Microwave-assisted hydrothermal synthesis of NiMoO4 nanorods for high-performance urea electrooxidation

A large surface area with high active site exposure is desired for the nano-scaled electrocatalysts fabrication.Herein,taking Ni Mo O₄nanorods for example,we demonstrated the advantages of the microwaveassisted hydrothermal synthesis method compared to the traditional hydrothermal approaches.Both monoclinic structured Ni Mo O₄in the nanorods morphology are found for these samples but it is more time-saving and efficient in the Ni-Mo synergism for the catalyst obtained by mi...     

Peculiarities of xonotlite synthesis from the raw materials with different SiO2 activities

In this work, the peculiarities of xonotlite hydrothermal synthesis at 200 °C from lime and SiO₂ materials with different pozzolanic activities (A_P) were investigated: calcinated opoka (A_p?=?170.1 mgCaO kg^?1), granite sawing waste (A_p?=?52.2 mgCaO g^?1) and reagent SiO₂·nH₂O (A_p?=?336.8 mgCaO kg^?1). By XRD, DSC, TG, SEM, FT-IR methods have been shown that the formation of crystalline calcium silicate hydrates and the sequence of the intermediate phases existence are influenced not only by SiO₂ component activity, but by other factors too. The use of the most active raw meal with SiO₂·nH₂O results in a very rapid formation of z-phase, C–S–H(I) and gyrolite, which hardly recrystallize into thermodynamically stable mineral—xonotlite. The impurities in the starting materials may promote the formation of some other compounds and retard the synthesis of stoichiometric ones: high content of Al-containing minerals in granite sawing waste (15.41% of Al₂O₃) predetermines that 1.13 nm tobermorite even after 72 h of hydrothermal curing did not recrystallize into xonotlite. Regardless of its average activity, calcinated opoka is an excellent material for the synthesis of crystalline calcium silicate hydrates. Amorphous SiO₂ from opoka begins to react first, followed by tridymite and cristobalite. 1.13 nm tobermorite and xonotlite are formed at the beginning of the hydrothermal synthesis (4 h), and this greatly reduces the probability of the existence of amorphous phases.

     

Synthesis of Flower-like NaY(MoO4)2 and Optical Property of NaY(MoO4)2:Eu3+

Flower-like NaY(MoO₄)₂ particles were synthesized through a microwave-assisted hydrother-mal process followed by a subsequent calcination process. The products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field-emission scanning electron mi-croscopy. The possible formation mechanism of the flower-like NaY(MoO₄)₂ precursor was proposed. The NaY(MoO₄)₂:Eu³⁺ phosphors were also prepared and their luminescence properties showed the NaY(MoO₄)₂:Eu³⁺ materials with the emission peak at 612 nm had potential application as a red phosphor for white light-emitting diodes. Furthermore, the microwave-assisted hydrothermal process followed by a subsequent calcination process could be extended to prepare the other lanthanide molybdates with the flower-like morphology.     

Advantage of low-temperature hydrothermal synthesis to grow stoichiometric crednerite crystals

This work reports a new approach for the growth of stoichiometric crednerite CuMnO₂ crystals. The hydrothermal reaction, starting from soluble metal sulphates as precursors, is assisted by ethylene glycol and the formation of crednerite is found to depend strongly on pH and temperature. This method allows obtaining small hexagonal platelets with the larger dimension about 1.0–1.5 μm and with a composition characterized by a Cu/Mn ratio of 1. Thus, these crystals differ from the needle-like millimetric ones obtained by the flux technique for which the composition departs from the expected one and is close to Cu_1.04Mn_0.96. This monitoring of the cationic composition in crednerite, using hydrothermal synthesis, is important as the Cu/Mn ratio controls the low temperature antiferromagnetic ground-state.     

Catalytic Double Carbon–Boron Bond Formation for the Synthesis of Cyclic Diarylborinic Acids as Versatile Building Blocks for π‐Extended Heteroarenes

The first catalytic synthesis of cyclic diarylborinic acids is developed using a dihydroaminoborane reagent as the boron source. Unlike previously reported methods that use organolithium reagents, this method allows the easy synthesis of cyclic diarylborinic acids bearing a range of functionalities including CN, CO₂Et, CONEt₂ and NMeCO₂^t Bu. Furthermore, these cyclic diarylborinic acids provide rapid access to skeletal diversity, in particular they enable the synthesis of six‐ to nine‐membered π‐extended heteroarenes through simple cross‐coupling reactions, which are important synthetic targets in both advanced materials and pharmaceuticals.     

Reduced Graphene Oxide‐Supported TiO2 Fiber Bundles with Mesostructures as Anode Materials for Lithium‐Ion Batteries

Although the synthesis of mesoporous materials is well established, the preparation of TiO₂ fiber bundles with mesostructures, highly crystalline walls, and good thermal stability on the RGO nanosheets remains a challenge. Herein, a low‐cost and environmentally friendly hydrothermal route for the synthesis of RGO nanosheet‐supported anatase TiO₂ fiber bundles with dense mesostructures is used. These mesostructured TiO₂‐RGO materials are used for investigation of Li‐ion insertion properties, which show a reversible capacity of 235 mA h g^?1 at 200 mA g^?1 and 150 mA h g^?1 at 1000 mA g^?1 after 1000 cycles. The higher specific surface area of the new mesostructures and high conductive substrate (RGO nanosheets) result in excellent lithium storage performance, high‐rate performance, and strong cycling stability of the TiO₂‐RGO composites.     

Water‐Splitting Electrocatalysis in Acid Conditions Using Ruthenate‐Iridate Pyrochlores

The pyrochlore solid solution (Na_0.33Ce_0.67)₂(Ir_1?xRu_x)₂O₇ (0≤x≤1), containing B‐site Ru^IV and Ir^IV is prepared by hydrothermal synthesis and used as a catalyst layer for electrochemical oxygen evolution from water at pH<7. The materials have atomically mixed Ru and Ir and their nanocrystalline form allows effective fabrication of electrode coatings with improved charge densities over a typical (Ru,Ir)O₂ catalyst. An in situ study of the catalyst layers using XANES spectroscopy at the Ir L_III and Ru K edges shows that both Ru and Ir participate in redox chemistry at oxygen evolution conditions and that Ru is more active than Ir, being oxidized by almost one oxidation state at maximum applied potential, with no evidence for ruthenate or iridate in +6 or higher oxidation states.     

Time‐Resolved In Situ MAS NMR Monitoring of the Nucleation and Growth of Zeolite BEA Catalysts under Hydrothermal Conditions

Time‐resolved ¹³C, ²³Na, ²⁷Al, and ²⁹Si MAS NMR has been applied in situ for monitoring the hydrothermal synthesis of zeolite BEA. Isotopic labelling with ²⁹Si and ¹³C isotopes has been used to follow the fate of siliceous species and structure directing agent ((¹³CH₃−CH₂)₄NOH). Two mechanistic pathways, namely solution‐mediated and solid–solid hydrogel rearrangement have been distinguished for two synthesis procedures studied. The mechanisms of structure‐directing behavior of TEA⁺ cations in two reaction pathways have been elucidated. The results show that multinuclear MAS NMR can serve as a superior tool for monitoring hydrothermal synthesis of various solids including zeolites, zeotypes, mesoporous materials, metal–organic frameworks and so on and for the design of novel outstanding materials for different applications.     

Cluster rhenium(III) complexes with adamantanecarboxylic acids: Synthesis and properties

Versatile procedures for the synthesis of possible structural types of dirhenium(III) halocarboxylates with adamantanecarboxylic acids were developed. A comprehensive study of the synthesis and interconversions of isomeric dirhenium(III) trans-and cis-tetrahalodi-μ-carboxylates led us to a discovery of a versatile route of prepation of trans derivatives in virtually stoichiometric yields in both the solid and liquid phases. It was found that successive replacement of halide ligands in the nearest environment of the binuclear Re ₂ ⁶⁺ ion by carboxylate ligands is accompanied by gradual hypsochromic shifting of the longest-wavelength absorption band and by a monotonic decline in its intensity, which allows this band to be assigned to the δ-δ* electronic transition.     

Synthesis and Characterization of the Orthorhombic Sn3O4 Polymorph

An unexplored tin oxide crystal phase (Sn₃O₄) was experimentally synthesized via a facile hydrothermal method. After tuning the often-neglected parameters for the hydrothermal synthesis, namely the degree of filling of the precursor solution and the gas composition in the reactor head space, an unreported X-ray diffraction pattern was discovered. Through various characterization studies, such as Rietveld analysis, energy dispersive X-ray spectroscopy, and first-principles calculations, this novel material was characterized as orthorhombic mixed-valence tin oxide with the composition Sn^II₂Sn^IVO₄. This orthorhombic tin oxide is a new polymorph of Sn₃O₄, which differs from the reported conventional monoclinic structure. Computational and experimental analyses showed that orthorhombic Sn₃O₄ has a smaller band gap (2.0 eV), enabling greater absorption of visible light. This study is expected to improve the accuracy of hydrothermal synthesis and aid the discovery of new oxide materials.     

Pre-potassiated hydrated vanadium oxide as cathode for quasi-solid-state zinc-ion battery

Zinc-ion batteries（ZIBs）, in particular quasi-solid-state ZIBs, occupy a crucial position in the field of energy storage devices owing to the superiorities of abundant zinc reserve, low cost, high safety and high theoretical capacity of zinc anode. However, as divalent Zn²⁺ions experience strong electrostatic interactions when intercalating into the cathode materials, which poses challenges to the structural stability and higher demand in Zn²⁺ions diffusion kinetics of the ...     

Enhanced electrochemical capacitance of nitrogen-doped carbon gels synthesized by microwave-assisted polymerization of resorcinol and formaldehyde

Nitrogen-doped carbon gels were synthesized by ammonia-assisted carbonization of resorcinol–formaldehyde (RF) polymers obtained under microwave irradiation without any basic catalyst. Compared with the RF polymer synthesized by the conventional hydrothermal method, microwave polymerization produced spherical beads with a higher surface area (1710 m²/g vs. 1080 m²/g), and smaller (∼700 nm vs. ∼5 μm) but more uniform bead sizes. The majority of their pores were micropores. As a result, the electrochemical capacitance of microwave-assisted nitrogen-doped carbons was significantly higher than that of materials prepared by the conventional hydrothermal method. Thus microwave-assisted polymerization followed by ammonia-assisted carbonization is a useful method to synthesize nitrogen-doped carbon gels for electrochemical double layer capacitors.     

Effect of Synthesis Parameters on Sol–Gel Silica Modified by Zirconia

An experimental strategy was developed to obtain mesoporous SiO₂-ZrO₂ mixed oxides via a sol–gel process, which involved the use of tetraethylorthosilicate (TEOS) and an inorganic Zr-containing salt. The effects of key process parameters on the properties of the materials were investigated, including the choice of Zr(IV) source (zirconium oxychloride or nitrate), the ZrO₂ content and the synthesis pressure (i.e. ambient pressure or hydrothermal conditions). The resulting solids were dried, calcined at 500 °C, and characterized by nitrogen physisorption, pyridine chemisorption, ²⁹Si Nuclear Magnetic Resonance and X-ray diffraction. The data revealed that mesoporous materials with very narrow pore diameter distribution were obtained when using the autoclave procedure from both zirconium nitrate and oxychloride salts. The surface areas and pore size distributions were a function of ZrO₂ content. Differences in acidity, as determined by pyridine adsorption, were observed depending on the synthesis parameters.     

Synthesis, characterization, and catalytic properties of stable mesoporous molecular sieve MCM-41 prepared from zeolite mordenite

Mesoporous molecular sieves (denoted as M-MCM-41) with ordered hexagonal structure have been successfully synthesized from the assembly of precursors from preformed zeolite Mordenite with CTAB surfactant micelle in alkaline media. The samples were characterized by XRD, N₂ adsorption, IR and DTG. The materials exhibit highly hydrothermal stability, as compared with conventional MCM-41. Characterization results indicate that the mesoporous walls of M-MCM-41 contain the secondary building units similar to those in microporous crystal of zeolite Mordenite. In catalytic dealkylation of C10⁺ aromatic hydrocarbon, M-MCM-41 shows higher activities in comparison with Mordenite and MCM-41, which would be ascribed to the combination of advantages of both MCM-41 (large pores) and Mordenite (strong acidity). Furthermore, this synthesis strategy could be used as a new general method for the preparation of hydrothermally stable mesoporous aluminosilicate materials under alkaline conditions.     

Defect‐Controlled Formation of Triclinic Na2CoP2O7 for 4 V Sodium‐Ion Batteries

Simple defects such as sodium deficiencies can induce the selective synthesis of triclinic Na₂CoP₂O₇, providing an increase in energy density of more than 40 % compared to the stoichiometric polymorph that is preferentially formed under the commonly used synthesis conditions. Such a significant improvement, which was achieved just by changing the crystal structure, suggests that controlling the polymorphism could be an effective and facile method for developing high‐performance electrode materials and that defects can play a remarkable role in this process.     

Revealing the Formation Mechanism of CsPbBr3 Perovskite Nanocrystals Produced via a Slowed‐Down Microwave‐Assisted Synthesis

We developed a microwave‐assisted slowed‐down synthesis of CsPbBr₃ perovskite nanocrystals, which retards the reaction and allows us to gather useful insights into the formation mechanism of these nanoparticles, by examining the intermediate stages of their growth. The trends in the decay of the emission intensity of CsPbBr₃ nanocrystals under light exposure are well correlated with their stability against decomposition in TEM under electron beam. The results show the change of the crystal structure of CsPbBr₃ nanocrystals from a deficient and easier to be destroyed lattice to a well crystallized one. Conversely the shift in the ease of degradation sheds light on the formation mechanism, indicating first the formation of a bromoplumbate ionic scaffold, with Cs‐ion infilling lagging a little behind. Increasing the cation to halide ratio towards the stoichiometric level may account for the improved radiative recombination rates observed in the longer reaction time materials.     

Water-Tolerant Superbase Polyoxometalate [H2(Nb6O19)]6− for Homogeneous Catalysis

Here, doubly protonated Lindqvist-type niobium oxide cluster [H₂(Nb₆O₁₉)]^6–, fabricated by microwave-assisted hydrothermal synthesis, exhibited superbase catalysis for Knoevenagel and crossed aldol condensation reactions accompanied by activating C−H bond with pK_a >26 and proton abstraction from a base indicator with pK_a=26.5. Surprisingly, [H₂(Nb₆O₁₉)]⁶⁻ exhibited water-tolerant superbase properties for Knoevenagel and crossed aldol condensation reactions in the presence of water, although it is well known that the strong basicity of metal oxides and organic superbase is typically lost by the adsorption of water. Density functional theory calculation revealed that the basic surface oxygens that share the corner of NbO₆ units in [H₂(Nb₆O₁₉)]⁸⁻ maintained the negative charges even after proton adsorption. This proton capacity and the presence of un-protonated basic sites led to the water tolerance of the superbase catalysis.     

Pb2BO3I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe2BO3F2 (KBBF) Family of Nonlinear Optical (NLO) Materials

Borate halides are an ideal materials class from which to design high‐performance nonlinear optical (NLO) materials. Currently, borate fluorides, chlorides, and bromides are extensively investigated while borate iodide materials discovery remains rare because of the perceived synthetic challenges. We report a new borate iodide, Pb₂BO₃I, synthesized by a straightforward hydrothermal method. The Pb₂BO₃I chemical formula conceals that the compound exhibits a structure similar to the well‐established KBe₂BO₃F₂ (KBBF), which we show supports the highest second‐harmonic generation (SHG) at 1064 nm in the KBBF family, 10 × KH₂PO₄ (KDP), arising from the inclusion of Pb²⁺ and I^? and the crystal chemistry. Our work shows that KBBF‐related compounds can be synthesized incorporating iodide and exhibit superior NLO responses.     

Mesoporous MnO2 synthesized by hydrothermal route for electrochemical supercapacitor studies

Poorly crystalline mesoporous MnO₂, which is suitable for supercapacitor studies, is synthesized from neutral KMnO₄ aqueous solution by hydrothermal route. But it requires a high temperature (180 °C) and also a long reaction time (24 h). Addition of a tri-block copolymer, namely, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123), which is generally used as a soft template for the synthesis of nano-structured porous materials, reduces the hydrothermal temperature to 140 °C and also reaction time to 2 h. When the reaction time is increased, the product morphology changes from nanoparticles to nanorods with a concomitant decrease in BET surface area. Also, the product tends to attain crystallinity. The electrochemical capacitance properties of MnO₂ synthesized under varied hydrothermal conditions are studied in 0.1 M Na₂SO₄ electrolyte. A specific capacitance of 193 F?g^?1 is obtained for the mesoporous MnO₂ sample consisting of nanoparticle and nanorod mixed morphology synthesized in 6 h using P123 at 140 °C.     

A facile synthesis of luminescent YVO4:Eu3+ hollow microspheres in virtue of template function of the SDS–PEG soft clusters

Hollow europium-doped yttrium orthovanadate (YVO₄:Eu³⁺) microspheres were fabricated via a sodium dodecyl sulfate (SDS)–polyethylene glycol (PEG)-assisted hydrothermal technique. The as-synthesized hollow YVO₄:Eu³⁺ microspheres were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). The obtained results showed that the morphology and size of the hollow microspheres have a strong dependence on the hydrothermal reaction time of the YVO₄:Eu³⁺ powders. It is believed that the SDS–PEG clusters perform a function of dual soft-template that results in a unique template-induced secondary assembly in the one-pot synthesis of hollow YVO₄:Eu³⁺ microspheres. The photoluminescence measurement revealed that the YVO₄:Eu³⁺ powders with a spherical hollow shape have better red luminescence compared to the YVO₄:Eu³⁺ solid microspheres. As a result, the controlled synthesis of hollow YVO₄:Eu³⁺ microspheres not only has a great theoretical significance in studying the three-dimensional control and selective synthesis of inorganic materials but also benefits the potential applications based on hollow YVO₄:Eu³⁺ microspheres owing to reducing the usage of expensive rare-earth elements.