Synthesis of three-dimensional ordered mesoporous MnO_2 and its catalytic performance in formaldehyde oxidation

Three-dimensional（3D）ordered mesoporous MnO2 was prepared using KIT-6 mesoporous molecular sieves as a hard template.The material was used for catalytic oxidation of HCHO.The material has high surface areas and the mesoporous characteristics of the template,with cubic symmetry（ia3d）.It consists of a β-MnO2 crystalline phase corresponding to pyrolusite,with a rutile structure.Transmission electron microscopy and X-ray photoelectron spectroscopy showed that the 3D-MnO2 catalyst has a large number of exposed Mn4＋ ions on the（110）crystal plane surfaces,with a lattice spacing of 0.311 nm; this enhances oxidation of HCHO.Complete conversion of HCHO to CO2 and H2O was achieved at 130 °C on 3D-MnO2; the same conversions on α-MnO2 and β-MnO2 nanorods were obtained at 140 and 180 °C,respectively,under the same conditions.The specific mesoporous structure,high specific surface area,and large number of surface Mn4＋ ions are responsible for the catalytic activity of 3D-MnO2 in HCHO oxidation.

Three-dimensional ordered macroporous perovskite-type La_(1-x)K_xNiO_3 catalysts with enhanced catalytic activity for soot combustion: the Effect of K-substitution

Three-dimensional ordered macroporous (3DOM) La1?xKxNiO3 perovskite-type catalysts were successfully prepared by a colloidal crystal template method and characterized by scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, energy-dispersive X-ray scattering elemental mapping, X-ray diffraction, Raman and X-ray photoelectron spectroscopy, and temperature-programmed reduction of H2. Further, their catalytic activity in soot combustion was determined by temperature-programmed oxidation reaction. K substitution into the LaNiO3 lattice led to remarkably improved catalytic activity of this catalyst in soot combustion. Amongst various catalysts, La0.95K0.05NiO3 exhibited the highest activity in soot combustion (with its T50 and CO2 S values being 338 °C and 98.2%, respectively), which is comparable to the catalytic activities of Pt-based catalysts under the condition of poor contact between the soot and the catalyst. K-substitution improves the valence state of Ni and increases the number of oxygen vacancies, thereby leading to increased density of surface-active oxygen species. The active oxygen species play a vital role in catalyzing the elimination of soot. The perovskite-type La1?xKxNiO3 nanocatalysts with 3DOM structure without noble metals have potential for practical applications in the catalytic combustion of diesel soot particles.

Efficient aerobic oxidative desulfurization via three-dimensional ordered macroporous tungsten-titanium oxides

A series of three-dimensional ordered macroporous(3 DOM)W-TiO_(2)catalysts have been prepared through a facile colloidal crystal template method.The prepared materials characterized in detail exhibited enhanced catalytic activity in aerobic oxidative desulfurization process.The experimental results indicated that the as-prepared materials possessed excellent 3 DOM structure,which is beneficial for the catalytic activity.The sample 3 DOM W-TiO_(2)-20 exhibited the highest activity in ODS process,and the sulfur removal can reach 98%in 6 h.Furthermore,the oxidative product was also analyzed in the reaction process.

Pore-filling Three-dimensionally Ordered Macroporous Polyimide Composite Proton Conducting Membranes

The silica opal templates were prepared from three silica colloids of different diameters of 230 nm, 500 nm and 1.5 mm by a filtration route. The large-scale stable opal template membranes after sintering the deposited SiO2 opal template can be successfully obtained by optimizing the pH value and NaCl concentration in silica colloidal solutions. The three-dimensionally ordered macroporous（3DOM） polyimide membranes without crack were fabricated by reproducing the structure of silica opal template. We prepared the pore-filling composite proton exchange membranes by filling the 3DOM structure with proton conducting organosilane sol. The result indicates that the composite membranes exhibit higher water uptake than pure filling organosilane gel. The proton conductivity increased with the increasing of pore cell in composite membranes.

Color tunable upconversion emission in CeO_2:Yb,Er three-dimensional ordered macroporous materials

The three-dimensional ordered macroporous CeO2：Yb,Er materials were prepared, and the influence of doping concentra- tion of Yb3＋ or Er3＋ ions on upconversion property was investigated. Green and red upconversion emissions were observed under the excitation of 980 nm at room temperature. It was found that the ratio of red to green upconversion emission intensity increased with increasing of concentration of the Yb3＋ or Er3＋ ions in the three-dimensional ordered macroporous CeO2：Yb,Er materials. When the concentration of Yb3＋ was 10 mol%, pure red upconversion emission was obtained. The varied mechanism of ratio of red to green upconversion emission intensity was discussed with the concentration of Yb3＋ or Er3＋ ions.

MicroED as a powerful technique for the structure determination of complex porous materials

Porous materials have garnered significant attention in recent years.Understanding the intrinsic relationship between their structures and properties requires precise knowledge of their atomic structures.Single-crystal X-ray diffraction(SCXRD)has traditionally been the primary method for elucidating such structures,but it demands large,high-quality crystals,often exceeding 5μm in size.The growth of these crystals can be a time-consuming process,especially for one-and two-dimensional materials.To explore structures at the nanoscale,MicroED(microcrystal electron diffraction(ED))offers unprecedented insights into the realm of nanomaterials.This revolutionary technique enables researchers to uncover intricate details within nanoscale structures,promising to reshape our fundamental understanding of materials.In this review,we delve into the applications of MicroED in the study of various porous materials,including zeolites,metal-organic frameworks(MOFs),and covalent organic frameworks(COFs).We emphasize the pivotal role of MicroED in nanomaterial characterization,enabling precise crystallographic analysis and phase identification.

Porous 3D carbon-based materials:An emerging platform for efficient hydrogen production

Due to their unique properties and uninterrupted breakthrough in a myriad of clean energy-related applications,carbon-based materials have received great interest.However,the low selectivity and poor conductivity are two primary difficulties of traditional carbon-based materials(zero-dimensional(0D)/one-dimensional(1D)/two-dimensional(2D)),enerating inefficient hydrogen production and impeding the future commercialization of carbon-based materials.To improve hydrogen production,attempts are made to enlarge the surface area of porous three-dimensional(3D)carbon-based materials,achieve uniform interconnected porous channels,and enhance their stability,especially under extreme conditions.In this review,the structural advantages and performance improvements of porous carbon nanotubes(CNTs),g-C_(3)N_(4),covalent organic frameworks(COFs),metal-organic frameworks(MOFs),MXenes,and biomass-derived carbon-based materials are firstly summarized,followed by discussing the mechanisms involved and assessing the performance of the main hydrogen production methods.These include,for example,photo/electrocatalytic hydrogen production,release from methanolysis of sodium borohydride,methane decomposition,and pyrolysis-gasification.The role that the active sites of porous carbon-based materials play in promoting charge transport,and enhancing electrical conductivity and stability,in a hydrogen production process is discussed.The current challenges and future directions are also discussed to provide guidelines for the development of next-generation high-efficiency hydrogen 3D porous carbon-based materials prospected.

A Three-Dimensional Silicon-Diacetylene Porous Organic Radical Polymer

Radical-containing porous organic polymers(POPs)have drawn great interest in various applications.However,the synthesis of radical POPs remains challenging due to the unstable nature of organic radicals.Here,a persistent and stable three-dimensional silicon-diacetylene porous organic radical polymer was synthesized via a classic Eglinton homocoupling reaction of tetraethynylsilane.The presence of carbon radicals in this material was confirmed by electron paramagnetic resonance,and its paramagnetic behavior was analyzed by a superconducting quantum interference device.This unique material has a low-lying lowest unoccupied molecular orbital(LUMO)energy level(−5.47 eV)and a small energy gap(ca.1.46 eV),which shows long-term cycling stability and excellent rate capability as an anode material for lithium-ion batteries,demonstrating potential application in energy fields.

THEORY AND APPLICATION OF FRACTIONAL STEP CHARACTERISTIC FINITE DIFFERENCE METHOD IN NUMERICAL SIMULATION OF SECOND ORDER ENHANCED OIL PRODUCTION

A kind of second-order implicit fractional step characteristic finite difference method is presented in this paper for the numerically simulation coupled system of enhanced （chemical） oil production in porous media. Some techniques, such as the calculus of variations, energy analysis method, commutativity of the products of difference operators, decomposition of high-order difference operators and the theory of a priori estimates are introduced and an optimal order error estimates in l^2 norm is derived. This method has been applied successfully to the numerical simulation of enhanced oil production in actual oilfields, and the simulation results ate quite interesting and satisfactory.

Synthesis of 3D ordered macroporous indium tin oxide using polymer colloidal crystal template

Three-dimensional (3D) ordered macroporous indium tin oxide (ITO) is pre- pared using a polymer colloidal crystal template that is formed by self-assembly of the monodisperse poly(methyl methacrylate) (PMMA) microspheres. The morphologies and BET surface area of the macroporous material is examined by scanning electron micro- scope, transmission electron microscopy and N2 adsorption/desorption. Results indicate that the macroporous material has highly ordered arrays of the uniform pores replicated from the PMMA colloidal crystal template when the polymer colloidal crystal template is removed by calcinations at 500℃. The pore diameter (about 450 nm) of macroporous ITO slightly shrank to the PMMA microspheres. The BET surface area and pore volume of the macroporous material are 389 m2·g-1 and 0.36 cm3·g-1, respectively. Moreover, the macroporous ITO, containing 5 mol% Sn and after annealing under vacuum, shows the minimum resistivity of ρ = 8.2×10-3 Ω· cm. The conductive mechanism of macroporous ITO is discussed, and it is believed that the oxygen vacancies are the major factor for excellent electrical properties.

Immobilization of Glucose Oxidase on Ordered Macroporous Silicas Functionalized with Amino Group

A novel glucose oxidase immobilized on three-dimensionally ordered macroporous （3DOM） material has been prepared by firstly preparation of hybrid 3DOM SiO2-NH2 materials using colloidal crystal method, and following covalent immobilization of glucose oxidase on the pore walls of the 3DOM materials. The materials were characterized by SEM, FTIR, DSC and BET techniques. SEM observation shows that the macropores are highly ordered and are interconnected by small windows. FTIR measurement shows that there are amino and organic groups in the pore walls. The surface area of the 3DOM SiO2-NH2 material is about 10.2 m2/g. The loaded amount of enzyme is increased with amino content in the materials. The immobilized enzyme has high activity, thermal stability and can be reused.

Preparation and characterization of 3-dimensionally ordered macroporous SiC

Three-dimensionally (3D) long range ordered macroporous SiC ceramics were prepared through infiltrating polymethylsilane (PMS) into the 3D ordered sacrificial silica template, pyrolysis and the template removal. It was found that the pore size (84―658 nm), BET surface area (299.44―584.64 m2/g) and micropore volume (0.25―0.64 cm3/g) of the achieved porous SiC can be tailored by utilizing different sizes silica sphere templates. There exist three kinds of pores in the porous ceramics: sphere inversed pores, windows and mesopores (2―5 nm). The sphere inversed pores were packed as hcp structure and three dimensionally penetrated through the windows, and the mesopores endowed the porous ceramics surprising high BET surface areas and micropore volumes.

Effects of Au-Ce strong interactions on catalytic activity of Au/CeO_2/3DOM Al_2O_3 catalyst for soot combustion under loose contact conditions

Au/3DOM（three-dimensionally ordered macroporous） Al2O3 and Au/CeO2/3DOM Al2O3 were prepared using a reduction-deposition method and characterized using scanning electron microscopy,N2 adsorption-desorption,X-ray diffraction,transmission electron microscopy,ultraviolet-visible spectroscopy,temperature-programmed hydrogen reduction,and X-ray photoelectron spectroscopy.Au nanoparticles of similar sizes were well dispersed and supported on the inner walls of uniform macropores.The norminal Au loading is 2%.Al-Ce-O solid solution in CeO2/3DOM Al2O3 catalysts can be formed due to the incorporation of Al^3＋ ions into the ceria lattice,which causes the creation of extrinsic oxygen vacancies.The extrinsic oxygen vacancies improved the oxygen-transport properties.The strong metal-support interactions between Au and CeO2 increased the amount of active oxygen on the Au nanoparticle surfaces,and this promoted soot oxidation.The activities of the Au-based catalysts were higher than those of the supports（Al2O3 or CeO2/3DOM Al2O3） at low temperature.Au/CeO2/3DOM Al2O3 had the highest catalytic activity for soot combustion,with T（10）,T（50）,and T（90） values of 273,364,and 412℃,respectively.

Theory and application of numerical simulation method of capillary force enhanced oil production

A kind of second-order implicit upwind fractional step finite difference methods are presented for the numerical simulation of coupled systems for enhanced （chemical） oil production with capillary force in the porous media. Some techniques, e.g., the calculus of variations, the energy analysis method, the commutativity of the products of difference operators, the decomposition of high-order difference operators, and the theory of a priori estimate, are introduced. An optimal order error estimate in the l2 norm is derived. The method is successfully used in the numerical simulation of the enhanced oil production in actual oilfields. The simulation results are satisfactory and interesting.

Buckling Analysis of FG Porous Truncated Conical Shells Resting on Elastic Foundations in the Framework of the Shear Deformation Theory

In this article,an analytical method is proposed to analyze of the linear buckling behavior of the FG porous truncated conical shells subjected to a uniform axial compressive load and resting on the Pasternak elastic foundation.The material properties including Young’s modulus,shear modulus and density are assumed to vary in the thickness direction.Three types of FG porous distributions including symmetric porosity distribution,non-symmetric porosity and uniform porosity distribution are considered.The governing equations of the FG porous truncated conical shells are obtained by using the first-order shear deformation theory(FSDT).With the help of the Galerkin method,the expressions for critical buckling loads are obtained in closed forms.The reliability of the obtained results is verified by comparing the present solutions with the published solutions.Finally,the numerical results show the effects of shell characteristics,porosity distribution,porosity coefficient,and elastic foundation on the critical buckling load.

A novel 3D printed technology to construct a monolithic ultrathin nanosheets Co_(3)O_(4)/SiO_(2) catalyst for benzene catalytic combustion

In this study,a novel three-dimensional(3D)-OMm-Co_(3)O_(4)/SiO_(2)-0.5AP(OMm=ordered macro–meso porous,AP=aluminum phosphate)monolithic catalyst was for the first time constructed successfully with the hierarchical Co-phyllosilicate ultrathin nanosheets growth on the surface of 3D printed ordered macropore–mesoporous SiO_(2)support.On the one hand,we discovered that the construction of ordered macropore–mesoporous structures is beneficial to the diffusion and adsorption of reactants,intermediates,and products.On the other hand,the formation of hierarchical Co-phyllosilicate ultrathin nanosheets could provide more active Co&+species,abundant acid sites,and active oxygen.The above factors are in favor of improving the catalytic performance of benzene oxidation,and then a 3D-OMm-Co_(3)O_(4)/SiO_(2)-0.5AP catalyst exhibited the superior catalytic activity.To explore the effect of catalysts structure and morphology,various Co-based catalysts were also constructed.Simultaneously,the 3D-OMm-Co_(3)O_(4)/SiO_(2)-0.5AP catalyst has excellent catalytic performance,water resistance,and thermal stability in the catalytic combustion of benzene due to the strong interactions between Co&+species and SiO_(2)in the phyllosilicate.Therefore,this study proposes a new catalyst synthesis method through 3D printing,and presents considerable prospects for the removal of VOCs from industrial applications.