Low-temperature synthesis of porous high-entropy (CoCrFeMnNi)3O4 spheres and their application to the reverse water-gas shift reaction as catalysts.

A high-entropy porous spinel oxide [(Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)3O4] was synthesized via a solvothermal method and calcination. Solvothermal conditions yielding homogeneous precursor composites with five metals were optimized. Low-temperature calcination of the amorphous composites at 500 °C for 60 min yielded porous spheres formed by small primary particles, with crystal structures attributed to single-phase spinels. The homogeneity of the five elements in the spheres was verified via scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy analysis. The high-entropy (Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)3O4 spheres exhibited superior catalytic activity and long-term stability for the reverse water-gas shift reaction at 700 °C for at least 15 h. The importance of the Cr component in stabilizing the spinel structure was demonstrated. Mn, Fe, Co, and Ni served as active sites in the reaction. The advantage of solvothermal synthesis for porous high-entropy materials was discussed.

Contribution of micropores in porous zirconia spheres to high optical transparency of dental resin composites.

Transparency to UV-Vis light and radiopacity of dental resin composites containing zirconia (ZrO2) fillers were investigated. The transparency of the resin composite containing porous ZrO2 spheres was much higher than that containing irregularly shaped ZrO2 particles. Calcination of the porous ZrO2 spheres at high temperatures led to dramatically reduced specific surface areas and pore volumes. The transparency of the resin composite containing the calcined porous ZrO2 spheres drastically decreased as the calcination temperature increased. Then, the enhanced UV-Vis transmittance of the resin composite containing porous ZrO2 spheres is attributed to the concentration and physical characteristics of the pores. The radiopacity of the resin composites containing porous ZrO2 spheres increased slightly with increasing calcination temperature. This study revealed that the internal structure of the ZrO2 fillers mainly influenced in the UV-Vis light transmittance of the resin composites.

Solvothermal synthesis of hair-like carbon nanotubes onto sub-micron-sized spherical metal oxide catalyst cores.

Long- and uniform-length, and high-density hair-like carbon nanotubes (CNTs) were produced by CNT growth on sub-micron-sized spherical catalyst supports. The nanosized catalysts (FeO x , CoO x , and NiO x ) that were supported in/on the sub-micron-sized spherical metal oxides (TiO2, ZrO2, SnO2, and CeO2) were prepared via one-step solvothermal and/or two-step impregnation methods. The nanosized catalysts supported in/on the spherical metal oxide supports were converted into CNT conjugates with the CNT-hair morphology via a chemical thermal vapor deposition technique using ethyne gas as a carbon source; the CNTs grew on the central spherical metal oxide core under the base growth process conditions. Among the many types of candidate spherical catalyst materials, the combination of FeO x as a catalyst for CNT growth and ZrO2 as a support led to the best growth of CNT-hair under the reaction conditions, which included a temperature of 730 °C, pressure of 65 Pa, a 10 sccm ethyne gas flow, and a reaction time of 10 s. The CNTs consisted of five-to-eight-layered multi-wall structures with lengths of approximately 3 µm. The CNT-hair that was obtained using the solvothermally embedded catalyst showed higher crystallinity and was dense, thick, and straight, while the corresponding CNT-hair obtained using the impregnated catalyst was slightly sparse, thin, and curly. A unique layer structure constructed using large quantities of uniform CNT-hair, including multiple CNT yarns similar to fuzzy balls or cotton candies, was assembled. The CNT-hair conjugate, specifically constructed in a layer structure with core FeO x /ZrO2 catalysts and tangled CNT yarns, had an appearance similar to frog eggs. Therefore, we successfully prepared suitable catalysts for CNT-hair production and fabricated a layer structure consisting of large numbers of CNT-hair conjugates. The unique structures are expected as a new metamaterial with intriguing physical properties, including isotropic absorption of polarized light and electromagnetic waves.

Influence of the nanostructural characteristics of inorganic fillers on the physical properties of resin cements.

Light-curing resin cements, each comprising one of five different inorganic fillers (non-porous and porous spherical SiO2 particles, irregularly shaped glass and ZrO2 particles, and porous ZrO2 spheres), monomers, and polymerization initiators were prepared to determine the effect of filler morphology on the adhesive strength of the resin cement. The strength of adhesion to a computer-aided design/computer-aided manufacturing (CAD/CAM) resin block was investigated mechanically by measuring the tensile bond strength, flexural strength, and elastic modulus. The resin cement containing sub-micron porous ZrO2 spheres had significantly higher tensile bond strength than the other resin cements. The resin cement containing the porous ZrO2 spheres had markedly lower flexural strength and elastic modulus values than the resin cements containing SiO2 and glass fillers.

Insights into the solvothermal reaction for synthesizing tin(iv) oxide porous spheres.

The solvothermal synthesis of SnO2 porous spheres was optimized by varying the reactants, solvents, additives, reaction temperature and reaction time. The products of these trials were characterized by X-ray diffraction, electron microscopy and X-ray fluorescence spectroscopy. SnO2 possessing a highly ordered spherical structure based on the aggregation of nanometer-sized primary particles was obtained using a simple one-pot solvothermal approach. These spheres were porous with a high specific surface area of more than 200 m2 g-1. The electrical conductivity of this material equaled or exceeded that of commercially available SnO2. SnO2-based spherical porous composites including various elements were easily synthesized by incorporating additional materials in the precursor solution.

One-Step Solvothermal Synthesis of Ni Nanoparticle Catalysts Embedded in ZrO2 Porous Spheres to Suppress Carbon Deposition in Low-Temperature Dry Reforming of Methane.

Ni nanoparticle catalysts embedded in ZrO2 porous spheres and ZrO2 porous composite spheres, SiO2-ZrO2, MgO-ZrO2, and Y2O3-ZrO2, with 83-115 nm diameter and 167-269 m2/g specific surface area were prepared by a one-pot and one-step solvothermal reaction from precursor solutions consisting of Ni(NO3)2‧6H2O, Zr(OnBu)4, and acetylacetone in moist ethanol combined with either Si(OEt)4, magnesium acetylacetate, or Y(OiPr)3. The obtained Ni catalysts have high specific surface areas of 130-196 m2/g, even after high-temperature reduction by H2 at 450 °C for 2 h. They were utilized as catalysts for low-temperature dry reforming of methane (DRM) at 550 °C to suppress carbon deposition on Ni nanoparticles. The Ni catalysts embedded in SiO2-ZrO2 and Y2O3-ZrO2 demonstrated high catalytic activity and long stability in the reaction. Moreover, carbon deposition on Ni nanoparticles in the DRM reaction was effectively suppressed in when using the SiO2-ZrO2 and Y2O3-ZrO2 composites.

Ce3+-enriched spherical porous ceria with an enhanced oxygen storage capacity.

Porous ceria was obtained using a unique solvothermal reaction in acetonitrile, applying high temperature and pressure. The resulting material comprised homogeneous and monodisperse spheres and exhibited an extremely large surface area of 152 m2 g-1. From catalytic performance evaluation by vapor- and liquid-phase reactions, the synthesized porous ceria showed superior and different reaction activity compared with commercial CeO2. To examine the origin of the reaction activity of the present porous ceria, synchrotron hard X-ray photoelectron spectroscopy (HAXPES) measurements were carried out. The systematic study of HAXPES measurements revealed that the obtained porous ceria with the present solvothermal method contained a very high concentration of Ce3+. Moreover, O2-pulse adsorption analyses demonstrated a significant oxygen adsorption capacity exceeding 268 µmol-O g-1 at 400 °C owing to its high contents of Ce3+ species.

Tailored Catalytic Nanoframes from Metal-Organic Frameworks by Anisotropic Surface Modification and Etching for the Hydrogen Evolution Reaction.

A facile anisotropic surface modification and etching strategy is presented for the synthesis of hollow structured ZIF-67 nanoframes. The strategy uses structural and compositional distinctions between each crystallographic facet of truncated rhombic dodecahedrons ZIF-67 (tZIF-67 RDs) and the moderate coordinating and etching effects of cyanuric acid (CA). The CA can anisotropically modify and protect the {110} facets from etching, causing the six {100} facets be selectively etched via an inside-out manner, and finally forming the hollow nanoframes. The surface-modified hollow tZIF-67 RDs can be facet-selectively etched by metal salts in an outside-in manner to give metal-doped tZIF-67 nanoframes. After calcination, the metal-tZIF-67 hybrids are converted into metal-Co alloy/C composite catalysts with hollow nanoframed structures. The PtCo/C catalyst with only 5.9 wt % Pt exhibits high catalytic activities and stabilities in the hydrogen evolution reaction (HER) in acidic solutions.

Nanoscale Effect of Zirconia Filler Surface on Mechanical Tensile Strength of Polymer Composites.

A characteristic effect of a nano-concave-convex structure of a zirconia nanoparticle assembly with an inherent porous structure and huge surface area enabled us to introduce systematic surface modification by thermal treatment to smooth surface and polymer impregnation to mask the nano-concave-convex structure of the zirconia nanoparticle assembly. A polymer composite prepared from 30 wt% poly(N-isopropylacrylamide) containing 0.02 wt% zirconia nanoparticle assembly with the inherent nano-concave-convex surface structure showed the highest tensile strength in mechanical tensile testing. However, both sintered zirconia nanoparticle assembly with smooth surface and zirconia nanoparticle assemblies with polymer masked surface showed lower strength with longer elongation at break in mechanical tensile testing.

Porous niobia spheres with large surface area: alcothermal synthesis and controlling of their composition and phase transition behaviour.

Submicron-sized niobia (Nb2O5) porous spheres with a high specific surface area (300 m2 g-1) and nano concave-convex surfaces were synthesized via a rapid one-pot single-step alcothermal reaction. Prolonged reaction time or high reaction temperatures resulted in a morphology change of Nb2O5 from amorphous sphere to rod crystals with hexagonal crystal phase. A similar alcothermal reaction yielded TiO2-Nb2O5 composite porous spheres, whose Ti : Nb molar ratio was controlled by changing the precursor solution component ratios. A simple thermal treatment of amorphous TiO2-Nb2O5 porous spheres consisting of 1 : 2 (molar ratio) Ti : Nb at 600 °C for 2 h induced crystal phase transfer from amorphous to a monoclinic crystal phase of submicron-sized TiNb2O7 porous spheres with a specific surface area of 50 m2 g-1.

Rapid One-Pot Solvothermal Batch Synthesis of Porous Nanocrystal Assemblies Composed of Multiple Transition-Metal Elements.

The ability of a rapid-heating solvothermal process to synthesize porous nanocrystal assemblies composed of the multiple transition metals was demonstrated. The rapid heating facilitated the quick formation of nascent nanocrystals to generate homogeneous mixed transition-metal oxides. Systematic studies of the synthesis of mixed-metal oxides under various experimental conditions indicated that the present simple method is suitable to develop a wide variety of binary and ternary transition-metal systems such as Co/Mn, Ni/Mn, and Co/Mn/Fe mixed-metal oxides. The products obtained from the rapid heating process were hierarchically assembled porous nanospheres composed of sub-10 nm nanocrystals, which had an extraordinarily high surface area and nano/mesopores. Electrochemical tests revealed the high catalytic ability of the porous nanocrystal assemblies in water oxidation.

A new approach to surface activation of porous nanomaterials using non-thermal helium atmospheric pressure plasma jet treatment.

Non-thermal helium atmospheric pressure plasma jet treatment is applied to the surface activation of porous TiO2 nanoparticle assemblies. Treatment conditions such as the working distance of the plasma discharge, helium gas flow rate, and treatment time are optimized for effective removal of contaminants from the assembly surface. Laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) is applied to detect trace amounts of contaminants on assembly surfaces. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations confirm that the nanoparticle assemblies retain their original perfect spherical structures as well as their ultra-fine convex-concave nano-surfaces even after the plasma jet treatment. N2 adsorption/desorption and X-ray diffraction (XRD) measurements show no significant changes in their BET specific surface areas and crystal structures, respectively. The plasma jet-treated TiO2 nanoparticle assemblies show a 3.8 fold improvement in their reaction rate constants for methylene blue degradation and a 2 fold enhancement of their photocurrents under UV irradiation when compared with untreated TiO2.

One-step synthesis of differently bis-functionalized isoxazoles by cycloaddition of carbamoylnitrile oxide with ß-keto esters.

A new protocol for synthesizing different functionalized isoxazoles is provided. Carbamoylnitrile oxide generated from nitroisoxazolone underwent inverse electron-demand 1,3-dipolar cycloaddition with 1,3-dicarbonyl compounds in the presence of magnesium acetate that formed magnesium enolate in situ. Although electron-deficient trifluoroacetoacetate did not undergo this cycloaddition under the same conditions, conversion to sodium enolate furnish the corresponding bis-functionalized trifluoromethylisoxazole. The DFT calculations using B3LYP 6-31G+(d,p) also supported the aforementioned reactivity.

Inverse electron-demand 1,3-dipolar cycloaddition of nitrile oxide with common nitriles leading to 3-functionalized 1,2,4-oxadiazoles.

A carbamoyl-substituted nitrile oxide was generated upon treatment of easily available 2-methyl-4-nitro-3-isoxazolin-5(2H)-one with THF (not dried); the reaction proceeded efficiently even in the absence of any special reagents and reaction conditions. The nitrile oxide caused 1,3-dipolar cycloaddition with common aliphatic nitriles or electron-rich aromatic nitriles to afford 3-functionalized 1,2,4-oxadiazoles, which are expected to serve as precursors for the preparation of a variety of functional materials by the chemical transformation of the carbamoyl group. While conventional preparative methods for 1,2,4-oxadiazoles involve the cycloaddition of an electron-rich nitrile oxide with an electron-deficient nitrile or a nitrile activated by a Lewis acid, our method employs the complementary combination of an electron-rich nitrile and an electron-deficient nitrile oxide- the inverse electron-demand 1,3-cycloaddition. The DFT calculations using B3LYP 6-31G* supported the abovementioned inverse reactivity, and also suggested the presence of an accelerating effect by the carbamoyl group as a result of hydrogen bond formation with a dipolarophilic nitrile.

Bicyclization involving pseudo-intramolecular imination with diamines.

α-Nitro-δ-keto nitriles and α-nitro-δ-keto ester were readily converted to diazabicyclo compounds having vicinal functionality upon treatment with diamines. The keto nitrile attracts the diamine nearby to an acidic hydrogen to cause the pseudo-intramolecular imination which proceeds efficiently without any catalyst at room temperature.

An anomalous hydration/dehydration sequence for the mild generation of a nitrile oxide.

A nitrile oxide containing a carbamoyl group is readily generated upon the treatment of 2-methyl-4-nitro-3-isoxazolin-5(2H)-one with water under mild reaction conditions, even in the absence of special reagents. The obtained nitrile oxide undergoes cycloaddition with dipolarophiles, alkynes and alkenes, to afford the corresponding isoxazol(in)es, which are useful intermediates in the synthesis of polyfunctionalized compounds. A plausible mechanism underlying the formation of the nitrile oxide is proposed, which involves an anomalous hydration/dehydration sequence. DFT calculations were also performed to support this mechanism.

A new chiral probe for sulfate anion: UV, CD, fluorescence, and NMR spectral studies of 1:1 and 2:1 complex formation and structure of chiral guanidinium-p-dimethylaminobenzoate conjugate with sulfate anion.

A new chiral chromophoric host 1, possessing a 4-(N,N-dimethylamino)benzoate (DMAB) group tethered to a chiral bicyclic guanidinium subunit, was synthesized and applied to the probe for sulfate anion. Host 1 showed typical successive 1:1 and 2:1 host:guest complexation behavior toward the divalent sulfate anion, as revealed by UV-vis, CD, fluorescence, and 1H NMR spectroscopic studies. The DMAB chromophore was shown to be a sensitive CD spectral probe for assessing not only the complexation behavior but also complex stoichiometry and structure. The stepwise 1:1 and 2:1 complexation constants (K1 and K2) were determined as 1.53 x 10(6) and 4.84 x 10(4) M(-1), respectively, by NMR titration in CD3CN. The CD exciton chirality method allowed us to determine the chiral sense (spatial arrangement) of the two DMAB moieties in the 2:1 complex as negative (counterclockwise). The dual fluorescence behavior of DMAB was employed for elucidating the role of the countercation upon complexation of host 1 with sulfates possessing lipophilic countercation(s) such as tetrabutylammonium.