One-pot synthesis of silica monoliths with hierarchically porous structure

Poly(furfuryl alcohol) (PFA) and block copolymer Pluronic F127 were used as pore templates to create mechanically robust silica monoliths with a hierarchical and interconnected macro-mesoporous network in an easy, reproducible bimodal scale templating process. Control over the morphology was obtained by varying the reactant ratios. Phase separation on the submicrometer scale occurred when furfuryl alcohol was cationically polymerized and therefore became immiscible with the solvent and the silica precursor. Upon a subsequent sol-gel reaction, a silica-F127 matrix formed around the PFA spheres, leading to macropore structures with mesoporous walls. Surface areas of the final structures ranged from 500 to 989 m² g⁻¹ and a maximum pore volume of 4.5 mL g⁻¹ was achieved. Under mildly acidic conditions, micelle-templated mesopores resulted. Interconnected macropores could be obtained by increasing the pH or the block copolymer concentration. The formation mechanism and the relationship between PFA, Pluronic F127 and acidity are discussed in detail.     

One-pot hydrothermal synthesis of nitrogen-doped hierarchically porous carbon monoliths for supercapacitors

The nitrogen-doped hierarchically porous carbon monoliths (N-HPCMs) were successfully synthesized by using dicyandiamide (DCDA) as nitrogen source, phenolic resol as carbon precursor and mixed triblock copolymers as templates via a one-pot hydrothermal approach. The obtained carbon monoliths possess tunable mesopore size (4.3–11.4 nm), large surface area (552–660 m²/g), and high nitrogen content (up to 12.1 wt%). Ascribed to the nitrogen-doped frameworks and hierarchical porosity, N-HPCMs exhibit good electrochemical performance as the supercapacitor electrode with specific capacitance of 268.9 F/g (in 6 M KOH) at a current density of 1 A/g, and a 4.1 % loss of the specific capacitance after 5,000 charge–discharge cycles, indicating a long-term cycling stability. Such unique features make N-HPCMs promising electrode materials for high performance supercapacitors.     

Facile synthesis of nitrogen and oxygen co-doped hierarchical porous carbon materials for high performance super capacitors

Journal of Porous Materials - Nitrogen and oxygen co-doped hierarchical porous carbons (NOPCs) is prepared by the pyrolysis of polyethylene glycol-200 (PEG) and triazine carbon forming agent (CFA)...     

Processing of highly porous bioglass monoliths by hydrothermal hot pressing

Porous bioglass monoliths have been processed by hydrothermal hot pressing (HyHP) from sol-gel and melt-derived bioglass powders of composition (in mol %): SiO₂–CaO–P₂O₅ (55.0-40.0-5.0) and SiO₂–CaO–Na₂O–P₂O₅ (47.2-26.4-23.8-2.6), respectively. An open porosity of >70% ever reached in 3D structures is reported for monoliths issued from sol-gel powders. Dissolution studies were performed in simulated body fluid (SBF) for 1–30 days. The monoliths were analysed using X-Ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) spectroscopy and Scanning Electron Microscopy (SEM) to observe the formation of an apatite-like layer and elemental concentration of SBF was evaluated using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). A higher kinetics in the development of apatite layer was observed for sol-gel derived monoliths. This result is explained by the high surface areas of the nanosized sol-gel powders and the possibility of HyHP to create large porosity (mesoporous monoliths) and retain large surface areas. HyHP is also effective in processing 3D-bioglass structures with porosity gradient by co-sintering powders of different size.     

Ultra-high specific capacitance of self-doped 3D hierarchical porous turtle shell-derived activated carbon for high-performance supercapacitors

The turtle shell of biomass waste is used as raw material, and the natural inorganic salt contained in it is used as a salt template in combination with a chemical activation method to successfully prepare a high-performance activated carbon with hierarchical porous structure. The role of hydroxyapatite (HAP) and KOH in different stages of preparation was investigated. The prepared turtle shell-derived activated carbon (TSHC-5) has a well-developed honeycomb pore structure, which gives it a high specific surface area (SSA) of 2828 m² g^?1 with a pore volume of 1.91 cm³ g^?1. The excellent hierarchical porous structure and high heteroatom content (O 6.88%, N 5.64%) allow it to have an ultra-high specific capacitance of 727.9 F g^?1 at 0.5 A g^?1 with 92.27% of capacitance retention even after 10,000 cycles. Excitingly, the symmetric supercapacitor assembled from TSHC-5 activated carbon exhibits excellent energy density and cycling stability in a 1 M Na₂SO₄ aqueous solution. The energy density is 45.1 Wh·kg^?1 at a power density of 450 W kg^?1, with 92.05% capacitance retention after 10,000 cycles. Therefore, turtle shell-derived activated carbon is extremely competitive in sustainable new green supercapacitor electrode materials.     

晶种法合成整体式多级孔ZSM-5分子筛

以四丙基氢氧化铵为模板,采用原位水热法,添加Silicalite-1晶种和十六烷基三甲基溴化铵,一步合成直径约为2cm、高约为0.8cm、中间部位向内凹、边缘部位凸起且表面较光滑的分子筛圆片集聚体。XRD、SEM和N2吸附-脱附表征结果表明,该分子筛圆片集聚体是由小晶粒堆积成的具有微孔和介孔的多级孔ZSM-5分子筛。     

Foam-gelcasting preparation,microstructure and thermal insulation performance of porous diatomite ceramics with hierarchical pore structures

Hierarchically pore-structured porous diatomite ceramics containing 82.9∼84.5% porosity were successfully prepared for the first time via foam-gelcasting using diatomite powder as the main raw material. Sizes of mesopores derived from the raw material and macropores formed mainly from foaming were 0.02∼0.1 μm and 109.7∼130.5 μm, respectively. The effect of sintering temperature, additive content and solid loading of slurry on pore size and distribution, and mechanical and thermal properties of as-prepared porous ceramics were investigated. Compressive strength of as-prepared porous ceramics increased with sintering temperature, and the one containing 82.9% porosity showed the highest compressive strength of 2.1 ± 0.14 MPa. In addition, the one containing 84.5% porosity and having compressive strength of 1.1 ± 0.07 MPa showed the lowest thermal conductivity of 0.097 ± 0.001 W/(m·K) at a test temperature of 200 ̊C, suggesting that as-prepared porous ceramics could be potentially used as good thermal insulation materials.     

Wet chemical synthesis of Gd+3 doped vanadium Oxide/MXene based mesoporous hierarchical architectures as advanced supercapacitor material

In this paper, Gd³⁺ doped V₂O₅/Ti₃C₂T_x MXene (GVO/MX) hierarchical architectures have been synthesized by wet chemical approach. As prepared GVO/MX composite, along undoped VO and unsupported GVO were well characterized by XRD, FESEM, EDX, FT-IR and BET techniques. Electrochemical performance of VO, GVO and GVO/MX was evaluated by CV, GCD and EIS measurements. Among the three electrodes, GVO/MX composite exhibited highest electrochemical activity with the optimum specific capacitance of 1024 Fg^-1 at 10 mVs^?1. The specific capacitance of GVO/MX was ～1.7 and ～3 times higher than unsupported GVO (585 Fg^-1) and VO (326 Fg^-1), respectively. The cyclic life of GVO/MX with capacitance retention 96.12% was observed at 60 mVs^?1. EIS measurements showed reduction in electrochemical impedance for GVO/MX as compared to GVO and VO. The corresponding impedance values of Rct and Resr for GVO/MX were calculated as 18 Ω and 1.8 Ω, respectively. The superior capacitive ability of GVO/MX can be ascribed to its unique morphology, short diffusion path and high surface area of fabricated composite. Considering it, the present work provides a feasible strategy to fabricate highly effective electrode materials for next generation energy storage devices.     

Synthesis of hierarchical carbon sphere@NiMoO4 composite materials for supercapacitor electrodes

In this work, hierarchical Carbon sphere@NiMoO₄ (C@NiMoO₄) composite was successfully synthesized by cost-effective two-step hydrothermal method. The samples were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction analysis and Thermogravimetric analysis. The Electrochemical measurement demonstrated that hierarchical C@NiMoO₄ electrode materials exhibited good specific capacitance (Csp) of 268.8 F g⁻¹ at a current density of 1 A g⁻¹ in 2 M NaOH aqueous electrolyte solution, as well as good cycling stability (88.4% retention after 2000 cycles). Compared to pure NiMoO₄, the excellent capacitive properties and stability suggest that the hierarchical structure C@NiMoO₄ could be promising electroactive material for supercapacitors.     

分级多孔炭的制备及其电化学性能研究

以间苯二酚和甲醛为前驱体,原位合成的Mg(OH)2为模板剂,KOH作为催化剂、沉淀剂、活化剂,一步法合成具有小/中/大孔的分级多孔炭。使用扫描电镜、透射电镜、氮气吸附、X射线衍射对样品的结构进行表征。通过恒流充放电、循环伏安、电化学阻抗谱,测试样品在1mol/L的(C2H5)4NBF4/碳酸丙烯酯(Propylene carbonatePC)电解液中的电化学性能。结果表明,随着KOH对间苯二酚用量的增加,材料的比表面积和孔容先增大后减小,其最大值分别为1300m2/g和0.89cm3/g。该材料具有良好的容量性能和功率性能,在电流密度0.1A/g时,最高质量比电容可以达到116F/g;当电流密度增大到5A/g时,电容保持率为78%。     

Pyrolyzing soft template-containing poly(ionic liquid) into hierarchical N-doped porous carbon for electroreduction of carbon dioxide

Heteroatom-doped carbon materials have demonstrated great potential in the electrochemical reduction reaction of CO₂ (CO₂RR) due to their versatile structure and function. However, rational structure control remains one challenge. In this work, we reported a unique carbon precursor of soft template-containing porous poly(ionic liquid) (PIL) that was directly synthesized via free-radical self-polymerization of ionic liquid monomer in a soft template route. Variation of the carbonization temperature in a direct pyrolysis process without any additive yielded a series of carbon materials with facile adjustable textural properties and N species. Significantly, the integration of soft-template in the PIL precursor led to the formation of hierarchical porous carbon material with a higher surface area and larger pore size than that from the template-free precursor. In CO₂RR to CO, the champion catalyst gave a Faraday efficiency of 83.0% and a current density of 1.79 mA·cm^-2 at -0.9 V vs. reversible hydrogen electrode (vs. RHE). The abundant graphite N species and hierarchical pore structure, especially the unique hierarchical small-/ultra-micropores were revealed to enable better CO₂RR performance.     

Promising carbon nanosheets decorated by self-assembled MoO2 nanoparticles: Controllable synthesis,boosting performance and application in symmetric coin cell supercapacitors

A composite containing self-assembled MoO₂ nanoparticles and functional carbon nanosheets was obtained via a facile and controllable strategy. Two-dimensional functional carbon nanosheets as matrices have close contact with MoO₂ nanoparticles, which assists in the improvement of electronic conductivity, provides efficient pathways and accelerates electron transfer. The carbon nanosheets have functional groups on the surface, which could serve as the nucleation sites for MoO₂. The MC-0.12 composite shows optimal specific capacitance (190.9 F g^-1 at 1 A g^-1) and excellent cycle stability between monomers and composites with different constituents. The assembled symmetrical coin cell supercapacitor using MC-0.12 possesses the maximum energy density of 10.3 Wh kg^-1 at a power density of 378 W kg^-1 and still maintains the energy density of 7.9 Wh kg^-1 at 1682 W kg^-1 with a larger potential window. The capacitance retention (92%) of the assembled device is maintained after 2000 cycles, showing outstanding cycle life. Therefore, the integration of self-assembled MoO₂ nanoparticles with 2D functional carbon nanosheets provides the composite superior electrochemical performance for supercapacitor applications.     

Preparation and electrochemical performance of polyaniline-based carbon nanotubes as electrode material for supercapacitor

Nitrogen-containing carbon nanotubes (CNTs) with open end and low specific surface area were prepared via the carbonization of polyaniline (PANI) nanotubes synthesized by a rapidly mixed reaction. On the basis of analyzing the morphologies and structures of the original and carbonized PANI nanotubes, the electrochemical properties of PANI-based CNTs obtained at different temperatures as electrode materials for supercapacitors using 30 wt.% aqueous solution of KOH as electrolyte were investigated by galvanostatic charge/discharge and cyclic voltammetry. It was found that the carbonized PANI nanotubes at 700 °C exhibit high specific capacitance of 163 F g⁻¹ at a current density of 0.1 A g⁻¹ and excellent rate capability in KOH solution. Using X-ray photoelectron spectroscopy measurement the nitrogen state and content in PANI-CNTs were analysed, which could play important roles for the enhancement of electrochemical performance. When the appropriate content of nitrogen is present, the presence of pyrrole or pyridone and quaternary nitrogen is beneficial for the improvement of electron mobility and the wettability of electrode.     

Stable superhydrophobic surface of hierarchical carbon nanotubes on Si micropillar arrays

It is of great importance to construct a stable superhydrophobic surface with low sliding angle (SA) for various applications. We used hydrophobic carbon nanotubes (CNTs) to construct the superhydrophobic hierarchical architecture of CNTs on silicon micropillar array (CNTs/Si-μp), which have a large contact angle of 153° to 155° and an ultralow SA of 3° to 5°. Small water droplets with a volume larger than 0.3 μL can slide on the CNTs/Si-μp with a tilted angle of approximately 5°. The CNTs growing on planar Si wafer lose their superhydrophobic properties after exposing to tiny water droplets. However, the CNTs/Si-μp still show superhydrophobic properties even after wetting using tiny water droplets. The CNTs/Si-μp still have a hierarchical structure after wetting, resulting in a stable superhydrophobic surface.     

Synthesis of hierarchical porous silicon oxycarbide ceramics from preceramic polymer and wood biomass composites

Hierarchical porous SiOC ceramics were successfully prepared using a polysiloxane preceramic polymer mixed with wood biomass by annealing at different temperatures under Ar atmosphere. These SiOC ceramics display a trimodal pore size distribution in the micro-, meso- (micropores + mesopores, 1.7–14 nm) and macro-size scale (1–15 μm). The mesopores and micropores mainly originate from the formation of large amounts of SiC crystals and nanowires, graphite-like microcrystallites, and nm-scale pores of ray parenchyma cells and pits of the wood biomass. The SiOC sample prepared at a higher temperature processes the specific surface area up to 180.5 m²/g. The specific surface area, pore volume and average pore width of the samples can be controlled by adjusting the pyrolysis temperature.     

纳米木质素基多孔炭的制备及其电化学性能

基于绿色低共熔溶剂（DES）高效分离麦草生物质组分以制备纳米木质素（LNP）,本文采用化学活化法并进一步热解炭化制备纳米木质素基多孔炭（LNPC）。借助SEM、Raman、BET-物理吸附等分析手段研究了锌系活化剂及热解炭化温度（600℃、700℃、800℃）对LNPC的结构特征及电化学性能的影响。研究结果表明,相对于LNP直接热解炭化后纳米碳粒子的极易团聚,经锌化物活化后所制备的LNPC表现出更好的分散性和多级孔道形貌结构。尤其,以ZnCO₃活化后制备的LNPC-ZnCO₃-800具有更突出的性能,较高石墨化程度（I_D/I_G为0.68）、较高BET比表面积（679m²/g）、高介孔率（86.7%）、均匀纳米碳粒子构成的介孔结构。此外,以LNPC-ZnCO₃-800制备的工作电极,在0.5A/g时的比电容可达179F/g,与直接热解炭化的LNPC-800（64F/g）相比,其比电容的容量提高了180%。     

Synthesis and dye separation performance of ferromagnetic hierarchical porous carbon

Ferromagnetic hierarchical porous carbon (FHPC) with nickel particles embedded in the hierarchical porous carbon skeleton was synthesized. The hierarchical macro–mesoporous skeleton was formed by dissolving a salt template of Na₂CO₃ and the ferromagnetic nickel particles were produced by in situ carbothermal reduction of nickel oxide. The saturation magnetization, remnant magnetization and coercive force of FHPC are 11.3 emu g⁻¹, 2.3 emu g⁻¹ and 55.7 Oe. The ferromagnetic property enables the magnetic separation of the FHPC from water. The surface chemical environments of the FHPC consist of different oxygen functional groups, like –OH, >COO and >CO groups, as well as a trace amount of aliphatic species of –CH₃ or -CH_2^- structures. Dye separation performance of the FHPC was investigated using methylene orange, and the adsorption capacity was 0.16 mg m⁻² with the adsorption kinetics constant of 2.2 m² mg⁻¹ min⁻¹, which is superior to that of magnetic carbon spheres.     

具有多级孔道结构的高比表面多孔炭活化策略及VOCs吸附性能

以废弃榛壳为前体,采用不同活化策略制备多孔炭,探究活化策略和活化温度对多孔炭挥发性有机化合物（VOCs）吸附性能的影响,以及多孔炭的结构、表面性质与VOCs吸附性能的构效关系。结果表明,H₃PO₄法制备的多孔炭介孔体积大,且炭结构缺陷较少,吸附位点较少; KOH法获得的微孔体积较大,孔径集中在0.5~0.7nm的微孔,不利于VOCs分子吸附位点的有效利用。H₃PO₄-KOH分步法在850℃下制备具有高比表面积,孔径集中在0.5~1nm的宽微介孔分布,且炭结构高度无序并含有丰富缺陷位的多孔炭,为VOCs吸附提供了充足的吸附位点并提高了吸附位点了利用率,相比于H₃PO₄与KOH活化法制备的多孔炭的VOCs饱和吸附量显著提升,特别是对于弱极性VOCs。另外,H₃PO₄-KOH分步法制备的多孔炭表面官能团含量较低,极性较低,对非极性VOCs的吸附量远大于极性VOCs。因此,H₃PO₄-KOH分步活化策略是制备具有高比表面积、高VOCs吸附性能多孔炭的最优策略与方案。