Preparation of biomass-derived phosphorus-doped microporous carbon material and its application in dye adsorption and CO2 capture

Microporous P-doped carbon materials are synthesized by a pyrolysis method using MCM-22 as a template, sucrose as a precursor, and phosphoric acid as phosphorus sources. The results show that the pore structure of the carbon materials can be adjusted by changing the amount of phosphoric acid and template. When the P/C molar ratio is 0.075, the obtained P-doped microporous carbon material shows excellent specific surface area up to 621 m²/g and shows a high adsorption capacity of 199.40 mg/g for crystal violet dye, with a removal rate of 98.9%. When testing the CO₂ adsorption capacity, it was found that the maximum adsorption capacity reached 63 mg/g and remained stable after 10 adsorption and desorption cycles, with excellent cycle stability. The adsorption obeys pseudo-second-order kinetic model, and the adsorption isotherm follows the Langmuir model.     

硬模板法合成磁性石墨化介孔碳及在中药废水吸附处理中的应用

以SBA-15为模板, 蔗糖为碳源, 硝酸铁辅助催化合成磁性石墨化介孔碳复合材料(Fe/GMC). 利用X射线粉末衍射(XRD)、透射电子显微镜(TEM)、N₂吸附-脱附(BET)、拉曼光谱等对反应产物进行了表征. 硝酸铁辅助催化可以在较低碳化温度(900℃)下实现介孔碳的部分石墨化, 并同步生成磁性Fe₃O₄颗粒, 合成的产物比表面积大、孔道有序、磁性强. 运用紫外-可见(UV-Vis)光谱考察了该复合材料对中药红花色素废水的吸附特性,复合材料的吸附速率快、吸附量高, 具有良好的脱色效果并能实现吸附剂的快速固液磁分离.     

Simple fabrication of a phosphorus-doped hierarchical porous carbon via soft-template method for efficient CO2capture

Hierarchical porous carbons are widely used as adsorbents, catalyst supports, electrode materials, and other applications because of their high specific surface area (SSA), varied pore structure, adjustable porosity, and excellent physicochemical stability. Introducing heteroatoms such as N, P, or S, with electronegativities different from that of carbon, into the carbon skeleton can change the chemical properties of the surface and the density of the electron cloud around the carbon matrix, thus altering interactions of CO₂molecules with the surface and improving CO₂adsorption capacity. Therefore, doping heteroatoms in carbon materials has attracted a great amount of attention. In this paper, the template method was used with F108 (polyethylene glycol–polypropylene glycolpolyethylene glycol) as the template, resorcinol and formaldehyde solutions as the carbon sources, phosphoric acid as the phosphorus source, and KOH as the activator to prepare phosphorus-doped hierarchical porous carbons. Through a series of characterization and CO₂adsorption experiments, the influence of the amount of KOH and template agent on the pore structure of carbon materials was studied. We conclude that these phosphorus-doped hierarchical porous carbon materials are promising CO₂adsorbents.     

Hierarchical porous carbon with designed pore architecture and study of its adsorptive properties

Ordered mesoporous carbon nanoparticles have been synthesized by a nanocasting procedure from furfuryl alcohol impregnation into alumino–silica UVM-7 material. By a proper adjustment of the synthesis parameters, furfuryl alcohol volume vs. template pore volume, it was possible to obtain a carbonaceous templated material which keeps the hierarchical bimodal porosity of the silica together with its high surface area (>1000 m²/g), as it was confirmed by means of electron transmission microscopy and N₂ adsorption isotherms. This carbon material was evaluated by testing it as a sorbent for several pesticides in aqueous solutions. Its absorption efficiency was compared with typical commercial solid phase extraction materials such as silica C₁₈ and graphitized carbon black GCB.     

Nitrogen-Doped Porous Carbon Materials Derived from Graphene Oxide/Melamine Resin Composites for CO2 Adsorption

CO₂ adsorption in porous carbon materials has attracted great interests for alleviating emission of post-combustion CO₂. In this work, a novel nitrogen-doped porous carbon material was fabricated by carbonizing the precursor of melamine-resorcinol-formaldehyde resin/graphene oxide (MR/GO) composites with KOH as the activation agent. Detailed characterization results revealed that the fabricated MR(0.25)/GO-500 porous carbon (0.25 represented the amount of GO added in wt.% and 500 denoted activation temperature in °C) had well-defined pore size distribution, high specific surface area (1264 m²·g⁻¹) and high nitrogen content (6.92 wt.%), which was mainly composed of the pyridinic-N and pyrrolic-N species. Batch adsorption experiments demonstrated that the fabricated MR(0.25)/GO-500 porous carbon delivered excellent CO₂ adsorption ability of 5.21 mmol·g⁻¹ at 298.15 K and 500 kPa, and such porous carbon also exhibited fast adsorption kinetics, high selectivity of CO₂/N₂ and good recyclability. With the inherent microstructure features of high surface area and abundant N adsorption sites species, the MR/GO-derived porous carbon materials offer a potentially promising adsorbent for practical CO₂ capture.     

Synthesis of High‐Surface‐Area Nitrogen‐Doped Porous Carbon Microflowers and Their Efficient Carbon Dioxide Capture Performance

Sustainable carbon materials have received particular attention in CO₂ capture and storage owing to their abundant pore structures and controllable pore parameters. Here, we report high‐surface‐area hierarchically porous N‐doped carbon microflowers, which were assembled from porous nanosheets by a three‐step route: soft‐template‐assisted self‐assembly, thermal decomposition, and KOH activation. The hydrazine hydrate used in our experiment serves as not only a nitrogen source, but also a structure‐directing agent. The activation process was carried out under low (KOH/carbon=2), mild (KOH/carbon=4) and severe (KOH/carbon=6) activation conditions. The mild activated N‐doped carbon microflowers (A‐NCF‐4) have a hierarchically porous structure, high specific surface area (2309 m² g^?1), desirable micropore size below 1 nm, and importantly large micropore volume (0.95 cm³ g^?1). The remarkably high CO₂ adsorption capacities of 6.52 and 19.32 mmol g^?1 were achieved with this sample at 0 °C (273 K) and two pressures, 1 bar and 20 bar, respectively. Furthermore, this sample also exhibits excellent stability during cyclic operations and good separation selectivity for CO₂ over N₂.     

Three‐Dimensional Ultralarge‐Pore Ia3d Mesoporous Silica with Various Pore Diameters and Their Application in Biomolecule Immobilization

Highly ordered mesoporous three‐dimensional Ia3d silica (KIT‐6) with different pore diameters has been synthesized by using pluronic P123 as surfactant template and n‐butanol as cosolvent at different synthesis temperatures in a highly acidic medium. The materials were characterized by XRD and N₂ adsorption. The synthesis temperature plays a significant role in controlling the pore diameter, surface area, and pore volume of the materials. The material prepared at 150 °C, KIT‐6‐150, has a large pore diameter (11.3 nm) and a high specific pore volume (1.53 cm³ g^?1). We also demonstrate immobilization of lysozyme, which is a stable and hard protein, on KIT‐6 materials with different pore diameters. The amount of lysozyme adsorbed on large‐pore KIT‐6 is extremely large (57.2 μmol g^?1) and is much higher than that observed for mesoporous silicas MCM‐41, SBA‐15, and KIT‐5, mesoporous carbons, and carbon nanocages. The effect of various parameters such as buffer concentration, adsorption temperature, concentration of the lysozyme, and the textural parameter of the adsorbent on the lysozyme adsorption capacity of KIT‐6 was studied. The amount adsorbed mainly depends on solution pH, ionic strength, adsorption temperature, and pore volume and pore diameter of the adsorbent. The mechanism of adsorption on KIT‐6 under different adsorption conditions is discussed. In addition, the structural stability of lysozyme molecules and the KIT‐6 adsorbent before and after adsorption were investigated by XRD, nitrogen adsorption, and FTIR spectroscopy.     

Highly Dispersible Hexagonal Carbon–MoS2–Carbon Nanoplates with Hollow Sandwich Structures for Supercapacitors

MoS₂, a typical layered transition-metal dichalcogenide, is promising as an electrode material in supercapacitors. However, its low electrical conductivity could lead to limited capacitance if applied in electrochemical devices. Herein, a new nanostructure composed of hollow carbon–MoS₂–carbon was successfully synthesized through an l -cysteine-assisted hydrothermal method by using gibbsite as a template and polydopamine as a carbon precursor. After calcination and etching of the gibbsite template, uniform hollow platelets, which were made of a sandwich-like assembly of partial graphitic carbon and two-dimensional layered MoS₂ flakes, were obtained. The platelets showed excellent dispersibility and stability in water, and good electrical conductivity due to carbon provided by the calcination of polydopamine coatings. The hollow nanoplate morphology of the material provided a high specific surface area of 543 m² g⁻¹, a total pore volume of 0.677 cm³ g⁻¹, and fairly small mesopores (≈5.3 nm). The material was applied in a symmetric supercapacitor and exhibited a specific capacitance of 248 F g⁻¹ (0.12 F cm⁻²) at a constant current density of 0.1 A g⁻¹; thus suggesting that hollow carbon–MoS₂–carbon nanoplates are promising candidate materials for supercapacitors.     

Facile synthesis of Fe3O4@C hollow nanospheres and their application in polluted water treatment

Nanostructured carbon-based materials, such as carbon nanotube arrays have shown respectable removal ability for heavy metal ions and organic dyes in aqueous solution. Although the carbon-based materials exhibited excellent removal ability, the separation of them from the aqueous solution is difficult and time-consuming. Here we demonstrated a novel and facile route for the large-scale fabrication of Fe₃O₄@C hollow nanospheres, with using ferrocene as a single reagent and SiO₂ as a template. The as-prepared Fe₃O₄@C hollow nanospheres exhibited adsorption ability for heavy metal ions and organic dyes from aqueous solution, and can be easily separated by an external magnet. When the as-prepared Fe₃O₄@C hollow nanospheres were mixed with the aqueous solution of Hg²⁺ within 15 min, the removal efficiency was 90.3%. The as-prepared Fe₃O₄@C hollow nanospheres were also exhibited a high adsorption capacity (100%) as the adsorbent for methylene blue (MB). In addition, the as-prepared Fe₃O₄@C hollow nanospheres can be used as the recyclable sorbent for water treatment via a simple magnetic separation.     

Solid Amine Adsorbent Prepared by Molecular Imprinting and Its Carbon Dioxide Adsorption Properties

A carbon dioxide imprinted solid amine adsorbent (IPEIA‐R) with polyethylenimine (PEI) as a skeleton was conveniently prepared by using glutaraldehyde to cross‐link carbon dioxide‐preadsorbed PEI. As confirmed by FTIR, FT‐Raman, and ¹³C NMR spectroscopy, CO₂ preadsorbed on PEI could occupy the reactive sites of amino groups and act as a template for imprinting in the cross‐linking process. The imino groups formed from the cross‐linking reaction between glutaraldehyde and PEI could be reduced by NaBH₄ to form CO₂‐adsorbable amino groups. The adsorption results indicated that CO₂ imprinting and reduction of imino groups by NaBH₄ endowed the adsorbent with a higher CO₂ adsorption capacity. Compared with PEI‐supported mesoporous adsorbents, the solid amine adsorbent with PEI as a skeleton can avoid serious pore blockage and CO₂ diffusion resistance, even with a high amine content. The solid amine adsorbent with PEI as a skeleton showed a remarkable CO₂ adsorption capacity (8.56 mmol g^?1) in the presence of water at 25 °C, owing to the high amine content and good swelling properties. It also showed promising regeneration performance and could maintain almost the same CO₂ adsorption capacity after 15 adsorption–desorption cycles.     

球形V-MCM-48的简单合成方法

活性金属掺杂的具有三维立方孔道结构的MCM-48在芳烃的氧化反应具有潜在应用价值。使用乙醇做助溶剂,在低的模板剂浓度下,经过一步水热法首次合成了球形的V-MCM-48。通过XRD,场发射扫描电镜,氮气吸附-脱附,红外,拉曼,核磁,X射线光电子能谱和ICP等技术对样品进行了表征。结果表明这些样品具有大的比表面积(1 005 m2.g),有序的孔道结构。当V/Si的物质的量比高达2.91%时,仍没有出现V2O5晶体。大部分的钒进入了硅的骨架。所合成材料在低温过氧化氢直接氧化苯乙烯的反应中表现出良好的催化性能。     

No More HF: Teflon‐Assisted Ultrafast Removal of Silica to Generate High‐Surface‐Area Mesostructured Carbon for Enhanced CO2 Capture and Supercapacitor Performance

An innovative technique to obtain high‐surface‐area mesostructured carbon (2545 m² g^?1) with significant microporosity uses Teflon as the silica template removal agent. This method not only shortens synthesis time by combining silica removal and carbonization in a single step, but also assists in ultrafast removal of the template (in 10 min) with complete elimination of toxic HF usage. The obtained carbon material (JNC‐1) displays excellent CO₂ capture ability (ca. 26.2 wt % at 0 °C under 0.88 bar CO₂ pressure), which is twice that of CMK‐3 obtained by the HF etching method (13.0 wt %). JNC‐1 demonstrated higher H₂ adsorption capacity (2.8 wt %) compared to CMK‐3 (1.2 wt %) at ?196 °C under 1.0 bar H₂ pressure. The bimodal pore architecture of JNC‐1 led to superior supercapacitor performance, with a specific capacitance of 292 F g^?1 and 182 F g^?1 at a drain rate of 1 A g^?1 and 50 A g^?1, respectively, in 1 m H₂SO₄ compared to CMK‐3 and activated carbon.     

Morphology and Texture of Silica Prepared by Sol–Gel Synthesis on the Surface of Fibrous Carbon Materials

Silica materials are synthesized by the sol–gel method including the deposition of tetraethoxysilane on various micro- and nanocarbon fibers. The use of nanofibrous carbon as a template makes it possible to prepare thermally stable mesoporous SiO₂ samples with unusually high surface areas (up to 1255 m²/g) and high porosity (up to 5.6 cm³/g). These silica materials and aerogels prepared by supercritical drying have comparable pore volumes. It is found by high-resolution electron microscopy that a thin-wall matrix permeated by channels is a prevailing structure of silica materials. When some catalytic fibrous carbons are used as templates, silica nanotubes can be prepared.     

An In Situ Carbonization–Replication Method to Synthesize Mesostructured WO3/C Composite as Nonprecious‐Metal Anode Catalyst in PEMFC

A meostructured WO₃/C composite with crystalline framework and high electric conductivity has been synthesized by a new in situ carbonization–replication route using the block copolymer (poly(ethylene glycol)‐block‐poly(propylene glycol)‐block‐poly(ethylene glycol)) present in situ in the pore channels of mesoporous silica template as carbon source. X‐ray diffraction, X‐ray photoelectron spectroscopy, transmission electron microscopy, thermogravimetry differential thermal analysis, and N₂ adsorption techniques were adopted for the structural characterization. Cyclic voltammetry, chronoamperometry, and single‐cell test for hydrogen electrochemical oxidation were adopted to characterize the electrochemical activities of the mesoporous WO₃/C composite. The carbon content and consequent electric conductivity of these high‐surface‐area (108–130 m² g^?1) mesostructured WO₃/C composite materials can be tuned by variation of the duration of heat treatment, and the composites exhibited high and stable electrochemical catalytic activity. The single‐cell test results indicated that the mesostructured WO₃/C composites showed clear electrochemical catalytic activity toward hydrogen oxidation at 25 °C, which makes them potential non‐precious‐metal anode catalysts in proton exchange membrane fuel cell.     

A facile soft-template synthesis of nitrogen doped mesoporous carbons for hydrogen sulfide removal

A series of nitrogen-doped mesoporous carbons (NMCs) were prepared using Pluronic F127 as a structure directing agent, phloroglucinol and formaldehyde as carbon precursor and dicyandiamide as nitrogen source. The obtained nitrogen-doped mesoporous carbons possess high nitrogen content of 6.37–19.28 wt%. Due to the feature of high nitrogen contents, NMCs show superior H₂S adsorption performance with breakthrough sulfur capacity of 0.48 mmol g^?1 at room temperature and ambient pressure. It is revealed that in addition to the nitrogen content, nitrogen configuration and porosity of the carbon materials also influence significantly their sulfur capacity. This work offers a facile strategy for the synthesis of porous carbon materials with excellent performance in the adsorptive removal of H₂S.     

Nitrogen‐doped mesoporous carbon materials for oxidative dehydrogenation of propane

The CN‐15‐x series materials with different doses of SBA‐15 template and the CN‐y‐2.0 series materials with different hard templates were prepared by the hard template method with hexamethylenetetramine as the carbon and nitrogen source. The obtained mesoporous carbon materials were characterized by X‐ray diffraction (XRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), Raman spectroscopy, and X‐ray photoelectron spectroscopy (XPS). The catalytic performance of propane oxidative dehydrogenation was determined. The characterization results indicate that the catalytic activity of CN‐15‐2.0 with a bipartite hexagonal ordered structure was higher than those of the other materials. The conversion of propane was 22.98%, and the selectivity toward propylene was 41.70%.     

Single‐Step Synthesis of Mesoporous Carbon Nitride/Molybdenum Sulfide Nanohybrids for High‐Performance Sodium‐Ion Batteries

Molybdenum disulfide (MoS₂) is a promising candidate as a high‐performing anode material for sodium‐ion batteries (SIBs) due to its large interlayer spacing. However, it suffers from continued capacity fading. This problem could be overcome by hybridizing MoS₂ with nanostructured carbon‐based materials, but it is quite challenging. Herein, we demonstrate a single‐step strategy for the preparation of MoS₂ coupled with ordered mesoporous carbon nitride using a nanotemplating approach which involves the pyrolysis of phosphomolybdic acid hydrate (PMA), dithiooxamide (DTO) and 5‐amino‐1H‐tetrazole (5‐ATTZ) together in the porous channels of 3D mesoporous silica template. The sulfidation to MoS₂, polymerization to carbon nitride (CN) and their hybridization occur simultaneously within a mesoporous silica template during a calcination process. The CN/MoS₂ hybrid prepared by this unique approach is highly pure and exhibits good crystallinity as well as delivers excellent performance for SIBs with specific capacities of 605 and 431 mAhg^?1 at current densities of 100 and 1000 mAg^?1, respectively, for SIBs.     

Building Hierarchical Microcubes Composed of One-Dimensional CoSe2@Nitrogen-Doped Carbon for Superior Sodium Ion Batteries

Designing and synthesizing highly stable anode materials with high capacity is critical for the practical application of sodium ion batteries (SIBs), however, to date, this remains an insurmountable barrier. The introduction of hierarchical architectures and carbon supports is proving an effective strategy for addressing these challenges. Thus, we have fabricated a hierarchical CoSe₂@nitrogen-doped carbon (CoSe₂@NC) microcube composite using the Prussian blue analogue Co₃[Co(CN)₆]₂ as template. The rational combination of the unique hierarchical construction from one to three dimensions and a nitrogen-doped carbon skeleton facilitates sodium ion and electron transport as well as stabilizing the host structure during repeated discharge/charge processes, which contributes to its excellent sodium storage capability. As expected, the as-prepared CoSe₂@NC composite delivered remarkable reversible capacity and ultralong cycling lifespan even at a high rate of 2.0 A g⁻¹ (384.3 mA h g⁻¹ after1800 loops) when serving as the anode material for SIBs. This work shows the great potential of the CoSe₂-based anode for practical application in SIBs, and the original strategy may be extended to other anode materials.     

Improving Na+ transport kinetics and Na+ storage of hierarchical rhenium-nickel sulfide (ReS2@NiS2) hollow architecture by assembling layered 2D-3D heterostructures

Mixed metal sulfides have been widely used as anode material of sodium-ion batteries (SIBs) because of their excellent conductivity and sodium ion storage performance. Herein, ReS₂@NiS₂ heterostructures have been triumphantly designed and prepared through anchoring ReS₂ nanosheet arrays on the surface of NiS₂ hollow nanosphere. Specifically, the carbon nanospheres was used as hard template to synthesize NiS₂ hollow spheres as the substrate and then the ultrathin two-dimensional ReS₂ nanosheet arrays were uniformly grown on the surface of NiS₂. The internal hollow property provides sufficient space to relieve the volume expansion, and the outer two-dimensional nanosheet realizes the rapid electron transport and insertion/extraction of Na⁺. Owing to the great improvement of the transport kinetics of Na⁺, NiS₂@ReS₂ heterostructure electrode can achieve a high specific capacity of 400 mAh/g at the high current density of 1 A/g and still maintain a stable cycle stability even after 220 cycles. This hard template method not only paves a new way for the design and construct binary metal sulfide heterostructure electrode materials with outstanding electrochemical performance for Na⁺ batteries but also open up the potential applications of anode materials of SIBs.     

Highly Crystalline Mesoporous C60 with Ordered Pores: A Class of Nanomaterials for Energy Applications

Highly ordered mesoporous C₆₀ with a well‐ordered porous structure and a high crystallinity is prepared through the nanohard templating method using a saturated solution of C₆₀ in 1‐chloronaphthalene (51 mg mL^?1) as a C₆₀ precursor and SBA‐15 as a hard template. The high solubility of C₆₀ in 1‐chloronaphthalene helps not only to encapsulate a huge amount of the C₆₀ into the mesopores of the template but also supports the oligomerization of C₆₀ and the formation of crystalline walls made of C₆₀. The obtained mesoporous C₆₀ exhibits a rod‐shaped morphology, a high specific surface area (680 m² g^?1), tuneable pores, and a highly crystalline wall structure. This exciting ordered mesoporous C₆₀ offers high supercapacitive performance and a high selectivity to H₂O₂ production and methanol tolerance for ORR. This simple strategy could be adopted to make a series of mesoporous fullerenes with different structures and carbon atoms as a new class of energy materials.