Preparation and characterization of ruthenium/carbon aerogel nanocomposites via a supercritical fluid route

Carbon-aerogel-supported ruthenium nanoparticles were synthesized by impregnating carbon aerogels with Ru(acac)3 or Ru(cod)(tmhd)2 from supercritical carbon dioxide (scCO2) solutions, followed by thermal reduction of these precursors. Two different carbon aerogels with pore diameters of 4 and 21 nm were synthesized. The kinetics and the thermodynamics of impregnation of carbon aerogels with the ruthenium coordination complexes were studied. The approach-to-equilibrium data indicated very fast adsorption, and the adsorption isotherms were found to follow the Langmuir model. The impregnated carbon aerogel complexes were reduced thermally at different temperatures between 300 and 1000 degrees C in the presence of nitrogen. The resulting nanocomposites were characterized using transmission electron microscopy (TEM) and hydrogen chemisorption. TEM micrographs showed that the ruthenium nanoparticles were dispersed homogeneously throughout the porous carbon aerogel matrix, and the average sizes obtained under different conditions ranged from 1.7 to 3.8 nm. Once complete decomposition of the precursor had been achieved, the mean size of the ruthenium particles increased with increasing reduction temperature.     

Highly crystalline and conductive nitrogen-doped mesoporous carbon with graphitic walls and its electrochemical performance

We present a rational and simple methodology to fabricate highly conductive nitrogen-doped ordered mesoporous carbon with a graphitic wall structure by the simple adjustment of the carbonization temperature of mesoporous carbon nitride without the addition of any external nitrogen sources. By simply controlling the heat-treatment temperature, the structural order and intrinsic properties such as surface area, conductivity, and pore volume, and the nitrogen content of ordered graphitic mesoporous carbon can be controlled. Among the materials studied, the sample heat-treated at 1000 °C shows the highest conductivity, which is 32 times higher than that for the samples treated at 800 °C and retains the well-ordered mesoporous structure of the parent mesoporous carbon nitride and a reasonable amount of nitrogen in the graphitic framework. Since these materials exhibit high conductivity with the nitrogen atoms in the graphitic framework, we further demonstrate their use as a support for nanoparticle fabrication without the addition of any external stabilizing or size-controlling agent, as well as the anode electrode catalysts. Highly dispersed platinum nanoparticles with a size similar to that of the pore diameter of the support can be fabricated since the nitrogen atoms and the well-ordered porous structure in the mesoporous graphitic carbon framework act as a stabilizing and size-controlling agent, respectively. Furthermore the Pt-loaded, nitrogen-doped mesoporous graphitic carbon sample with a high conductivity shows much higher anodic electrocatalytic activity than the other materials used in the study.     

Conductive and mesoporous single-wall carbon nanohorn/organic aerogel composites

Conductive and mesoporous single-wall carbon nanohorn/resorcinol-formaldehyde aerogel composites were fabricated by embedding organic resorcinol-formaldehyde aerogels with single-wall carbon nanohorns. Samples were characterized with transmission electron microscopy, field emission scanning electron microscopy, nitrogen adsorption at 77 K, and direct-current volume electrical conductivity measurement. It was demonstrated that these composites have important properties, such as controllable nanoporosity and high electrical conductivity in the range of 10-4 S m-1, which enables many potential applications.     

Preparation and characterization of bilayer carbon/polymer membranes

The objective of the present research work was to develop a membrane with a high H₂O/alcohol selectivity for pervaporation and for use in direct alcohol fuel cells. Sulfonated poly (ether ether ketone) (SPEEK) was coated with a thin continuous carbon molecular sieve (CMS) layer. The membranes obtained had 180- and 400-nm thick CMS layers that led to a clear reduction of alcohol crossover. The water/alcohol selectivity increased with the size of the alcohol molecules as follows: methanol < ethanol < n-propanol < iso-propanol. A water/n-propanol selectivity of up to 34,000 was obtained, confirming the molecular sieving effect. The system was tested in a direct methanol fuel cell using standard electrodes, and demonstrated a better performance than with plain membranes. In a later stage Pt was introduced in the CMS layer during the preparation of the membrane electrode assemblies, this had the advantage that the CMS layer not only acted as an alcohol barrier but also as a catalyst support.     

Preparation and characterization of nitrogen-doped titanium dioxides

A type of high visible-light active titanium oxinitride(TiO2-xNx) powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric furnace at high temperatures. The hydrated titanium dioxide was synthesized as the precursor of TiO2-xNx using titanic acid as raw material,which came from sulfate technique of produc-ing titanium white. The effects of temperature and reaction time on the nitrogen content,grain size and crystal structure were studied. The visible-light activity and photocatalysis capability of the powder were also investigated.     

Preparation of a kind of mesoporous carbon and its performance in adsorptive desulfurization

Carbon materials were prepared using mesoporous silica HMS with different pore sizes as the hard templates and water-soluble phenolic resin as the carbon source. The obtained materials were characterized by powder X-ray diffraction, transmission electron microscopy and N₂ physical adsorption, and were used in adsorptive desulfurization. It has been shown that the carbon material prepared using HMS with larger pore size (>3 nm) presented uniform wormlike mesopore of 2.3 nm and large BET surface area (1903 m²/g). The mesoporous carbon was an excellent adsorbent to remove the refractory sulfur compound in diesel, especially dibenzothiophene and 4, 6-dimethyldibenzothiophene.     

Comparative study on pore structures of mesoporous ZSM-5 from resorcinol-formaldehyde aerogel and carbon aerogel templating

Resorcinol-formaldehyde aerogels and carbon aerogels of different mesoporosities have been used as templates for preparing bimodal zeolites of mesopores. Samples were thoroughly characterized with X-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, N(2) adsorption at 77 K, as well as FT-IR spectroscopy and (29)Si nuclear magnetic resonance spectroscopy. The mesoporous ZSM-5 zeolites have additional mesopores of 9-25 nm in widths and 0.07-0.2 cm(3)/g in volumes, besides their perfect inherent micropores. Experimental results show the mesoporous systems of the finally obtained zeolites can be influenced by proper preparation of resorcinol-formaldehyde aerogels and carbon aerogels through solution chemistry. Consequently, zeolites of tunable mesoporosities can be prepared with this unique methodology.     

热解条件对氮杂有序介孔炭材料电催化性能的影响

氧还原反应是燃料电池及金属空气电池中极其重要的电化学反应之一,贵金属铂基催化剂被认为是最有效的氧还原反应电催化剂.然而,贵金属铂的资源稀缺以及高成本问题阻碍了相关技术的大规模应用,探索发展廉价高效的贵金属替代型催化剂是推动燃料电池发展的根本解决方案.近年来,人们在非贵金属催化剂开发方面取得了显著进展,其中新型纳米结构掺杂炭材料研究尤为活跃.氮杂有序介孔炭材料由于其高比表面积和独特的孔结构,在燃料电池技术上具有广泛的应用前景.在氮杂有序介孔炭材料的制备过程中,热解条件对炭材料组成、结构及电催化性能有着重要影响.然而,目前尚未见对氮杂炭材料制备过程中热解条件的影响进行系统研究.
　　本文采用我们发展的蒸汽化-毛细管冷凝法,以SBA-15为硬模板浸渍前驱体吡咯,制备出具有高比表面积和独特孔结构的氮杂有序介孔炭材料,系统研究了热解条件(包括热解温度、热解时间和升温速率)对炭材料组成、结构及电催化性能的影响,采用N2吸附-脱附等温线、X射线光电子能谱(XPS)及Raman光谱等方法考察了氮杂有序介孔炭材料的结构和组成,采用循环伏安法与旋转环盘电极研究了其电化学行为与氧还原反应电催化活性及选择性.
　　N2吸附-脱附等温线显示,氮杂炭材料对应IV型吸附-脱附等温线,孔径主要分布在2–10 nm,表明所制材料具有介孔结构.随着热处理温度升高,氮杂有序介孔炭材料比表面积先增加而后降低,热处理时间的延长有利于比表面积增大,但升温速率对所制炭材料比表面积没有明显影响,当升温速率为30 oC/min,900 oC焙烧3 h时,氮杂有序介孔炭材料的比表面积达到最大值888 m2/g. XPS测试结果表明,随着热处理温度升高,氮杂有序介孔炭材料中含氮基团的分解进一步加深,使N含量逐渐降低.延长热处理时间亦然,而升温速率的改变对N含量无明显影响.在热处理温度较低时(600 oC),所得材料中N主要以吡咯氮和吡啶氮的形式存在;当温度达到800 oC以上,吡咯氮转化为吡啶氮和骨架氮,且主要以骨架氮形式存在,说明氮杂有序介孔炭材料的石墨化程度逐渐升高. Raman光谱结果显示,随着热处理温度升高, ID/IG逐渐降低,进一步印证了温度对石墨化程度的影响.
　　电化学测试结果表明,随着热处理温度升高,氮杂有序介孔炭材料的氧还原反应电催化活性逐渐升高,但是当热处理温度从900 oC升至1000 oC时,氧还原反应活性增加很小;升温速率与热处理时间对氧还原反应电催化活性的影响均不明显.与商品Pt/C催化剂相比,900 oC以上所制催化剂均表现出更优异的氧还原电催化活性与选择性.由此可见,热处理温度是决定碳源热化学行为的关键因素,进而决定炭材料表面组成与结构.电化学研究结果表明,800 oC以上进行热处理碳化,所生成石墨化微晶可有效促进电子传递,降低欧姆极化损失,同时,较高的处理温度可促进骨架氮掺杂,从而构建出高效氧还原反应活性位点.因此,氮杂型炭催化剂的组成、结构与电化学性能更多地受控于热处理过程中的热力学,而非热解动力学过程.     

Electrocatalytic hydrogen peroxide formation on mesoporous non-metal nitrogen-doped carbon catalyst

Direct electrochemical formation of hydrogen peroxide(H2O2) from pure O2 and H2on cheap metal-free earth abundant catalysts has emerged as the highest atom-efficient and environmentally friendly reaction pathway and is therefore of great interest from an academic and industrial point of view. Very recently,novel metal-free mesoporous nitrogen-doped carbon catalysts have attracted large attention due to the unique reactivity and selectivity for the electrochemical hydrogen peroxide formation [1–3]. In this work,we provide deeper insights into the electrocatalytic activity, selectivity and durability of novel metal-free mesoporous nitrogen-doped carbon catalyst for the peroxide formation with a particular emphasis on the influence of experimental reaction parameters such as p H value and electrode potential for three different electrolytes. We used two independent approaches for the investigation of electrochemical hydrogen peroxide formation, namely rotating ring-disk electrode(RRDE) technique and photometric UV–VIS technique. Our electrochemical and photometric results clearly revealed a considerable peroxide formation activity as well as high catalyst durability for the metal-free nitrogen-doped carbon catalyst material in both acidic as well as neutral medium at the same electrode potential under ambient temperature and pressure. In addition, the obtained electrochemical reactivity and selectivity indicate that the mechanisms for the electrochemical formation and decomposition of peroxide are strongly dependent on the p H value and electrode potential.     

Self-supported bimodal-pore structured nitrogen-doped carbon fiber aerogel as electrocatalyst for oxygen reduction reaction

Self-supported 3-dimensional (3D) nitrogen-doped bimodal-pore structured carbon fiber aerogel is synthesized via a facile carbonization process using prawn shells as the raw material. The fabricated N-doped carbon fiber aerogel possesses micro- and meso-porous pores with an N doping level of 5.9% and a high surface area of 526 m² g^− 1. As an electrocatalyst, the resultant N-doped carbon fiber aerogel exhibits superior electrocatalytic activity towards oxygen reduction reaction (ORR) with a more positive ORR onset-potential, better stability and high resistance to crossover effect compared to the commercial Pt/C electrocatalyst.     

Different non-radical oxidation processes of persulfate and peroxymonosulfate activation by nitrogen-doped mesoporous carbon

Activated persulfate oxidation is an emerging advanced oxidation process for organic pollutant degradation. Own to different molecular structures and oxidation potentials, persulfate (PDS) and peroxymonosulfate (PMS) may show different degradation performances due to various catalytic mechanisms even by the same catalysts. In this study, the nitrogen-doped mesoporous carbon (N-OMC) was applied to activate PDS and PMS for degrading a model organic pollutant phenol to reveal their activation mechanisms. Results show that both PDS and PMS could be efficiently activated by N-OMC. The degradation of phenol fitted well with pseudo-first-order kinetics, whose kinetic constants increased with the increase of pH, PDS/PMS dosage, and N-OMC dosage. Based on quenching experiments and electron spin resonance spin-trapping technique, the N-OMC was found to activate PDS and PMS via non-radical process of electron transfer and singlet oxygen formation, respectively, instead of the commonly observed radical process. This work will be useful to understand the activation processes of PDS and PMS, and benefit for the development of catalysts for pollutant degradation.     

Synthesis and characterization of monolithic carbon aerogel nanocomposites containing double-walled carbon nanotubes

We report the synthesis and characterization for the first examples of monolithic low-density carbon aerogel (CA) nanocomposites containing double-walled carbon nanotubes. The CA nancomposites were prepared by the sol-gel polymerization of resorcinol and formaldehyde in an aqueous surfactant-stabilized suspension of double-walled carbon nanotubes (DWNTs). The composite hydrogels were then dried with supercritical CO 2 and subsequently carbonized under an inert atmosphere to yield monolithic CA structures containing uniform dispersions of DWNTs. The microstructures and electrical conductivities of these CA nanocomposites were evaluated for different DWNT loadings. These materials exhibited high BET surface areas (>500 m (2)/g) and enhanced electrical conductivities relative to pristine CAs. The details of these results are discussed in comparison with theory and literature.     

Preparation and characterization of novel mesoporous ceria-titania

Synthesis of a novel thermally stable mesoporous ceria-titania phase using a neutral templating route is reported. The as-made inorganic-template hybrid mesostructured matrix showed a broad low-angle XRD peak characteristic of mesoporous materials. Careful thermal treatment of the matrix allowed the subsequent densification (of the pore walls) of the inorganic component and removal of the organic component so that a high-quality mesoporous ceria-titania was formed as observed by TEM analysis. The calcined material showed the formation of fluorite type structure of CeO(2) but no crystalline titania phase was observed. The mesoporous structure remained even after high-temperature treatment. The material had high surface area after calcination up to the temperature of 973 K, with well-dispersed ceria and titania components and negligible bulk oxide formation (from XRD, UV-vis, and XPS analysis). These novel mesoporous ceria-titania materials showed high performance for the removal of volatile organic compound (toluene). The toluene removal performance was further enhanced for Pt impregnated mesoporous ceria-titania.     

多壁碳纳米管表面L-组氨酸手性印迹聚合材料的制备及性能表征

通过酰胺化反应在多壁碳纳米管（MWNTs）表面接枝双键,以L-组氨酸（L-His）为模板,甲基丙烯酸（MAA）为功能单体,乙二醇二甲基丙烯酸酯（EGDMA）为交联剂,偶氮二异丁腈（AIBN）为引发剂,利用表面印迹技术,在MWNTs表面制备印迹聚合物（MWNTs-MIPs）．采用红外光谱,扫描电子显微镜和热重分析表征印迹聚合物的性质,结果表明MWNTs表面成功接枝了一层稳定的、厚度为35～40nm具有识别能力的印迹聚合材料．结合高效液相色谱技术,通过填充色谱柱在线色谱分析,探讨不同pH值的流动相下该印迹材料对L-His的分离行为,结果表明MWNTs—MIPs色谱柱在流动相pH=7．0时分离效果最好,能够选择性地识别L-His和D-His,分离度R为1．78,选择因子α为1．28．     

Preparation of polyaniline‐coated mesoporous carbon and its enhanced electrochemical properties

Polyaniline/MC (mesoporous carbon) composite was synthesized by in situ chemical polymerization method and was used as a new electrode material for supercapacitor. The composite was characterized by N₂ adsorption and scanning electron microscope. The electrochemical capacitance performance of the composite was investigated by cyclic voltammetry (CV) and galvanostatic charge–discharge tests with a three‐electrode system in a 10 wt% H₂SO₄ solution. The polyaniline/MC composite electrode shows much higher specific capacitance than pure MC electrode, which is attributed to the incorporation of polyaniline onto the pore surface of MC. Copyright © 2009 John Wiley & Sons, Ltd.     

有序介孔石墨相氮化碳的合成及催化Knoevenagel缩合研究

以二氰二胺为前驱体,不同晶化温度的SBA-15为硬模板,用纳米浇铸法合成了一系列比表面和孔体积可调的介孔石墨相氮化碳(CND-SBA15)。通过N2吸-脱附、TEM、小角XRD、XPS、FT IR、CO2-TPD等手段研究了材料的织构、微观形貌、孔结构的有序性、化学组成和碱性质等。在以苯甲醛和丙二腈为底物的Knoevenagel缩合反应中,CND-SBA15材料表现出了很好的催化活性和稳定性。     

Synthesis of mesoporous carbons using ordered and disordered mesoporous silica templates and polyacrylonitrile as carbon precursor

Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs.     

Synthesis of Co-containing mesoporous carbon foams using a new cobalt-oxo cluster as a precursor

A novel trinuclear cobalt-oxo cluster 2[Co₃O(Ac)₆(H₂O)₃]·H₂O (Co-OXO) has been obtained and characterized by X-ray single-crystal diffraction and elemental analysis. The structure of Co-OXO displays 3D supramolecular networks through hydrogen bonds and generates boron nitride (bnn) topology. Co-OXO was further used as a precursor to synthesize Co-containing mesoporous carbon foams (Co-MCFs), which exhibit highly ordered mesostructure with specific surface area of 614 m² g^?1 and uniform pore size of 2.7 nm. Charge–discharge tests show that the specific discharge capacitance of Co-MCFs is 7% higher than that of the MCFs at the current density of 100 mA g^?1, and 26% higher than that of MCFs at the current density of 3 A g^?1. The electrochemical behaviors of Co-MCFs are obviously improved due to the improved wettability, increased graphitization degree and the pseudo-capacitance through additional faradic reactions arising from cobalt.     

Preparation and characterization of RF aerogel on UV irradiation method

The UV irradiation method provides us a new way of preparing resorcinol–formaldehyde (RF) aerogel. In this paper, water soluble, neutral photo-initiator 659 was used to synthesize RF aerogel by using free radical UV initiator. Incorporation of the UV initiators during the sol–gel stage usually decreases the gel-time. On changing the performed time and initiators quantities in synthesizing RF aerogel, The results will be discussed that gel-time of the RF aerogel definitely depends on the polymerization time and initiators quantities. The paper will also be discussed the RF aerogel developed for UV irradiation method and Sol–gel method by IR spectrum, Scanning electron microscopy, N₂ adsorption/desorption to show that light initiator does not play any role in the formation of the aerogel skeleton; The RF aerogel using UV irradiation method still maintain a high pore structure, shorter gel-time and the three-dimensional size block.