Synthesis of an ordered porous carbon with the dual nitrogen-doped interfaces and its ORR catalysis performance

Both nitrogen-doping feature and pore structure are critical factors for developing nitrogen-doped carbons based catalysts with a high performance toward oxygen reduction reaction(ORR).Herein,a simple one-step CVD of acetylene and acetonitrile vapor method using silanized SBA-15 as a template has been developed to synthesize an ordered porous carbon(OPC) with dual nitrogen-doped interfaces.The optimized sample as prepared with the CVD of 4 h at 750℃ contains two types of ordered mesopores that one type is the ordered cylindrical pores inheriting from the pores of SBA-15 and has a pore width of4.0~5.0 nm,the other type is the ordered quasi-hexagonal pores with a width of 3.0~4.0 nm produced by etching the pore walls of SBA-15.These two types of pores whose pore walls are built by the nitrogen doped carbon layers resulted by the CVD and thus it actually makes the dual nitrogen-doped interfaced OPC(DN-OPC).Meanwhile,DN-OPC contains a few of micropores and a large SSA of 1430 m~2/g.This dualordered pores and dual nitrogen-doped interfaces cannot only facilitate mass transport but also utilize the active sites of DN-OPC for ORR.Therefore,as metal-free ORR catalyst,DN-OPC exhibits a good activity close to commercial Pt/C catalyst,and an excellent durability and methanol tolerance.     

Hierarchical porous silica materials with a trimodal pore system using surfactant templates

Porous silica exhibiting a hierarchically ordered trimodal pore system with a well-defined reverse opal microstructure and bimodal mesoporosity in the walls has been prepared by using polystyrene latex spheres, a novel block copolymer and an ionic liquid surfactant as templates. The resulting materials exhibit hierarchical order at three length scales (small mesopores: 2-3 nm; large mesopores: 11-12 nm; macropores: 360 nm).     

Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas

Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.     

Solvent evaporation induced aggregating assembly approach to three-dimensional ordered mesoporous silica with ultralarge accessible mesopores

A solvent evaporation induced aggregating assembly (EIAA) method has been demonstrated for synthesis of highly ordered mesoporous silicas (OMS) in the acidic tetrahydrofuran (THF)/H(2)O mixture by using poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA) as the template and tetraethylorthosilicate (TEOS) as the silica precursor. During the continuous evaporation of THF (a good solvent for PEO-b-PMMA) from the reaction solution, the template molecules, together with silicate oligomers, were driven to form composite micelles in the homogeneous solution and further assemble into large particles with ordered mesostructure. The obtained ordered mesoporous silicas possess a unique crystal-like morphology with a face centered cubic (fcc) mesostructure, large pore size up to 37.0 nm, large window size (8.7 nm), high BET surface area (508 m(2)/g), and large pore volume (1.46 cm(3)/g). Because of the large accessible mesopores, uniform gold nanoparticles (ca. 4.0 nm) can be introduced into mesopores of the OMS materials using the in situ reduction method. The obtained Au/OMS materials were successfully applied to fast catalytic reduction of 4-nitrophenol in the presence of NaHB(4) as the reductant. The supported catalysts can be reused for catalytic reactions without significant decrease in catalysis performance even after 10 cycles.     

Development of mesophase pitch derived mesoporous carbons through a commercially nanosized template

Mesoporous carbons (MCs) with a high surface area (up to 900 m2/g), large pore volume (up to 2.1 cm3/g), high mesopore ratio (94%), and high yield (70%) were successfully prepared from an AR mesophase pitch, using a commercially nanosized silica template. The removal of the template provided some larger mesopores of 25-50 nm (pore I) with a surface area of ca. 300 m2/g, while the successive carbonization opened the closed pores within the carbon body to give smaller mesopores of 2-10 nm (pore II) with a similar surface area. During the carbonization of pitch precursor, the evaporation of volatile components swells the carbon to introduce the second mesopores among the domains and even microdomain units because of their rearrangements and overlappings in the process. The addition of iron salt with the silica template resulted in a remarkable increase of the surface area (ca. 300 m2/g) by introducing mesopores of 3-5 nm. The resultant MCs maintained some graphitizable natures derived from the anisotropic precursor. Their graphitization at 2400 degrees C provided the graphitic structure with large surface areas (270-460 m2/g) and mesoporosity.     

Ordered Large‐Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Ordered mesoporous metal–organic frameworks (mesoMOFs) were constructed with a uniform pore size up to about 10 nm and thick microporous walls, opening up the possibility for the mass diffusion of large‐size molecules through crystalline MOFs. The synergistic effects based on triblock copolymer templates and the Hofmeister salting‐in anions promote the nucleation of stable MOFs in aqueous phase and the in situ crystallization of MOFs around templates, rendering the generation of a microcrystal with periodically arranged large mesopores. The improved mass transfer benefiting from large‐pore channels, together with robust microporous crystalline structure, endows them as an ideal nanoreactor for the highly efficient digestion of various biogenic proteins. This strategy could set a guideline for the rational design of new ordered large‐pore mesoMOFs with a variety of compositions and functionalities and pave a way for their potential applications with biomacromolecules.     

Novel ice structures in carbon nanopores: pressure enhancement effect of confinement

We report experimental results on the structure and melting behavior of ice confined in multi-walled carbon nanotubes and ordered mesoporous carbon CMK-3, which is the carbon replica of a SBA-15 silica template. The silica template has cylindrical mesopores with micropores connecting the walls of neighboring mesopores. The structure of the carbon replica material CMK-3 consists of carbon rods connected by smaller side-branches, with quasi-cylindrical mesopores of average pore size 4.9 nm and micropores of 0.6 nm. Neutron diffraction and differential scanning calorimetry have been used to determine the structure of the confined ice and the solid-liquid transition temperature. The results are compared with the behavior of water in multi-walled carbon nanotubes of inner diameters of 2.4 nm and 4 nm studied by the same methods. For D(2)O in CMK-3 we find evidence of the existence of nanocrystals of cubic ice and ice IX; the diffraction results also suggest the presence of ice VIII, although this is less conclusive. We find evidence of cubic ice in the case of the carbon nanotubes. For bulk water these crystal forms only occur at temperatures below 170 K in the case of cubic ice, and at pressures of hundreds or thousands of MPa in the case of ice VIII and IX. These phases appear to be stabilized by the confinement.     

ZSM-5 monolith of uniform mesoporous channels

A ZSM-5 monolith of uniform mesopores(meso-ZSM-5) was synthesized with the template method using carbon aerogel of uniform mesopores of great pore volume. The pore size distribution determined by N2 adsorption showed the presence of mesopores with an average pore width of 11 nm and micropores with an average pore width of 0.51 nm. Field emission scanning electron micrograph observation revealed the presence of uniform mesopores. X-ray diffraction and FT-IR provided evidence that the synthesized meso-ZSM-5 monolith has a highly crystalline ZSM-5 structure.     

Amphiphilic block copolymers directed synthesis of mesoporous nickel-based oxides with bimodal mesopores and nanocrystal-assembled walls

Ordered mesoporous Fe-doped NiO with dual mesopores, high surface area and well-interconnected crystalline porous frameworks have been synthesized via solvent evaporation-induced co-assembly (EICA) method, by using PS-b-P4VP as structure-directing agent, Ni(acac)₂ and Fe (acac)₃ as binary inorganic precursor, and showed superior ethanol sensing performances with good sensitivity, high selectivity and fast response-recovery dynamics.     

Ordered mesoporous silicas and carbons with large accessible pores templated from amphiphilic diblock copolymer poly(ethylene oxide)-b-polystyrene

Highly ordered mesoporous carbons and silicas with ultralarge accessible pores have been successfully synthesized by using laboratory-made poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymers as templates via the evaporation-induced self-assembly (EISA) approach. Resols and tetraethyl orthosilicate (TEOS) serve as carbon and silica precursors, respectively. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) measurements show that the mesoporous carbons (denoted as C-FDU-18) possess face centered cubic closed-packing (fcc) mesostructure (Fm3m) with large-domain ordering. N2 sorption isotherms reveal a large mesopore at the mean value of 22.6 nm with a narrow pore-size distribution. Mesoporous silicas (Si-FDU-18) also display a highly ordered fcc closed-packing mesostructure with an ultralarge unit cell (a = 54.6 nm). A hydrothermal recrystallization was introduced for the first time to produce micropores in thick silica walls (approximately 7.7 nm) and thus to generate ultralarge accessible mesopores (30.8 nm). Notably, the amphiphilic diblock copolymer with high molecular weight (PEO125-PS230, 29700 g mol-1) in this report was prepared via a simple method of atom transfer radical polymerization (ATRP). It can be easily available for chemists even without any experience in polymer synthesis.     

双模板法制备介孔／大孔复合孔结构硅胶独石

采用双模板法,向正硅酸甲酯的水解体系中同时引入聚乙二醇和三嵌段共聚物,成功制备出具有双连续大孔、同时孔壁中分布着有序介孔的复合孔结构硅胶独石材料. 产物的比表面积高达880 m2/g, 大孔孔径为0.2～5 μm, 介孔高度集中地分布在 5 nm. 结合物理吸附、扫描电镜、粉末X射线衍射和透射电镜等表征手段,发现合成条件如原料组成、反应温度和pH值等对反应体系中凝胶化转变和相分离发生的相对速度有重要影响,进而影响产物复合孔结构的生成. 此外,通过对合成条件的优化,一方面增强了无机骨架的强度,另一方面降低了湿凝胶干燥过程中的毛细管压力降,有效缓和了凝胶结构在干燥过程中的开裂和变形,使复合孔结构硅胶独石在厘米尺度内具有良好的整体性能.     

A "teardown" method to create large mesotunnels on the pore walls of ordered mesoporous silica

A "teardown" method to create large mesotunnels (approximately 9 nm) on the pore walls of ordered mesoporous silicas is demonstrated by digesting the organic constituents from polymer-silicate nanocomposites. The ordered mesostructured polymer-silicate composites were first obtained via the evaporation-induced triconstituent co-assembly method by using a low-molecular-weight phenolic resin (resols) as an organic precursor; prehydrolyzed TEOS as an inorganic precursor, and triblock copolymer F127 as a template. All of organic components including F127 and phenolic resins are removed by the microwave digestion (MWD) method from mesostructured polymer-silica composites. While the removal of triblock copolymer F127 generates main pore channels, the phenolic resins can also be torn down from the pore walls, yielding mesotunnels between the channels. The resulting silica products exhibit ordered 2-D hexagonal mesostructure, large pore volume (up to 1.92 cm(3)/g), and very large pore size (up to 22.9 nm), which is even larger than their mesostructural cell parameter (14.2 nm). TEM images confirm the existence of mesotunnels on the silica pore walls. FT-IR and (29)Si solid-state NMR results reveal that these silica products have a large number of silanol groups.     

Hierarchical control of porous silica by pH adjustment: Alkyl polyamines as surfactants for bimodal silica synthesis and its carbon replica

Bimodal macro-mesoporous silica networks have been prepared in a simple one-pot synthesis using an inexpensive tetramine surfactant and tetraethoxysilane as a silica precursor. These novel materials show high pore volumes and templated mesopores (average pore size 3.0 nm) embedded in 20 nm thick walls forming interparticle large meso/macropores. The judicious control of the pH during the silica formation allows for the precise control of the interparticle condensation, likely due to the change in the interaction between the tetramine surfactant and the silica precursors. Finally, a highly porous carbon replica with bimodal porosity was prepared by using the bimodal silica as a hard sacrificial template. The microstructure of the silica template was accurately transferred to the carbon material obtaining high surface areas (up to 1300 m² g⁻¹) and total pore volumes ≥2 cm³ g⁻¹.     

双峰孔分布薄壁中孔碳的便捷制备

以廉价的γ-氧化铝为模板制备薄壁中孔碳材料,且可在制备过程中方便地对碳材料的孔结构、微孔率等参数进行调控.以原位聚合的酚醛树脂为碳源取代蔗糖,简化了制备流程.制得的碳材料不仅可以较好地复制氧化铝模板的孔结构,且比表面积比以蔗糖为碳源的样品显著提高.在此基础上,选用模板堆积孔径与模板自身直径差异较大的长棒状氧化铝为模板,成功地以一种模板、经过一次聚合-碳化过程制备出了具有双峰孔分布(PSD)结构的薄壁碳材料,两个峰分别位于4 nm附近的较小中孔区和13 nm附近的较大中孔区.此外,所得碳材料的比表面积(>1800 m2·g-1)和孔容(>4.5 cm3·g-1)均很高,而微孔率却较低,具有优异的中孔特性.将所得碳材料用作电化学电容器的电极,电容可达200 F·g-1,且当电流密度从0.1 A·g-1升至1.0 A·g-1时,比电容仅衰减10%,表现出良好的电容性能.     

Amphiphilic block copolymers directed synthesis of mesoporous nickel-based oxides with bimodal mesopores and nanocrystal-assembled walls

Mesoporous late-transition metal oxides have great potential in applications of energy,catalysis and chemical sensing due to their unique physical and chemical properties.However,their synthesis via the flexible and scalable soft-template method remain a great challenge,due to the weak organic-inorganic interaction between the frequently used surfactants(e.g.,Pluronic-type block copolymers) and metal oxide precursors,and the low crystallization temperature of metal oxides.In this study,ordered mesoporous NiO with dual mesopores,high surface area and well-interconnected crystalline porous frameworks have been successfully synthesized via the facile solvent evaporation-induced co-assembly(EICA) method,by using lab-made amphiphilic diblock copolymer polystyrene-b-poly(4-vinylpyridine)(PS-b-P4 VP) as both the structure-directing agent(the soft template) and macromolecular chelating agents for nickel species,THF as the solvent,and nickel acetylacetonate(Ni(acac)2) as inorganic precursor.Similarly,by using Ni(acac)2 and Fe(acac)3 as the binary precursors,ordered mesoporous Fedoped NiO materials can be obtained,which have bimodal mesopores of large mesopores(32.5 nm) and secondary mesopores(4.0-11.5 nm) in the nanocrystal-assembled walls,high specific surface areas(～74.8 m~2/g) and large pore value(～0.167 cm~3/g).The obtained mesoporous Fe-doped NiO based gas sensor showed superior ethanol sensing performances with good sensitivity,high selectivity and fast response-recovery dynamics.     

薄壁中孔碳材料的精细控制合成

利用γ-氧化铝为模板, 精细控制合成了一系列具有不同孔径的中孔碳材料. 在优化的条件下, 所得的碳材料具有孔径分布窄、比表面积高(>1000 m²·g^-1)、孔容大(最高3.82 cm³·g^-1)、中孔率高(>99%)的特点, 并且孔壁厚度仅有1-2个石墨层. 选用了三种不同来源的氧化铝为模板, 考察了模板与所得碳材料织构的相关性, 并提出用无序模板可控制备碳材料的机理. 即在碳包覆氧化铝的复合物前体中, 若碳层完整覆盖氧化铝表面并且足够强韧, 则所得碳材料可近似复制模板的孔结构, 并且碳材料的孔一部分由去除模板所生成, 另一部分来源于模板原有的孔. 据此模型对所得碳材料的孔容进行了理论计算, 其结果有力支持了上述机理.     

甲烷在中孔分子筛MCM-41中吸附的计算机模拟

采用巨正则系综Monte Carlo方法研究了甲烷在两个不同孔径的MCM-41中不同温度下的吸附等温线和其在孔中的相行为和排列方式.模拟结果显示,在较小孔径的MCM-41中,流体分子达到毛细凝聚所需的化学位较小,并且观察到两个孔径下计算机模拟得到的亚稳态区域都非常宽,使得层状转变（如果有的话）被包含在这个区域.通过比较两种孔径下达到毛细凝聚后的构型,可以看出,在3.5 nm的孔中流体的分子结构出现非常有序的排列,而在5.0 nm的孔中则没有.在常温300 K时甲烷的吸附的计算机模拟表明,孔壁对流体分子的作用仅仅影响较靠近壁面附近的流体分子的排列,而对孔中间的分子几乎没有影响.     

Ordered Large-Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Ordered mesoporous metal–organic frameworks (mesoMOFs) were constructed with a uniform pore size up to about 10 nm and thick microporous walls, opening up the possibility for the mass diffusion of large-size molecules through crystalline MOFs. The synergistic effects based on triblock copolymer templates and the Hofmeister salting-in anions promote the nucleation of stable MOFs in aqueous phase and the in situ crystallization of MOFs around templates, rendering the generation of a microcrystal with periodically arranged large mesopores. The improved mass transfer benefiting from large-pore channels, together with robust microporous crystalline structure, endows them as an ideal nanoreactor for the highly efficient digestion of various biogenic proteins. This strategy could set a guideline for the rational design of new ordered large-pore mesoMOFs with a variety of compositions and functionalities and pave a way for their potential applications with biomacromolecules.     

Hierarchically porous carbon membranes derived from PAN and their selective adsorption of organic dyes

Porous carbon membranes were favorably fabricated through the pyrolysis of polyacrylonitrile(PAN) precursors, which were prepared with a template-free technique-thermally induced phase separation. These carbon membranes possess hierarchical pores, including cellular macropores across the whole membranes and much small pores in the matrix as well as on the pore walls. Nitrogen adsorption indicates micropores(1.47 and 1.84 nm) and mesopores(2.21 nm) exist inside the carbon membranes, resulting in their specific surface area as large as 1062 m2/g. The carbon membranes were used to adsorb organic dyes(methyl orange, Congo red, and rhodamine B) from aqueous solutions based on their advantages of hierarchical pore structures and large specific surface area. It is particularly noteworthy that the membranes present a selective adsorption towards methyl orange, whose molecular size(1.2 nm) is smaller than those of Congo red(2.3 nm) and rhodamine B(1.8 nm). This attractive result can be attributed to the steric structure matching between the molecular size and the pore size, rather than electrostatic attraction. Furthermore, the used carbon membranes can be easily regenerated by hydrochloric acid, and their recovery adsorption ratio maintains above 90% even in the third cycle. This work may provide a new route for carbon-based adsorbents with hierarchical pores via a template-free approach, which could be promisingly applied to selectively remove dye contaminants in aqueous effluents.     

Construction of a hierarchical architecture in a wormhole-like mesostructure for enhanced mass transport

A unique hierarchical architecture is successfully constructed in a wormhole-like mesopore structure via a multiple nanocasting route. This novel type of hierarchical porous carbon (HPC) consists of three-dimensional ordered macropores (ca. 150 nm) with interconnecting pore windows, and the walls of these macropores are rich in wormhole-like mesopores (ca. 2.7 nm) and large spherical mesopores (ca. 10 nm), as well as a significant microporosity, presenting a macro-meso-microporous structure with a three-dimensional interconnectivity. Such a hierarchically porous structure may provide fine diffusion pathways for reaction species, which is demonstrated by the experimental result of an enhanced performance in a supercapacitor. For example, with the introduction of a hierarchical porous structure for fast transport and effective access of ions, the as-prepared HPC exhibits a specific capacitance as high as 247 F g(-1), whereas traditional wormhole-like mesoporous carbon has only a specific capacitance of 176 F g(-1).