Three-dimensionally Ordered Macroporous Phosphotungstic Acid/SiO2 for Efficient Catalytic Oxidative Desulfurization

Three-dimensionally ordered（3DOM） macroporous phosphotungstic acid/SiO_2（HPW/SiO_2） materials were prepared by using colloidal crystal as templates and applied for oxidative desulfurization（ODS） of the model fuel oil. The obtained HPW/SiO_2 materials were characterized through scanning electron microscopy, powder X-ray diffraction, N_2 sorption, and Fourier transform infrared spectroscopy. The results indicated that 3 DOM HPW/SiO_2 possessed hierarchical pore architectures which contained ordered macropores and disordered mesopores, with the Keggin type HPW embedded in the framework of pore structure. The removal rate of dibenzothiophene（DBT） could reach 100% under the optimum conditions, moreover. The performance was only slightly decreased for the regenerated catalyst after 7 cycles.

Three-dimensionally ordered macroporous cross-linked polystyrene incorporating functional group via hydrophilic spacer arm

A versatile and effective method for incorporating functional groups on the pore wall of three-dimensionally ordered macroporous cross-linked polystyrene（3DOM CLPS） by hydrophilic spacer arm has been investigated.The 3DOM CLPS with pore size 865 nm was prepared by sacrifice template method.The hydrophilic spacer arm（polyethylene glycol,molecular weight is 600） was grafted to the 3DOM CLPS via nucleophilic substitution reaction.The other side of active hydroxyl can be further converted into a lot of other functional groups.In this report,the chelating ligand 2-mercaptobenzothiazole（MBZ） group was introduced on the end of the PGE chain to evidence the versatile functionalization approach.The functionalized ordered macroporous materials were characterized by FT-IR,element analyzer,SEM.The results reveal that the pores were successfully bonded with 2-mercaptobenzothiazole groups via hydrophilic spacer arms and the original morphology of ordered macroporous materials were remained after functionalization.The MBZ group density is 0.052 mmol/m^2.The functionalized 3DOM CLPS are expected to application as heavy metal ions adsorbent.

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.

Ultrasmall NiS_(2)Nanocrystals Embedded in Ordered Macroporous Graphenic Carbon Matrix for Efficiently Pseudocapacitive Sodium Storage

Sodium-ion hybrid capacitor(SIHC)is one of the most promising alternatives for large-scale energy storage due to its high energy and power densities,natural abundance,and low cost.However,overcoming the imbalance between slow Na^(+)reaction kinetics of battery-type anodes and rapid ion adsorption/desorption of capacitive cathodes is a significant challenge.Here,we propose the high-rate-performance NiS_(2)@OMGC anode material composed of monodispersed NiS_(2) nanocrystals(8.8±1.7 nm in size)and N,S-co-doped graphenic carbon(GC).The NiS_(2)@OMGC material has a three-dimensionally ordered macroporous(3DOM)morphology,and numerous NiS_(2) nanocrystals are uniformly embedded in GC,forming a core-shell structure in the local area.Ultrafine NiS_(2) nanocrystals and their nano-microstructure demonstrate high pseudocapacitive Na-storage capability and thus excellent rate performance(355.7 mAh/g at 20.0 A/g).A SIHC device fabricated using NiS_(2)@OMGC and commercial activated carbon(AC)cathode exhibits ultrahigh energy densities(197.4 Wh/kg at 398.8 W/kg)and power densities(43.9 kW/kg at 41.3 Wh/kg),together with a long life span.This outcome exemplifies the rational architecture and composition design of this type of anode material.This strategy can be extended to the design and synthesis of a wide range of high-performance electrode materials for energy storage applications.

Three-dimensionally ordered macro-porous Pt/TiO_2 catalyst used for water-gas shift reaction

Three-dimensionally ordered macro-porous （3DOM） Pt/TiO2 catalysts were prepared by template and impregnation methods, and the resultant samples were characterized by using TG-DTA, XRD, SEM, TEM, and TPR techniques. The catalytic performance for water-gas shift （WGS） reaction was tested, and the influences of some conditions, such as reduction temperature of catalysts, the amount of Pt loadings and space velocity on catalytic performance were investigated. It was shown that Pt particles were homogeneously dispersed on 3DOM TiO2. The reduction of TiO2 surface was important for the catalytic performance. The activity test results showed that the 3DOM Pt/TiO2 catalysts exhibited very good catalytic performance for WGS reaction even at high space velocity, which was owing to the better mass transfer of 3DOM porous structure besides the high intrinsic activity of Pt/TiO2.

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.

Fabrication of Large-area 3-D Ordered Silvercoated Colloidal Crystals and Macroporous Silver Films Using Polystyrene Templates

The highly ordered silver-coated colloidal crystals arrays and macroporous silver films were derived through an electrostatics-induced adsorption effect using polystyrene(PS) as templates. Carboxyl-modified PS microspheres were prepared by emulsifier-free emulsion polymerization using methacrylic acid(MAA) as the functional monomer. PS microspheres were self-assembled into close packing colloidal crystals of facecentered cubic arrays to the substrate with vertical deposition method. These colloidal crystals were modified using dopamine(DA) to form poly-dopamine(PDA) during its oxidative polymerization. Through electrostatic interaction, the silver nanoparticles were deposited and adsorbed onto the surfaces of colloidal crystals templates by exposing [Ag(NH_3)_2]^+solution to infrared irradiation. Removal of the polymeric template by etching with methylbenzene solvent resulted in 3D ordered macroporous silver films. The structural and properties of the ordered silver-coated arrays and macroporous silver films were characterized by field emission scanning electron microscopy(FE-SEM), X-ray diffraction(XRD), UV-vis spectroscopy and surface-enhanced Raman spectroscopy(SERS). The results indicate that the prepared silver-coated arrays and macroporous silver films possess the features of ordered multilayer arrangement, uniformity and repeatability as well as an ideal SERS effect.

Synergistically boosting the elementary reactions over multiheterogeneous ordered macroporous Mo2C/NC-Ru for highly efficient alkaline hydrogen evolution

Simultaneously enhancing the reaction kinetics,mass transport,and gas release during alkaline hydrogen evolution reaction(HER)is critical to minimizing the reaction polarization resistance,but remains a big challenge.Through rational design of a hierarchical multiheterogeneous three-dimensionally(3D)ordered macroporous Mo_(2)C-embedded nitrogen-doped carbon with ultrafine Ru nanoclusters anchored on its surface(OMS Mo_(2)C/NC-Ru),we realize both electronic and morphologic engineering of the catalyst to maximize the electrocatalysis performance.The formed Ru-NC heterostructure shows regulative electronic states and optimized adsorption energy with the intermediate H*,and the Mo_(2)C-NC heterostructure accelerates the Volmer reaction due to the strong water dissociation ability as confirmed by theoretical calculations.Consequently,superior HER activity in alkaline solution with an extremely low overpotential of 15.5 mV at 10 mAcm^(−2)with the mass activity more than 17 times higher than that of the benchmark Pt/C,an ultrasmall Tafel slope of 22.7 mV dec−1,and excellent electrocatalytic durability were achieved,attributing to the enhanced mass transport and favorable gas release process endowed from the unique OMS Mo_(2)C/NC-Ru structure.By oxidizing OMS Mo_(2)C/NC-Ru into OMS MoO_(3)-RuO_(2)catalyst,it can also be applied as efficient oxygen evolution electrocatalyst,enabling the construction of a quasi-symmetric electrolyzer for overall water splitting.Such a device's performance surpassed the state-of-the-art Pt/C||RuO2 electrolyzer.This study provides instructive guidance for designing 3D-ordered macroporous multicomponent catalysts for efficient catalytic applications.

Oxidative Desulfurization of Fuel Oil at Room Temperature Catalyzed by Ordered Meso-macroporous HPW/SiO2

A serial of ordered meso-macroporous phosphotungstic acid(HPW) supported on SiO2 nanocomposites were successfully prepared by a homogeneous precipitation method, using monodispersed polystyrene(PS) microspheres and cationic surfactant as structure directing agent. These nanocomposites were used as catalysts for oxidative desulfurization(ODS) of model fuel. The materials were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 adsorption-desorption isothrem, X-ray diffraction(XRD), and Fourier transform infrared spectra(FTIR). The characterization results suggested that the as-prepared material possessed ordered meso-macroporous architectures with Keggin type phosphotungstic acid dispersed homogeneously in SiO2 matrix. Under the selected reaction conditions, dibenzothiophene(DBT) in model fuel can be removed within 2 h at room temperature(30 ℃). In addition, only 1.2% of efficiency lose than the fresh catalyst even after 5 cycles.

Alkali/alkaline-earth metal-modified MnO_(x) supported on three-dimensionally ordered macroporous–mesoporous Ti_(x)Si+(1-x)O_(2) catalysts:Preparation and catalytic performance for soot combustion

The performance of catalysts used in after-treatment systems is the key factor for the removal of diesel soot,which is an important component of atmosphericfine particle emissions.Herein,three-dimensionally ordered macroporous–mesoporous Ti_(x)Si+(1-x)O_(2)(3DOM-m Ti_(x)Si+(1-x)O_(2)) and its supported MnO_(x)catalysts doped with different alkali/alkaline-earth metals (AMnO_(x)/3 DOM-m Ti_(0.7)Si_(0.3)O_(2)(A:Li,Na,K,Ru,Cs,Mg,Ca,Sr,Ba)) were prepared by mesoporous template (P123)-assisted colloidal crystal template (CCT) and incipient wetness impregnation methods,respectively.Physicochemical characterizations of the catalysts were performed using scanning electron microscopy,X-ray diffraction,N_(2)adsorption–desorption,H_(2)temperature-programmed reduction,O_(2)temperature-programmed desorption,NO temperature-programmed oxidation,and Raman spectroscopy techniques;then,we evaluated their catalytic performances for the removal of diesel soot particles.The results show that the 3DOM-m Ti_(0.7)Si_(0.3)O_(2)supports exhibited a well-defined 3DOM-m nanostructure,and AMnO_(x)nanoparticles with 10–50 nm were evenly dispersed on the inner walls of the uniform macropores.In addition,the as-prepared catalysts exhibited good catalytic performance for soot combustion.Among the prepared catalysts,CsMnO_(x)/3DOM-m Ti_(0.7)Si_(0.3)O_(2)had the highest catalytic activity for soot combustion,with T10,T50,and T90(the temperatures corresponding to soot conversion rates of 10%,50%,and 90%) values of 285,355,and 393℃,respectively.The high catalytic activity of the CsMnO_(x)/3 DOM-m Ti_(0.7)Si_(0.3)O_(2)catalysts was attributed to their excellent low-temperature reducibility and homogeneous macroporous–mesoporous structure,as well as to the synergistic effects between Cs and Mn species and between CsMnO_(x)and the Ti_(0.7)Si_(0.3)O_(2)support.

Three‑Dimensional Ordered Mesoporous Carbon Spheres Modified with Ultrafine Zinc Oxide Nanoparticles for Enhanced Microwave Absorption Properties

Currently,electromagnetic radiation and interference have a significant effect on the operation of electronic devices and human health systems.Thus,developing excellent microwave absorbers have a huge significance in the material research field.Herein,a kind of ultrafine zinc oxide(ZnO)nanoparticles(NPs)supported on three-dimensional(3D)ordered mesoporous carbon spheres(ZnO/OMCS)is prepared from silica inverse opal by using phenolic resol precursor as carbon source.The prepared lightweight ZnO/OMCS nanocomposites exhibit 3D ordered carbon sphere array and highly dispersed ultrafine ZnO NPs on the mesoporous cell walls of carbon spheres.ZnO/OMCS-30 shows microwave absorbing ability with a strong absorption(−39.3 dB at 10.4 GHz with a small thickness of 2 mm)and a broad effective absorption bandwidth(9.1 GHz).The outstanding microwave absorbing ability benefits to the well-dispersed ultrafine ZnO NPs and the 3D ordered mesoporous carbon spheres structure.This work opened up a unique way for developing lightweight and high-efficient carbon-based microwave absorbing materials.

A New Fourth Order Difference Approximation for the Solution of Three-dimensional Non-linear Biharmonic Equations Using Coupled Approach

This paper deals with a new higher order compact difference scheme, which is, O(h4) using coupled approach on the 19-point 3D stencil for the solution of three dimensional nonlinear biharmonic equations. At each internal grid point, the solution u(x,y,z) and its Laplacian Δ4u are obtained. The resulting stencil algo-rithm is presented and hence this new algorithm can be easily incorporated to solve many problems. The present discretization allows us to use the Dirichlet boundary conditions only and there is no need to discretize the derivative boundary conditions near the boundary. We also show that special treatment is required to handle the boundary conditions. Convergence analysis for a model problem is briefly discussed. The method is tested on three problems and compares very favourably with the corresponding second order approximation which we also discuss using coupled approach.

Superior performance in visible-light-driven hydrogen evolution reaction of three-dimensionally ordered macroporous SrTiO_(3) decorated with Zn_(x)Cd_(1−x)S

It is of broad interest to develop emerging photocatalysts with excellent light-harvesting capacity and high charge carrier separation efficiency for visible light photocatalytic hydrogen evolution reaction.However,achieving satisfying hydrogen evolution efficiency under noble metal-free conditions remains challenging.In this study,we demonstrate the fabrication of three-dimensionally ordered macroporous SrTiO_(3)decorated with Zn_(x)Cd_(1−x)S nanoparticles for hydrogen production under visible light irradiation(λ>420 nm).Synergetic enhancement of photocatalytic activity is achieved by the slow photon effect and improved separation efficiency of photogenerated charge carriers.The obtained composites could afford very high hydrogen production efficiencies up to 19.67 mmol·g^(−1)·h^(−1),with an apparent quantum efficiency of 35.9%at 420 nm,which is 4.2 and 23.9 times higher than those of pure Zn_(0.5)Cd_(0.5)S(4.67 mmol·g^(−1)·h^(−1))and CdS(0.82 mmol·g^(−1)·h^(−1)),respectively.In particular,under Pt-free conditions,an attractive hydrogen production rate(3.23 mmol·g^(−1)·h^(−1))was achieved,providing a low-cost and high-efficiency strategy to produce hydrogen from water splitting.Moreover,the composites showed excellent stability,and no obvious loss in activity was observed after five cycling tests.

3D ordered macroporous sulfur-doped g-C_(3)N_(4)/TiO_(2)S-scheme photocatalysts for efficient H_(2)O_(2)production in pure water

Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a clean and cost-efficient alternative to the traditional anthraquinone oxidation approach.Herein,a step-scheme(S-scheme)heterojunction photocat-alyst is fabricated by coupling TiO_(2)with three dimensionally ordered macroporous sulfur-doped graphitic carbon nitride(3DOM SCN/T)by electrostatic self-assembly.The optimized photocatalyst achieved a high photocatalytic H_(2)O_(2)production activity with a yield of 2128μmol h^(−1)g^(−1)without the addition of hole scavengers.The remarkable performance was attributed to the synergy between the 3DOM framework and the S-scheme heterojunction.The former enhances light harvesting and provides abundant active sites for surface reactions,while the latter promotes the spatial separation of photogenerated carriers and enhances the redox power.Finally,the mechanism of photocatalytic H_(2)O_(2)production over the 3DOM SCN/T S-scheme composite is proposed.This work provides novel insights into the development of effi-cient photocatalysts for H_(2)O_(2)production from water and O_(2).

有序大孔HPW/SiO_(2)催化剂制备及其对燃油深度脱硫性能研究

利用单分散聚苯乙烯微球(PS)、TEOS和HPW,制备出HPW负载量为20%(质量分数)的有序大孔HPW/SiO_(2)催化剂。该催化剂大孔规整,排列有序,孔径约340 nm,比表面积约288.1 m~2·g^(-1),并存在一定量烧结介孔,孔径平均为8 nm。在60℃、O/S为12、加入量为0.5 g条件下,该催化剂对模拟燃油中的有机硫表现出优异的催化氧化特性,2 h内对DBT脱硫转化率达99.3%,重复使用7次脱硫转化率仅下降3.9%。该催化剂对燃油中另外两种主要的有机硫BT、4,6-DMDBT的催化氧化效率分别为90.6%、84.4%。

Enhanced photocatalytic performance of Bi_(4)O_(5)Br_(2)with threedimensionally ordered macroporous structure for phenol removal

Herein,a series of three-dimensionally ordered macroporous(3DOM)Bi_(4)O_(5)Br_(2)photocatalysts with different macropore sizes were successfully fabricated via a polymethyl methacrylate(PMMA)template method.The photocatalytic activity for phenol degradation over 3DOM Bi_(4)O_(5)Br_(2)first increased and then decreased with the rise in macropore size.Specifically,3DOM Bi_(4)O_(5)Br_(2)-255(macropore diameter ca.170 nm)exhibits the best photocatalytic activity in the static system,which is about 4.5,7.3,and 11.9 times higher than those of bulk Bi_(4)O_(5)Br_(2),Bi_(2)WO_(6),and g-C_(3)N_(4),respectively.Meanwhile,high phenol conversion(75%)is also obtained over 3DOM Bi_(4)O_(5)Br_(2)-255 in the flow system under full spectrum irradiation.Furthermore,3DOM Bi_(4)O_(5)Br_(2)-255 also shows strong mineralization capacity owing to the downward shift of valance band position(0.15 V)as compared with Bi_(4)O_(5)Br_(2).Total organic carbon(TOC)removal rate over 3DOM Bi_(4)O_(5)Br_(2)-255(62%)is much higher than that of Bi_(4)O_(5)Br_(2)(17%).The enhancement in photocatalytic performance of 3DOM Bi_(4)O_(5)Br_(2)-255 is attributable to its better phenol adsorption,O_(2)activation,and charge separation and transfer abilities.This work combines the advantages of 3D structure and surface dangling bonds,providing new possibilities for designing highly efficient photocatalysts for pollutants removal.

C9PR加氢催化剂孔道要求及其制备的研究进展

综述了适合于C9石油树脂(C9PR)加氢催化剂孔道结构的要求、孔道结构的制备及调节方法,并提出需加快对C9PR加氢催化剂孔道结构的研究。

乳化沥青对3DOM TiO_(2)雾封层材料的微观裹覆特征研究

采用三维有序大孔二氧化钛(3DOM TiO_(2))与雾封层技术相结合的方法降解路表附近的汽车尾气,可降低纳米TiO_(2)的团聚现象,提高尾气降解效果,但乳化沥青破乳后,3DOM TiO_(2)的微观裹覆特征与宏观降解性能之间的关系尚需进一步研究。因此,首先采用扫描电子显微镜(SEM)、物理吸附试验(BET)和压汞试验(MIP)测试并分析了不同孔径(200~500 nm)的3DOM TiO_(2)颗粒被乳化沥青裹覆前后的表面微观形貌、比表面积、孔径分布和孔体积。其次采用课题组自主设计的光催化性能测试分析系统测试了不同孔径的3DOM TiO_(2)雾封层材料对NO_x的降解效果,并结合孔径对3DOM TiO_(2)微观裹覆特征的影响规律,分析验证了3DOM TiO_(2)的微观裹覆特征与宏观降解性能之间的关系。研究结果表明:当孔径为300 nm时,3DOM TiO_(2)颗粒被沥青裹覆后材料中的有效孔道和比表面积最大,降解率最高。当光催化剂掺量为2%、孔径为300 nm时,3DOM TiO_(2)雾封层材料的降解率较纳米TiO_(2)雾封层材料提高了15.1%;较孔径为200、500 nm的3DOM TiO_(2)雾封层材料分别提高了5.2%、12.5%。

Preparation of the glucose sensor based on three-dimensional ordered macroporous gold film and room temperature ionic liquid

A novel type of glucose sensor was fabricated based on a glucose oxidase(GOD)-N,N-dimethtylformamide(DMF)-[BMIm][BF4] composites modified three-dimensional ordered macroporous(3DOM) gold film electrode.The immobilized GOD exhibits a pair of well-defined reversible peaks in 50 mM pH 7.0 phosphate buffer solutions(PBS),which could be attributed to the redox of flavin adenine dinucleotide(FAD) in GOD.The research results show that ionic liquid([BMIm][BF4]),DMF and 3DOM gold film are crucial for GOD to exhibit a pair of stable and reversible peaks.It is believed that the large active area of 3DOM gold film can increase the amount of immobilized GOD.Simultaneously,the application of IL enhances the stability of GOD and facilitates the electron transfer between GOD and the electrode.The synergetic effect of DMF can help the GOD to maintain its bioactivity better.GOD immobilized on the electrode exhibits the favorable electrocatalytic property to glucose,and the prepared sensor has a linear range from 10 to 125 nM with a detection limit of 3.3 nM at a signal-to-noise ratio of 3σ.The apparent Km(Michaelis-Menten constant) for the enzymatic reaction is 0.018 mM.

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.