Changes in Surface Property and Catalysis of Mesoporous Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> from Amorphous to Crystalline Pore Walls

Abstract  

The amorphous inorganic phase of an ordered amorphous mesoporous Nb₂O₅ with two dimensional hexagonal (2D-hex) structure was crystallized with maintaining the original well arranged porous structure. The difference in surface property between amorphous and crystalline Nb₂O₅ with similar ordered mesoporous structure was compared. It was found from water adsorption–desorption isotherms and observation by infrared (IR) spectroscopy that the amorphous sample was hydrophilic and that the surface OH groups were acidic. On the other hand, the OH groups on crystalline mesoporous Nb₂O₅ were non-acidic and inside the pores was less hydrophilic. The surface property was also compared by a catalytic reaction, oxidation of cyclohexe by an aqueous solution of H₂O₂. The high (95%) selectivity for 1,2-epoxycyclohexane was obtained at 40 °C for 2 h in methanol solvent over crystalline mesoporous Nb₂O₅ at 12% conversion, while amorphous mesoporous Nb₂O₅ showed high (68%) selectivity for 1,2-cyclohexanediol in acetonitrile solvent at 60 °C for 2 h at 22% conversion. The differences in selectivity and the optimal solvent between amorphous and crystalline samples were interpreted in terms of the acidic feature of surface OH groups and hydrophilicity. While similar selectivity was observed over non-porous crystalline Nb₂O₅, much higher conversion over crystalline mesoporous Nb₂O₅ was attained at the same surface area. Thus, an advantage of mesoporous structure is attributed to the higher contact time of molecules inside the pores to the catalyst surface than those outside the particles.     

Preparation and properties of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods as supercapacitor material

Co₃O₄ nanorods have been successfully synthesized by thermal decomposition of the precursor prepared via a facile and efficient microwave-assisted hydrothermal method, using cetyltrimethylammonium bromide (CTAB) with ordered chain structures as soft template for the first time. The obtained Co₃O₄ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical measurements. The results demonstrate that the as-synthesized nanorods are single crystalline with an average diameter of about 20 to 50 nm and length up to several micrometers. Preliminary electrochemical studies, including cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) measurements, are carried out in 6 M KOH electrolyte. Specific capacitance of 456 F g⁻¹ for a single electrode could be achieved even after 500 cycles, suggesting its potential application in electrochemical capacitors. This promising method could provide a universal green chemistry approach to synthesize other low-cost and environmentally friendly transition metal hydroxide or oxide.     

Effective Utilization of the Catalytically Active Phase: NH<Subscript>3</Subscript> Oxidation Over Unsupported and Supported Co<Subscript>3</Subscript>O<Subscript>4</Subscript>

Abstract  

The performance of pellets of unsupported and silica-supported Co₃O₄ in the ammonia oxidation was investigated as a function of the particle size to investigate the utilization of the catalytically active phase in these materials. The obtained activity in terms of ammonia conversion over the silica-supported Co₃O₄ is higher compared to the conversion over the unsupported Co₃O₄, despite a lower cobalt oxide loading and more severe diffusional limitations. The effectiveness factor for the silica-supported catalyst is slightly lower than the effectiveness factor for the unsupported catalyst in the form of pellets of similar size. However, the effective utilization of cobalt within the catalyst is higher for the silica-supported catalyst, mainly due to the higher dispersion of the catalytically active phase.     

Synthesis of nickel catalysts supported on Zr-doped ordered mesoporous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and their catalytic performance for low-temperature CO<Subscript>2</Subscript> reforming of CH<Subscript>4</Subscript>

A series of Zr-doped ordered mesoporous Al₂O₃ with various Zr contents were synthesized by evaporation-induced self-assembly strategy and the Ni-based catalysts supported on these Al₂O₃ materials were prepared by impregnation method. These catalysts with large specific surface area, big pore volume, uniform pore size possess excellent catalytic performance for the low-temperature carbon dioxide reforming of methane. The activities of these catalysts were tested in carbon dioxide reforming of methane reaction with temperature increasing from 500 to 650?°C and the stabilities of these catalysts were evaluated for long time reaction at 650?°C. It was found that when Zr/(Zr?+?Al) molar ratio?=?0.5%, the Ni/0.5ZrO₂–Al₂O₃ catalyst showed the highest activity, and exhibited superior stabilization compared to the Ni-based catalyst supported on traditional ordered mesoporous Al₂O₃. The “confinement effect” from mesoporous channels of alumina matrix is helpful to stabilize the Ni nanoparticles. As a promoter, Zr could stabilize the ordered mesoporous framework by reacting with Al₂O₃ to form ZrO₂–Al₂O₃ solid solution. Since ZrO₂ enhances the dissociation of carbon dioxide, more oxygen intermediates are given to remove the carbon formed during the reaction.     

NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> Nanoparticles Stabilized by Porous Silica Shells

Abstract  

NiFe₂O₄ nanoparticles stabilized by porous silica shells (NiFe₂O₄@SiO₂) were prepared using a one-pot synthesis and characterized for their physical and chemical stability in severe environments, representative of those encountered in industrial catalytic reactors. The SiO₂ shell is porous, allowing transport of gases to and from the metal core. The shell also stabilizes NiFe₂O₄ at the nanoparticle surface: NiFe₂O₄@SiO₂ annealed at temperatures through 973 K displays evidence of surface Ni, as verified by H₂ TPD analyses. At 1,173 K, hematite forms at the surface of the metallic cores of the NiFe₂O₄@SiO₂ nanoparticles and surface Ni is no longer observed. Without the silica shell, however, even mild reduction (at 773 K) can draw Fe to the surface and eliminate surface Ni sites.     

Highly ordered mesoporous CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> and CuFe<Subscript>2</Subscript>O<Subscript>4</Subscript> with crystalline walls

The highly ordered mesoporous CoFe₂O₄ and CuFe₂O₄ with crystalline walls can be synthesized by hard template with using mesoporous silica SBA-15 as hard template and using ferric nitrate, cobalt nitrate, and copper nitrate as metal precursors. These new mesoporous materials above have high surface areas, narrow pore size distribution, and large pore volumes, which are believed to be valuable for the potential application in the field of sensors, catalysis, message recording, magnetics, and biology. This work provides a method to fabricate the highly ordered mesoporous materials composed of multi-metal oxides with crystalline walls. The development of such versatile approach is of great significance in practical application. It can be envisaged that this established method is significantly expandable to the controlled synthesis of the mesoporous functional materials with diverse compositions.     

Characterization of Fischer–Tropsch Cobalt-Based Catalytic Systems (Co/SiO<Subscript>2</Subscript> and Co/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) by X-ray Diffraction and Magnetic Measurements

Results of the characterization of six Co-based Fischer–Tropsch (FT) catalysts, with 15% Co loading and supported on SiO₂ and Al₂O₃, are presented. Room temperature X-ray diffraction (XRD), temperature and magnetic field (H) variation of the magnetization (M), and low-temperature (5 K) electron magnetic resonance (EMR) are used for determining the electronic states (Co⁰, CoO, Co₃O₄, Co²⁺) of cobalt. Performance of these catalysts for FT synthesis is tested at reaction temperature of 240 °C and pressure of 20 bars. Under these conditions, 15% Co/SiO₂ catalysts yield higher CO and syngas conversions with higher methane selectivity than 15% Co/Al₂O₃ catalysts. Conversely the Al₂O₃ supported catalysts gave much higher selectivity towards olefins than Co/SiO₂. These results yield the correlation that the presence of Co₃O₄ yield higher methane selectivity whereas the presence of Co²⁺ species yields lower methane selectivity but higher olefin selectivity. The activities and selectivities are found to be stable for 55 h on-stream.     

Self-Metathesis of 1-Octene Using Alumina-Supported Re<Subscript>2</Subscript>O<Subscript>7</Subscript> in Supercritical CO<Subscript>2</Subscript>

In this contribution we describe the use of heterogeneous catalysts for the liquid-phase self-metathesis of 1-octene in supercritical CO₂. Our work aims at addressing the mass-transfer problems associated with such reaction systems. By coupling a heterogeneous supported Re₂O₇ catalyst with the use of scCO₂, the self-metathesis of 1-octene takes place by and large much more rapidly than in traditional solvent media, and furthermore, by using scCO₂ the overall efficiency and sustainability of the transformation can be improved.

Aqueous-Phase Hydrogenolysis of Glycerol to 1,3-propanediol Over Pt-H<Subscript>4</Subscript>SiW<Subscript>12</Subscript>O<Subscript>40</Subscript>/SiO<Subscript>2</Subscript>

Abstract  

Hydrogenolysis of glycerol to 1,3-propanediol in aqueous-phase was investigated over Pt-H₄SiW₁₂O₄₀/SiO₂ bi-functional catalysts with different H₄SiW₁₂O₄₀ (HSiW) loading. Among them, Pt-15HSiW/SiO₂ showed superior performance due to the good dispersion of Pt and appropriate acidity. It is found that Br?nsted acid sites facilitate to produce 1,3-PDO selectively confirmed by Py-IR. The effects of weight hourly space velocity, reaction temperature and hydrogen pressure were also examined. The optimized Pt-HSiW/SiO₂ catalyst showed a 31.4% yield of 1,3-propanediol with glycerol conversion of 81.2% at 200 °C and 6 MPa.     

Morphology-Controlled Synthesis of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> Materials and its Electrochemical Catalytic Properties Towards Oxygen Evolution Reaction

In the present study, we present a facile strategy to synthesis Co₃O₄ materials with different morphology. Experimental results show that Co₃O₄ materials with flower-like, fiber, sheet-like and rod morphologies have been successfully prepared by hydrothermal synthesis in different solvent. The effect of the morphology on the electrochemical catalytic properties were also studied. It is found that sheet-like Co₃O₄ exhibits the best activity towards oxygen evolution reaction (η₁₀?=?390 mV) in 1 M KOH, which can be attribute to its short electrolyte infiltration diffusion path lengths and low charge transfer resistant.

Graphical Abstract

LSV curves measured at 5 mV/s in 1 M KOH solution for OER, the inset image is FE-SEM image of prepared Co₃O₄ materials. a Flower, b fiber, c sheet and d rod.

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Structural characterization and electrochemical properties of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> anode materials synthesized by a hydrothermal method

Cobalt oxide [Co₃O₄] anode materials were synthesized by a simple hydrothermal process, and the reaction conditions were optimized to provide good electrochemical properties. The effect of various synthetic reaction and heat treatment conditions on the structure and electrochemical properties of Co₃O₄ powder was also studied. Physical characterizations of Co₃O₄ are investigated by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller [BET] method. The BET surface area decreased with values at 131.8 m²/g, 76.1 m²/g, and 55.2 m²/g with the increasing calcination temperature at 200°C, 300°C, and 400°C, respectively. The Co₃O₄ particle calcinated at 200°C for 3 h has a higher surface area and uniform particle size distribution which may result in better sites to accommodate Li⁺ and electrical contact and to give a good electrochemical property. The cell composed of Super P as a carbon conductor shows better electrochemical properties than that composed of acetylene black. Among the samples prepared under different reaction conditions, Co₃O₄ prepared at 200°C for 10 h showed a better cycling performance than the other samples. It gave an initial discharge capacity of 1,330 mAh/g, decreased to 779 mAh/g after 10 cycles, and then showed a steady discharge capacity of 606 mAh/g after 60 cycles.     

Promoting Effect of Triglyme on Lean NO<Subscript>x</Subscript> Reduction Over Ag/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Abstract  

The highly oxygenated hydrocarbon triethylene glycol dimethyl ether or triglyme (CH₃O–(C₂H₄O–)₃CH₃) was found to efficiently reduce NO_x under lean conditions over Ag/Al₂O₃, but gave a low NO_x conversion over Cu-ZSM-5. Furthermore, triglyme showed an extraordinary promoting effect when added together with propene as reducing agent for NO_x over Ag/Al₂O₃ at low temperature. This is most likely due to that triglyme promotes the activation of propene.     

Selective Synthesis of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanowires Via a Single Precursor: A General Method for Metal Oxide Nanowires

Hematite (α-Fe₂O₃) and magnetite (Fe₃O₄) nanowires with the diameter of about 100 nm and the length of tens of micrometers have been selectively synthesized by a microemulsion-based method in combination of the calcinations under different atmosphere. The effects of the precursors, annealing temperature, and atmosphere on the morphology and the structure of the products have been investigated. Moreover, Co₃O₄ nanowires have been fabricated to confirm the versatility of the method for metal oxide nanowires.     

Preparation and Characterization of Mesoporous MoO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> Composite with High Surface Area by Self-Supporting and Ammonia Method

Abstract  

A mesoporous MoO₃/TiO₂ composite was prepared from titanate derivative by consecutive self-supporting and ammonia method. All samples were characterized by X-ray Diffraction, N₂ adsorption–desorption, Raman Spectra and Field-Emission Scanning Electron Microscopy. The results showed that mesoporous MoO₃/TiO₂ composite had a higher surface area (173 m²/g) and a better MoO₃ dispersion than that prepared by traditional impregnation (90 m²/g). As for hydrodesulfurization tests, mesoporous MoO₃/TiO₂ composite in this case presented a better catalytic performance, attributed to its high surface area and good dispersion of MoO₃. It can be found that self-supporting played a key role in preparing mesoporous MoO₃/TiO₂ composite with high surface area. Additionally, aqueous ammonia could effectively dissolve excess MoO₃, which helped to obtain mesoporous MoO₃/TiO₂ composite with better dispersion of MoO₃.     

Catalytic properties of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles for rechargeable Li/air batteries

Three types of Co₃O₄ nanoparticles are synthesized and characterized as a catalyst for the air electrode of a Li/air battery. The shape and size of the nanoparticles are observed using scanning electron microscopy and transmission electron microscopy analyses. The formation of the Co₃O₄ phase is confirmed by X-ray diffraction. The electrochemical property of the air electrodes containing Co₃O₄ nanoparticles is significantly associated with the shape and size of the nanoparticles. It appears that the capacity of electrodes containing villiform-type Co₃O₄ nanoparticles is superior to that of electrodes containing cube- and flower-type Co₃O₄ nanoparticles. This is probably due to the sufficient pore spaces of the villiform-type Co₃O₄ nanoparticles.     

LiNi<Subscript>0.4</Subscript>Co<Subscript>0.3</Subscript>Mn<Subscript>0.3</Subscript>O<Subscript>2</Subscript> thin film electrode by aerosol deposition

LiNi_0.4Co_0.3Mn_0.3O₂ thin film electrodes are fabricated from LiNi_0.4Co_0.3Mn_0.3O₂ raw powder at room temperature without pretreatments using aerosol deposition that is much faster and easier than conventional methods such as vaporization, pulsed laser deposition, and sputtering. The LiNi_0.4Co_0.3Mn_0.3O₂ thin film is composed of fine grains maintaining the crystal structure of the LiNi_0.4Co_0.3Mn_0.3O₂ raw powder. In the cyclic voltammogram, the LiNi_0.4Co_0.3Mn_0.3O₂ thin film electrode shows a 3.9-V anodic peak and a 3.6-V cathodic peak. The initial discharge capacity is 44.6 μAh/cm², and reversible behavior is observed in charge-discharge profiles. Based on the results, the aerosol deposition method is believed to be a potential candidate for the fabrication of thin film electrodes.     

Synthesis and Thermoelectric Properties of Ceramics Based on Bi<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Co<Subscript>1.7</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Oxide

Layered ceramics based on bismuth–calcium cobaltite with varied cobalt oxide contents is synthesized by the solid-phase method, the ceramics phase composition is determined, and the microstructure, thermal expansion, electroconductivity, and thermal electromotive force are investigated. The formation of just one compound, ternary oxide composed of Bi₂Ca₂Co_1.7O _y , is established within the quasi-binary Bi₂Ca₂O₅–CoO _z system. The effect of the cobalt oxide content on the Bi₂Ca₂Co _x O _y ceramics’ microstructure and physicochemical properties is analyzed. The single-phased ceramic sample Bi₂Ca₂Co_1.7O _y demonstrated the highest power factor value among all the investigated samples—26.0 μW/(m K²) at a temperature of 300 K. This sample showed the lowest value of the thermal linear expansion coefficient of 9.72 × 10^–6 K^–1.     

Combined Steam and Carbon Dioxide Reforming of Methane on Ni/MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: Effect of CeO<Subscript>2</Subscript> Promoter to Catalytic Performance

Abstract  

The catalytic performance during combined steam and carbon dioxide reforming of methane (SCR) was investigated on Ni/MgAl₂O₄ catalyst promoted with CeO₂. The SCR catalyst was prepared by co-impregnation method using nickel and cerium metal precursors on hydrotalcite-like MgAl₂O₄ support. In terms of catalytic activity and stability, CeO₂-promoted Ni/MgAl₂O₄ catalyst is superior to Ni–CeO₂/Al₂O₃ or Ni/MgAl₂O₄ catalysts because of high resistance to coke formation and suppressed aggregation of nickel particles. The role of CeO₂ on Ni/MgAl₂O₄ catalyst was elucidated by carrying out the various characterization methods in the viewpoint of the aggregation of nickel particles and metal-support interactions. The observed superior catalytic performance on CeO₂-promoted Ni/MgAl₂O₄ catalyst at the weight ratio of MgO/Al₂O₃ of 3/7 seems to be closely related to high dispersion and low aggregation of active metals due to their strong interaction with the MgAl₂O₄ support and the adjacent contact of Ni and CeO₂ species. The CeO₂ promoter also plays an important role to suppress particle aggregation by forming an appropriate interaction of NiO–CeO₂ as well as Ni–MgAl₂O₄ with the concomitant enhancement of mobile oxygen content.     

Selective Hydrogenation of <Emphasis Type="Italic">trans</Emphasis>-Cinnamaldehyde over SiO<Subscript>2</Subscript>-Supported Co–Ir Bimetallic Catalysts

Selective hydrogenation of trans-cinnamaldehyde was studied on SiO₂-supported Co–Ir bimetallic catalysts. Addition of Ir to Co/SiO₂ increased the hydrogenation selectivity and activity of cinnamaldehyde to the corresponding cinnamyl alcohol (UOL). A selectivity as higher as 93% to UOL at ambient temperature under H₂ pressure of 2.0 MPa was obtained over catalyst with loadings of 10 wt% Co and 0.5 wt% Ir (Co_10.0Ir_0.5/SiO₂). The XRD, Raman and TPR results showed that the higher dispersed Co₃O₄ particles were formed on SiO₂ due to the addition of Ir, which increased the reducibility of Co₃O₄ to Co⁰. The reduction of oxidized Co–Ir/SiO₂ samples occurred at the temperatures with about 200 K lower than that of the one without Ir species as evidenced by the observations of TPR and in-situ Raman characterizations. The XPS results indicated that the large parts of Co₃O₄ in the sample of Co–Ir/SiO₂ were reduced to Co⁰, but only small parts of that were reduced to Co⁰ in the sample of Co/SiO₂ under flowing 5%H₂/Ar at 673 K. The CO chemisorptions revealed that the irreversible uptakes of CO on the reduced Co–Ir/SiO₂ sample was much higher than those on the reduced Co/SiO₂ and Ir/SiO₂, and also higher than the combination of that on the reduced Co/SiO₂ and Ir/SiO₂, respectively. The experimental data suggested that the presence of Ir played a key role in the reduction of Co₃O₄ to Co⁰ through a strong interaction between them and that the amount of Co⁰ at the catalyst surfaces was correlated to the activity and more importantly to the UOL selectivity.     

Synthesis and optical property of one-dimensional spinel ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> nanorods

Spinel zinc manganese oxide (ZnMn₂O₄) nanorods were successfully prepared using the previously synthesized α-MnO₂ nanorods by a hydrothermal method as template. The nanorods were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-Vis absorption, X-ray photoelectron spectroscopy, surface photovoltage spectroscopy, and Fourier transform infrared spectroscopy. The ZnMn₂O₄ nanorods in well-formed crystallinity and phase purity appeared with the width in 50-100 nm and the length in 1.5-2 μm. They exhibited strong absorption below 500 nm with the threshold edges around 700 nm. A significant photovoltage response in the region below 400 nm could be observed for the nanorods calcined at 650 and 800°C.