Synthesis of K-doped three-dimensionally ordered macroporous Mn_(0.5)Ce_(0.5)O_δ catalysts and their catalytic performance for soot oxidation

A series of K-doped Mn0.5Ce0.5Oδ （K-MCO） catalysts with three-dimensionally ordered macroporous （3DOM） structure and different K loadings were successfully synthesized using simple methods. These catalysts exhibited well-defined 3DOM nanostructure, which consisted of extensive interconnecting networks of spherical voids. The effects of the calcination temperature and calcination time on the morphological characteristics and crystalline forms of the catalysts were systematically studied. The catalysts showed high catalytic activity for the combustion of soot. 3DOM 20% K-MCO-4h catalyst, in particular, showed the highest catalytic activity of all of the catalysts studied （e.g., Ts0 = 331 ~C and Smco2 = 95.3%）. The occurrence of structural and synergistic effects among the K, Mn, and Ce atoms in the catalysts was favorable for enhancing their catalytic activity towards the combustion of diesel soot. Furthermore, the temperatures required for the complete combustion of the soot （〈400 ℃） were well within the exhaust temperature range （175-400 ℃）, which means that the accumulated soot can be removed under the conditions of the diesel exhaust gas. These catalysts could therefore be used in numerous practical applications because they are easy to synthesize, exhibit high catalytic activity, and can be made from low cost materials.

Hierarchically ordered porous carbon with atomically dispersed cobalt for oxidative esterification of furfural

Nitrogen-rich zeolitic imidazolate frameworks(ZIFs)are ideal precursors for the synthesis of metal single atoms anchored on N-doped carbon.However,the microporous structures of conventional ZIFs lead to low mass transfer efficiency and low metal utilization of their derivatives.Here,we construct a composite of Co single atoms anchored on nitrogen-doped carbon with a three-dimensional ordered macroporous structure(Co-SA/3DOM-NC)by two-step pyrolysis of ordered macro/microporous ZnCo-ZIF.Co-SA/3DOM-NC shows high activity in the oxidative esterification of furfural,achieving a 99%yield of methyl 2-furoate under mild reaction conditions,which is significantly superior to the microporous and the Conanoparticle counterparts.The high activity of Co-SA/3DOM-NC should be attributed to the CoN4 centers with high intrinsic activity and the ordered macroporous structure,promoting the mass transfer of reactants and accessibility of active sites.

Ordered macroporous boron phosphate crystals as metal-free catalysts for the oxidative dehydrogenation of propane

Ordered macroporous materials with rapid mass transport and enhanced active site accessibility are essential for achieving improved catalytic activity.In this study,boron phosphate crystals with a three-dimensionally interconnected ordered macroporous structure and a robust framework were fabricated and used as stable and selective catalysts in the oxidative dehydrogenation(ODH)of propane.Due to the improved mass diffusion and higher number of exposed active sites in the ordered macroporous structure,the catalyst exhibited a remarkable olefin productivity of^16 golefin gcat^-1 h^-1,which is up to 2–100 times higher than that of ODH catalysts reported to date.The selectivity for olefins was 91.5%(propene:82.5%,ethene:9.0%)at 515℃,with a propane conversion of 14.3%.At the same time,the selectivity for the unwanted deep-oxidized CO2 product remained less than 1.0%.The tri-coordinated surface boron species were identified as the active catalytic sites for the ODH of propane.This study provides a route for preparing a new type of metal-free catalyst with stable structure against oxidation and remarkable catalytic activity,which may represent a potential candidate to promote the industrialization of the ODH process.

A novel adsorbent of three-dimensional ordered macro/mesoporous carbon for removal of malachite green dye

Three-dimensional ordered macro/mesoporous carbon(3DOM/m-C)with high specific surface area was synthesized by colloid crystal template method with chemical activation by KOH and used as the adsorbent for removing malachite green(MG)in aqueous solution.The microstructures of the adsorbents were characterized by FESEM,TEM and BET,and the effects of initial dye concentration,contact time,solution pH,and temperature on adsorption performance were investigated.The results show that the 3DOM/m-C exhibits extremely high adsorption capacity of 3541.1 mg/g within 2 h,which could be attributed to the novel ordered hierarchical structure with mesopores on three-dimensional ordered macroporous carbon walls.And the adsorption behavior conforms to the pseudo-second-order kinetic and Langmuir adsorption isotherm.3DOM/m-C can be recycled after being desorbed by absolute ethanol,and still maintains a high capacity of 2762.06 mg/g after 5 cycles.

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.

Fabrication of ultrafine Pd nanoparticles on 3D ordered macroporous TiO_2 for enhanced catalytic activity during diesel soot combustion

Nanocatalysts consisting of three‐dimensionally ordered macroporous(3DOM)TiO2‐supported ultrafine Pd nanoparticles(Pd/3DOM‐TiO2‐GBMR)were readily fabricated by gas bubbling‐assisted membrane reduction(GBMR)method.These catalysts had a well‐defined and highly ordered macroporous nanostructure with an average pore size of 280 nm.In addition,ultrafine hemispherical Pd nanoparticles(NPs)with a mean particle size of 1.1 nm were found to be well dispersed over the surface of the 3DOM‐TiO2 support and deposited on the inner walls of the material.The nanostructure of the 3DOM‐TiO2 support ensured efficient contact between soot particles and the catalyst.The large interface area between the ultrafine Pd NPs and the TiO2 also increased the density of sites for O2 activation as a result of the strong metal(Pd)‐support(TiO2)interaction(SMSI).A Pd/3DOM‐TiO2‐GBMR catalyst with ultrafine Pd NPs(1.1 nm)exhibited higher catalytic activity during diesel soot combustion compared with that obtained from a specimen having relatively large Pd NPs(5.0 nm).The T10,T50 and T90 values obtained from the former were 295,370 and 415°C.Both the activity and nanostructure of the Pd/3DOM‐TiO2‐GBMR catalyst were stable over five replicate soot oxidation trials.These results suggest that nanocatalysts having a 3DOM structure together with ultrafine Pd NPs can decrease the amount of Pd required,and that this approach has potential practical applications in the catalytic combustion of diesel soot particles.

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.

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.

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.

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.

Pt/Co_3O_4/3DOM Al_2O_3:Highly effective catalysts for toluene combustion

Three-dimensionally ordered macro-/mesoporous alumina（3DOM Al2O3）-supported cobalt oxide and platinum nanocatalysts（xPt/yCo3O4/3DOM Al2O3,Pt mass fraction（x%）= 0-1.4%,Co3O4 mass fraction（y%） = 0-9.2%） were prepared using poly（methyl methacrylate） templating,incipient wetness impregnation and polyvinyl alcohol-protected reduction.The resulting xPt/yCo3O4/3DOM Al2O3 samples displayed a high-quality 3DOM architecture with macropores（180-200 nm in diameter） and mesopores（4-6 nm in diameter） together with surface areas in the range of 94 to 102m^2/g.Using these techniques,Co3O4 nanoparticles（NPs,18.3 nm） were loaded on the 3DOM Al2O3 surface,after which Pt NPs（2.3-2.5 nm） were uniformly dispersed on theyCo3O4/3DOM Al2O3.The1.3Pt/8.9Co3O4/3DOM Al2O3 exhibited the best performance for toluene oxidation,with a T（90%） value（the temperature required to achieve 90%toluene conversion） of 160 ℃ at a space velocity of20000 mL g^（-1） h^（-1）.It is concluded that the excellent catalytic performance of the 1.3Pt/8.9Co3O4/3DOM Al2O3 is owing to well-dispersed Pt NPs,the high concentration of adsorbed oxygen species,good low-temperature reducibility,and strong interaction between the Pt and Co3O4 NPs,as well as the unique bimodal porous structure of the support.

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.

INVERSE OPALINE STRUCTURE TITANIA PHOTONIC CRYSTALS BY FUNCTIONALLY MODIFIED COLLOIDAL CRYSTALS TEMPLATING

Ordered macroporous titania photonic crystals （PCs） and photonic balls were fabricated by functional modified polymer colloidal crystals. The TiO2 PCs and balls formed through this method exhibit no cracks and lacunae in large areas on their surface and their inner structures.

MESO-STRUCTURED POLYMERIC HYDROGELS

Meso-structured (opal and inverse opal) polymeric hydrogels of varied morphology and composition wereprepared by using two methods: post-modification of the template-synthesized structured polymers and template-polymerization of functional monomers. A polyacrylic acid based inverse opal hydrogel was chosen to demonstrate its fastpH response by changing color, which is important in designing tunable photonic crystals. Template effects of the hydrogelson controlling structure of the template-synthesized inorganic materials were discussed. The catalytic effect of acid groups inthe templates was emphasized for a preferential formation of TiO_2 in the region containing acid groups, which allowedduplicating inorganic colloidal crytals from colloidal crystal hydrogels (or macroporous products from macroporoushydrogels) via one step duplication.

Enhanced hydrogen evolution performance by 3D ordered macroporous Ru-CoP@NC electrocatalysts

Electrocatalytic water splitting coupled with sustainable energies is identified as an environmentally friendly and renewable strategy to generate high-quality hydrogen for the fuel cells.However,the main challenge is to develop high performance,low cost and chemically stable electrocatalysts to decline the energy barriers and enhance the sluggish kinetics of hydrogen evolution reaction(HER).Herein,a three-dimensional hierarchically ordered macroporous Ru-CoP@NC electrocatalyst(3DOM Ru-CoP@NC)derived from ordered macro-microporous metal-organic frameworks has been prepared using the precursor@template and double-solvent methods.The prepared 3DOM Ru-CoP@NC catalyst exhibits an overpotential of 15 mV(j=10 mA·cm^(-2))and a reaction Tafel slope of 38 mV·dec^(-1)in alkaline electrolyte,which are superior to commercial Pt@C catalyst.Additionally,the overpotential and reaction Tafel slope of this catalyst in acidic media are 45 mV and 50 mV·dec^(-1),respectively.The outstanding HER activities of 3DOM Ru-CoP@NC catalysts are ascribed to the 3D highly interconnectedreticular nanospaces that can increase effective reaction active sites.The N dope d carbon framework improves the electronic properties and conductivity.Moreover,the strong interaction of Ru and CoP nanoparticles also boosts the HER process.These results indicate that 3DOM Ru-CoP@NC catalysts with high catalytic activities have a broad application prospect in the future.

Maximizing hydrogen evolution via Co-Ni dual atoms and nanoclusters on hierarchically ordered porous carbon framework

Efficient hydrogen production through water splitting relies on the development of high-performance catalysts for the hydrogen evolution reaction(HER).In this study,we synthesized the CoNi SAs@NPs-NC catalyst using multi-metal single-crystal ordered macroporous metal-organic frameworks(MOFs)as precursors.This catalyst features a hierarchical porous structure with ordered macropores and micropores,which not only provides a high specific surface area but also promotes efficient mass diffusion.Furthermore,the incorporation of bimetallic components,coupled with synergistic interactions between single atoms(SAs)and nanoparticles(NPs),significantly enhances its catalytic activity.The CoNi SAs@NPs-NC nanocatalysts demonstrated exceptional activity in the HER,recording overpotentials of 90 mV in 1 M KOH and 61 mV in 0.5 M H_(2)SO_(4),both at a current density of 10 mA cm^(−2).In addition,density functional theory(DFT)analysis was employed to investigate the synergistic interactions among CoNi NPs,SAs,and nitrogen dopants.Our finding highlights the promising potential of the CoNi SAs@NPs-NC catalyst for efficient hydrogen evolution,making it a valuable candidate for advancing the field of water splitting.

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 polystyrene-based monolith with ordered macroporous structure

In this paper,polystyrene-based monoliths with highly ordered macroporous structure were synthesized by using SiO_2 colloidal crystal as template.SEM observation shows that the macropores are highly ordered and are interconnected by small windows.The BET surface area of PS monolith is about 36.17 m^2/g.The polymer monoliths can resist 5 MPa pressure,showing high mechanical and compressive strength.

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).