanum species with particle sizes of 5–10 nm on the surface of silica gel were formed. The catalysts were all amorphous and the surface areas were 336.5–530.2 m²/g. NH₃‐TPD analysis showed that all samples exhibited similar acid strength with different acid amounts. FT‐IR measurement indicated that the component of lanthanum species on the catalyst surface were La(OH)₃, LaOOH and hydrated La₂O₃. Also, the peak value of the absolute amount of LaOOH was obtained with 4.3 wt% lanthanum loading. The BET surface area decreased dramatically when the lanthanum loading was above 4.3 wt%. In consideration of the results obtained from the catalytic reactions, it could be concluded that LaOOH was the possible active species and high surface area was important for the high catalytic activity.     

Continuous Dehydrogenation of n‐Pentanol over a Cr Modified Cu/γ‐Al2O3‐La2O3 Catalyst

The oxidant‐free dehydrogenation of n‐pentanol over copper based catalysts was investigated in this paper. The effect of metal modification on the activity and stability of the copper catalyst supported on γ‐Al₂O₃ and La₂O₃ (Cu/γ‐Al₂O₃‐La₂O₃) was clarified and a Cr modified Cu/Al₂O₃‐La₂O₃ (Cu‐Cr/γ‐Al₂O₃‐La₂O₃) showed the best catalytic performance. The conversion of n‐pentanol was 70.0% and the selectivity for n‐pentanal increased to 97.1% over Cu‐Cr/γ‐Al₂O₃‐La₂O₃. X‐ray diffraction and temperature programmed reduction of H₂ indicated that the addition of Cr favors the formation and reduction of the copper oxide, and the dispersion of the active Cu⁰ species, accounting for the good activity and stability of this catalyst. Furthermore, the lower amount of acidic sites in Cu‐Cr/γ‐Al₂O₃‐La₂O₃ is suggested to suppress the dehydration in oxidant‐free dehydrogenation of n‐pentanol, accounting for the higher selectivity for n‐pentanal.     

Hydrothermal Synthesis of g‐C3N4/NiFe2O4 Nanocomposite and Its Enhanced Photocatalytic Activity

Herein, for the first time, a direct Z‐scheme g‐C₃N₄/NiFe₂O₄ nanocomposite photocatalyst was prepared using facile one‐pot hydrothermal method and characterized using XRD, FT‐IR, DRS, PL, SEM, EDS, TEM, HRTEM, XPS, BET and VSM characterized techniques. The result reveals that the NiFe₂O₄ nanoparticles are loaded on the g‐C₃N₄ sheets successfully. The photocatalytic activities of the as‐prepared photocatalysts were evaluated for the degradation of methyl orange (MO) under visible light irradiation. It was shown that the photocatalytic activity of the g‐C₃N₄/NiFe₂O₄ nanocomposite is about 4.4 and 3 times higher than those of the pristine NiFe₂O₄ and g‐C₃N₄ respectively. The enhanced photocatalytic activity could be ascribed to the formation of g‐C₃N₄/NiFe₂O₄ direct Z‐scheme photocatalyst, which results in efficient space separation of photogenerated charge carriers. More importantly, the as‐prepared Z‐scheme photocatalyst can be recoverable easily from the solution by an external magnetic field and it shows almost the same activity for three consecutive cycles. Considering the simplicity of preparation method, this work will provide new insights into the design of high‐performance magnetic Z‐scheme photocatalysts for organic contaminate removal.     

An investigation into synergistic effects of rare earth oxides on intumescent flame retardancy of polypropylene/poly (octylene‐co‐ethylene) blends

Synergistic effects of two kinds of rare earth oxides (REOs), neodymium oxide (Nd₂O₃) or lanthanum oxide (La₂O₃) on the intumescent flame retardancy of thermoplastic polyolefin (TPO) made by polypropylene/poly (octylene‐co‐ethylene) blends were investigated systemically by various methods. The limiting oxygen index (LOI) of flame retardant TPO (FRTPO) filled by 30 wt% intumescent flame retardants (IFR) composed of ammonium polyphosphate (APP) and pentaerythritol (PER) has been increased from 30 to 32.5 and 33.5 when 0.5 wt% of IFR was substituted by La₂O₃ and Nd₂O₃, respectively. Cone calorimetry tests also reveal the existence of synergistic effects. Thermalgravimetric analyses (TGA) demonstrate that the presence of REOs promotes the esterification and carbonization process in low‐temperature range while enhances the thermal stability of IFR and FRTPO in high‐temperature range. X‐ray diffraction (XRD) reveals that the interaction of Nd₂O₃ with IFR results in the formation of neodymium phosphate (NdP₅O₁₄) with high‐thermal stability. Thermal scanning rheological tests show that the presence of REOs increases complex viscosity of FRTPO in the temperature range of 190～300°C so as to suppress melt dripping but decreases the complex viscosity and increases the loss factors tan δ in temperature range of 300～400°C to make the carbonaceous strucuture more flexible and viscous to resist stress, expand better and keep intact. Copyright © 2009 John Wiley & Sons, Ltd.     

A Facile Molten‐Salt Route for Large‐Scale Synthesis of NiFe2O4 Nanoplates with Enhanced Lithium Storage Capability

Binary metal oxides have been deemed as a promising class of electrode materials for high‐performance lithium ion batteries owing to their higher conductivity and electrochemical activity than corresponding monometal oxides. Here, NiFe₂O₄ nanoplates consisting of nanosized building blocks have been successfully fabricated by a facile, large‐scale NaCl and KCl molten‐salt route, and the changes in the morphology of NiFe₂O₄ as a function of the molten‐salt amount have been systemically investigated. The results indicate that the molten‐salt amount mainly influences the diameter and thickness of the NiFe₂O₄ nanoplates as well as the morphology of the nanosized building blocks. Cyclic voltammetry (CV) and galvanostatic charge–discharge measurements have been conducted to evaluate the lithium storage properties of the NiFe₂O₄ nanoplates prepared with a Ni(NO₃)₂/Fe(NO₃)₃/KCl/NaCl molar ratio of 1:2:20:60. A high reversible capacity of 888 mAh g^?1 is delivered over 100 cycles at a current density of 100 mA g^?1. Even at a current density of 5000 mA g^?1, the discharge capacity could still reach 173 mAh g^?1. Such excellent electrochemical performances of the NiFe₂O₄ nanoplates are contributed to the short Li⁺ diffusion distance of the nanosized building blocks and the synergetic effect of the Ni²⁺ and Fe³⁺ ions.     

A unique two‐dimensional coordination network of 1‐benzofuran‐2,3‐dicarboxylate with lanthanum(III) obtained by solvothermal synthesis

The title compound, poly[bis[diaqualanthanum(III)]‐tris(μ‐1‐benzofuran‐2,3‐dicarboxylato)], [La₂(C₁₀H₄O₅)₃(H₂O)₄]_n, was obtained under solvothermal conditions by reacting lanthanum trinitrate hexahydrate with 1‐benzofuran‐2,3‐dicarboxylic acid in a strongly basic environment. It forms an extended two‐dimensional coordination network, wherein every lanthanum ion links to four deprotonated diacid ligands, while two of the latter bridge between adjacent metal cations. The component species are additionally linked to one another by hydrogen bonds. The polymeric arrays are tightly stacked one on top of the other, without incorporating any solvent in the interface zones between them, which are lined with the lipophilic benzofuran residues. This study provides the first example of coordination networking with the aid of the 1‐benzofuran‐2,3‐dicarboxylate ligand.     

Tetrakis(μ‐2,3‐dimethoxybenzoato)bis[(2,2′‐bipyridine)(2,3‐dimethoxybenzoato)lanthanum(III)]

The title compound, tetrakis(μ‐2,3‐di­methoxy­benzoato)‐κ⁴O:O′;κ⁶O,O′:O′‐bis[(2,2′‐bi­pyridine‐N,N′)(2,3‐di­methoxy­benzoato‐O,O′)lanthanum(III)], [La₂(2,3‐DMOBA)₆(2,2′‐bpy)₂], where 2,3‐DMOBA is 2,3‐di­methoxy­benzoate (C₉H₉O₄) and 2,2′‐bpy is 2,2′‐bi­pyridine (C₁₀H₈N₂), is a dimer with a centre of inversion between the La atoms bridged by four carboxyl­ate ligands. The central La atom is ennea‐coordinated and has a distorted monocapped square‐antiprism geometry.     

Kinetics of phase formation upon the treatment of La<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>3</Subscript> and La<Subscript>2</Subscript>O<Subscript>2</Subscript>SO<Subscript>4</Subscript> in a hydrogen flow

The sequence of phases occurring during treatment of lanthanum sulfate, La₂(SO₄)₃ and lanthanum oxysulfate, La₂O₂SO₄ in a hydrogen flow is established. The temperature ranges in which homogeneous La₂O₂S is produced are revealed: when La₂(SO₄)₃ is a precursor, the range is 770–1220 K; in the case of La₂O₂SO₄, the interval is 950–1220 K. The kinetic curves showing the time dependence of the yield of La₂O₂S is constructed and treated using the Avrami-Erofeev and contracting volume equations. The activation energies of the reactions are determined.     

Synthesis of 3‐Methylindole from Glycerol Cyclization with Aniline over CuCr/Al2O3 Catalysts Modified by Alkali Earth Oxides

In the present work, CuCr catalysts supported on γ‐Al₂O₃ are prepared and modified with alkali earth elements by impregnation, characterized by N₂ adsorption–desorption, XRD, H₂‐TPR (temperature‐programmed reduction by H₂), CO₂‐TPD and NH₃‐TPD (temperature‐programmed desorption of NH₃ or CO₂), and applied in the synthesis of 3‐methylindole (3‐MI) with a N‐heterocycle from glycerol and aniline in the fixed‐bed reactor. The results show that the introduction of alkali earth elements into the CuCr/Al₂O₃ catalyst can improve the yield of target 3‐MI in the order of Mg < Ca < Sr < Ba. CuCr‐Ba/Al₂O₃ gives rise to a high 3‐MI yield of 39.09% and 65.17% in N₂ as a carrier gas and 20%H₂–N₂ mixture gas, respectively. According to catalysts characterization and catalytic tests, the reaction pathway of glycerol cyclization with aniline is proposed, the formation of 3‐MI and 3H‐indol‐3‐yl methanol is hypothesized to be through the aniline cyclization with 2,3‐hydroxypropanal from glycerol dehydrogenation over Cu⁰ centers and basic sites. The acidic sites mainly play a role on activating aniline, which interacts with glycerol to form 3‐MI or quinoline through cyclization and dehydration.     

Sunlight‐Driven Hydrogen Peroxide Production from Water and Molecular Oxygen by Metal‐Free Photocatalysts

Design of green, safe, and sustainable process for the synthesis of hydrogen peroxide (H₂O₂) is a very important subject. Early reported processes, however, require hydrogen (H₂) and palladium‐based catalysts. Herein we propose a photocatalytic process for H₂O₂ synthesis driven by metal‐free catalysts with earth‐abundant water and molecular oxygen (O₂) as resources under sunlight irradiation (λ>400 nm). We use graphitic carbon nitride (g‐C₃N₄) containing electron‐deficient aromatic diimide units as catalysts. Incorporating the diimide units positively shifts the valence‐band potential of the catalysts, while maintaining sufficient conduction‐band potential for O₂ reduction. Visible light irradiation of the catalysts in pure water with O₂ successfully produces H₂O₂ by oxidation of water by the photoformed valence‐band holes and selective two‐electron reduction of O₂ by the conduction band electrons.     

La2Si2O7 im I—Typ: Gemäß La6[Si4O13][SiO4]2 kein echtes Lanthandisilicat

I‐Type La₂Si₂O₇: According to La₆[Si₄O₁₃][SiO₄]₂ not a Real Lanthanum Disilicate In attempts to synthesize lanthanum telluride silicate La₂Te[SiO₄] (from La, TeO₂, SiO₂ and CsCl, molar ratio: 1 : 1: 1 : 20, 950 °C, 7 d) or fluoride‐rich lanthanum fluoride silicates (from LaF₃, La₂O₃, SiO₂ and CsCl, molar ratio: 5 : 2 : 3 : 17, 700 °C, 7 d) in evacuated silica tubes, colourless lath‐shaped single crystals of hitherto unknown I‐type La₂Si₂O₇ (monoclinic, P2₁/c; a = 726.14(5), b = 2353.2(2), c = 1013.11(8) pm, β = 90.159(7)°) were found in the CsCl‐flux melts. Nevertheless, this new modification of lanthanum disilicate does not contain any discrete disilicate groups [Si₂O₇]^6‐ but formally three of them are dismutated into one catena‐tetrasilicate ([Si₄O₁₃]^10‐ unit of four vertex‐linked [SiO₄]^4‐ tetrahedra) and two ortho‐silicate anions (isolated [SiO₄]^4‐ tetrahedra) according to La₆[Si₄O₁₃][SiO₄]₂. This compound can be described as built up of alternating layers of these [SiO₄]^4‐ and the horseshoe‐shaped [Si₄O₁₃]^10‐ anions along [010]. Between and within the layers the high‐coordinated La ³⁺ cations (CN = 9 ‐ 11) are localized. The close structural relationship to the borosilicates M₃[BSiO₆][SiO₄](M = Ce ‐ Eu) is discussed and structural comparisons with other catena‐tetrasilicates are presented.     

catena‐Poly­[[heptakis­(di­methyl­form­amide‐κO)­di‐μ4‐oxo‐tetra‐μ3‐oxo‐hexa­deca‐μ2‐oxo‐tetra­oxo­lan­than­um(III)­octamolybdenum(IV)]‐μ‐sodium(I)]

The title compound, [NaLaMo₈O₂₆(C₃H₇NO)₇]_n, contains infinite chains of [Mo₈O₂₆]⁴⁻ units supporting di­methyl­form­amide‐coordinated La^III cations and linked by Na⁺ cations. The lanthanum center adopts a nine‐coordinate geometry and the Na atom is sandwiched between two β‐[Mo₈O₂₆]⁴⁻ units.     

La4B14O27: Ein Lanthan‐ultra‐Oxoborat mit Raumnetzstruktur

La₄B₁₄O₂₇: A Lanthanum ultra‐Oxoborate with a Framework Structure Single crystals of La₄B₁₄O₂₇ could be synthesized by the reaction of La₂O₃, LaCl₃ and B₂O₃ with an access of CsCl as fluxing agent in gastightly sealed platinum ampoules within twenty days at 710 °C and appear as colourless, transparent and waterresistant platelets. The new lanthanum oxoborate La₄B₁₄O₂₇ (monoclinic, C2/c; a = 1120.84(9), b = 641.98(6), c = 2537.2(2) pm, β = 100.125(8)°; Z = 4) is built of a three‐dimensional boron‐oxygen framework containing seven crystallographically different boron atoms. Four of these B³⁺ cations are surrounded by four O^2? anions tetrahedrally, whereas the other three have only three oxygen neighbours with nearly plane triangular coordination figures. Three of the [BO₄]^5? tetrahedra form [B₃O₉]^9? rings by cyclic vertex‐condensation, which are further linked via [BO₃]^3? units to infinite layers. Two of these layers connect via one [B₂O₇]^8? unit of two corner‐shared [BO₄]^5? tetrahedra to double layers, which themselves build up a three‐dimensional framework together with chains consisting of two [BO₄]^5? tetrahedra and one [BO₃]^3? triangle. One of the two crystallographically independent La³⁺ cations (La1) is surrounded by ten O^2? anions and resides within the oxoborate double layers. (La2)³⁺ shows a (8+2)‐fold coordination of O^2? anions and occupies channels along the [110] direction.