爆轰裂解法制备纳米石墨粉的吸附性能研究

 在酸含量不同的原材料中,通过爆轰的方法制备纳米石墨粉,并利用BET方程以及BJH方法对所得纳米石墨粉进行比表面积和孔径分布分析。分析结果表明,所得爆轰产物中有的比表面积大致为天然鳞片石墨的5.3~9.2倍,而且随酸含量的增大逐渐增大,产物的等温线中存在吸附滞后现象。其中,增大的比表面积主要由分布在3 nm至7 nm之间的孔引起的,而且在爆轰后,孔径4 nm左右的孔,其数量达到最大值。通过对纳米石墨粉的研究,分析了酸在爆轰过程中的积极作用,并为纳米石墨粉的进一步应用提供了结构信息。     

炸药爆轰法制备纳米石墨粉及其在高压合成金刚石中的应用

介绍了一种制备纳米石墨粉的新方法——负氧平衡炸药爆轰法. 对合成的黑粉产物进行x射线衍射分析，确认其为石墨结构，平均晶粒度为2.58 nm. 透射电子显微分析的结果表明，炸药爆轰法制备的黑粉为六方结构的纳米石墨粉，颗粒呈球形或椭球形. 用小角x射线散射法测定纳米石墨粉的粒度分布在1—50 nm，有92.6wt%的粉末粒度小于16 nm. 平均粒径为8.9 nm. 纳米石墨粉的比表面积约为500—650 m²/g. 在六面顶压机中用纳米石墨粉在Fe粉触媒的作用下进行金刚石的高压合成实验 关键词： 纳米石墨粉 爆轰 金刚石 合成     

炸药爆轰制备纳米石墨粉储放氢性能实验研究

介绍了一种新的制备纳米石墨粉的方法——炸药爆轰法.通过对爆轰合成的黑色粉末进行x射线衍射分析，确认其为六方结构的纳米石墨，平均晶粒度为1.86—2.61nm.用BET气体吸附仪测试纳米石墨粉的比表面积约为500—650m2/g，由比表面积计算得到的纳米石墨粒度为4.41—6.85nm.在室温（≈290K）和12MPa压力条件下对纳米石墨粉进行储放氢气性能测试，结果表明纳米石墨粉样品的储放氢量为0.33wt%—0.37wt％.在相同实验条件下，纳米石墨粉原始样品的储放氢能力较原始纳米炭纤维（0.15wt%—0.35wt％）和多壁碳纳米管（0.15wt%—0.20wt％）的储放氢能力略强,但低于超级活性炭（0.92wt%—0.98wt％）.纳米碳材料的比表面积在其储放氢实验中起关键作用. 关键词： 爆轰 纳米石墨粉 比表面积 储放氢量     

五羰基铁气相爆轰法合成纳米碳胶囊

采用气相爆轰法,以乙炔气体、氧气和五羰基铁为原料成功地合成了比表面积为253.857m~2/g的胶囊状碳纳米材料。对反应的前置实验九羰基二铁的热分解反应的研究表明,在60～140℃之间,九羰基二铁热分解为五羰基铁和十二羰基三铁。对爆轰产物进行了XRD、TEM和BET物理吸附实验,结果表明:产物XRD图谱石墨峰明显,产物主要为具有石墨化倾向的薄层胶囊状无定形碳结构;实验产物比表面积为253.857m~2/g,孔体积为0.940cm~3/g,平均孔径为2.731nm;吸附-脱附曲线回滞环类型为H3型,孔结构主要为颗粒堆积而形成的狭缝孔;爆轰产物比表面积较大,具有较强的吸附能力。证实了同样采用铁作为触媒,乙炔在不添加惰性气体作为缓冲剂的情况下,由于爆速过高而无法用于合成碳纳米管。     

气相/凝聚炸药爆轰合成的碳包铜纳米颗粒特征

采用凝聚炸药爆轰和气相爆轰分别制备碳包铜纳米颗粒,并利用XRD,Raman和TEM等方法对合成纳米产物进行对比分析。其中凝聚炸药爆轰法以柠檬酸铜干凝胶、油酸和黑索金为原料按照一定比例配成爆炸源,在氮气的保护氛围中引爆；而气相爆轰法以乙酰丙酮铜为原料,分别以H2和O2,H2和空气为爆炸源,在负氧条件下引爆。通过XRD,Raman和TEM分析结果表明,两类爆轰法均可得到分散性良好的碳包覆铜纳米颗粒,碳壳石墨化程度较高。气相爆轰可以合成10 nm以下的纳米晶粒,而凝聚炸药爆轰合成的晶粒尺寸在20~40 nm,且存在较多空壳结构；气相爆轰产物其碳壳尺寸在2~3 nm,凝聚炸药爆轰产物其碳壳尺寸在2~5 nm。     

压汞法分析生物质焦孔隙结构

对于稻壳、树叶、棉花杆、玉米杆四种生物质焦,通过压汞法测量了其在大孔和部分中孔范围内的孔隙结构,发现热解温度、热解保持时间、热解快／慢速都会影响着焦样的比表面积和平均孔径。四种生物质中,树叶焦样的比表面积最大,玉米杆的比表面积最小;稻壳焦样的平均孔径最小,玉米杆的平均孔径最大。不同生物质焦样的孔径分布规律有很大不同。热解温度、热解速度和热解保持时间对孔径分布规律的影响不大,决定孔径分布规律的是生物质本身。在中孔和大孔的范围内,四种生物质焦样的孔径分布曲线都呈现出双峰结构。     

炸药爆轰法制备的纳米石墨粉的拉曼光谱

负氧平衡炸药爆轰法合成的纳米石墨粉,是一种新型的具有良好实用前景的纳米粉体材料。采用负氧平衡炸药梯恩梯(TNT),在分别充有氮气、氩气、二氧化碳等保护性气体、压力为0.25～2 atm的密闭容器内爆轰制备了纳米石墨粉。用激光拉曼光谱对制备的样品进行了测试,结果表明样品为石墨结构。纳米石墨粉的Raman峰与块体石墨相比,其峰位向高波数方向偏移了约5 cm-1。纳米石墨粉Raman峰的半高宽约为22 cm-1,由此可计算出纳米石墨粉的颗粒大小为2.97～3.97 nm。与高纯石墨Raman峰相比,纳米石墨粉的Raman峰由于尺寸效应出现了蓝移现象, 并对此现象进行了讨论。用X射线衍射仪(XRD)和透射电子显微镜(TEM)测定了纳米石墨粉的物相,并对其颗粒粒径进行了估算,其结果为2.58 nm(酸处理前)和1.86 nm(酸处理后),与Raman光谱的结果基本吻合。     

纳米二氧化钛粉体的气相爆轰制备

 介绍了利用氢氧混合气体为原料、以四氯化钛为前驱体、气相爆轰制备纳米二氧化钛粉体的方法。利用XRD衍射结果分析证明，产物为金红石相和锐钛矿相的二氧化钛混晶，其晶粒尺度为纳米量级。通过XRD、SEM、TEM分析可以得出，粒子基本为球形，大部分粒子粒径为10~20 nm，也有少量的100 nm左右的粒子产生。分析后发现，反应发生在爆燃转爆轰的过程中和爆轰管中的湍流现象是导致大粒子产生的主要原因。在对在氢过量和氧过量两种状况下，对爆轰所产生的产物的形貌进行了对比，分析发现两种状况产生纳米二氧化钛粉末粒径分布和形貌并没有太大变化。     

介孔二氧化钛光催化降解乙醛及其影响因素

"应用溶剂蒸发自组装的方法合成了具有蠕虫状孔道的介孔二氧化钛粉末和薄膜．考察了不同焙烧温度对材料介孔结构和光催化性能的影响．乙醛光催化降解实验用来表征不同焙烧温度下介孔材料的光催化性能．结果表明实验中合成的介孔二氧化钛材料的光催化活性明显高于颗粒二氧化钛(Degussa P25)．其中400 oC焙烧的样品具有平均孔径为6.0 nm的窄的孔径分布和117 m2/g的大的比表面积．通过对光催化活性结果的分析,发现介孔二氧化钛的活性主要受其比表面积和结晶性的共同影响．对介孔二氧化钛薄膜材料进行了同样的光催化表     

爆轰合成碳包覆钴、镍磁性纳米颗粒的探索

 介绍了爆轰法合成碳包覆钴、镍纳米磁性颗粒研究的初步结果。以黑索今炸药为主体,加入钴、镍金属硝酸盐与有机碳源材料,在爆炸容器中氮气保护下用导爆管雷管引爆,成功地合成了碳包覆钴、镍纳米磁性颗粒。为了探求爆轰固体产物的形貌特征及性能,分别采用了TEM、XRD、VSM等测试手段对其进行表征。实验结果表明,爆轰产物中主要含有碳包覆纳米钴、纳米镍磁性颗粒,成球体或者椭球体,具有完好的核壳结构形貌。合成的碳包覆钴颗粒分布在30~50 nm之间,碳包覆的镍颗粒分布在25~60 nm之间,外层碳壳层主要由无定形碳和石墨构成。磁性测试表明,所得碳包金属钴、镍颗粒在室温下具有良好的软磁特性。     

Comparison of the adsorptive properties of papyex and uncompressed exfoliated graphite

The adsorption isotherms of krypton at 77.3 and 90 K, methane at 77.3 K and xenon at 105 K have been compared when respectively determined on uncompressed exfoliated graphite and Papyex (compressed exfoliated graphite), in the first monolayer range. An alteration of the isotherms on Papyex has been observed, due to the compression of the initial exfoliated graphite. This compression leads to an increase of the surface heterogeneity and a decrease of the uniform patch size. Nevertheless, the main characteristics of the isotherms are preserved. Moreover, during the first monolayer formation, according to the state of the film, some differences in the kinetics appear, which are not noticeable in the case of uncompressed exfoliated graphite: high speed of adsorption when the film is mobile, and low speed in the case of a 2D solid.     

Modeling multilayer adsorption of interacting polyatomic species on heterogeneous surfaces

In the present work, a generalized lattice-gas model to study multilayer adsorption of interacting polyatomic species on heterogeneous surfaces is introduced. Using an approximation in the spirit of the well-known Brunauer-Emmet-Teller (BET) model, a new theoretical isotherm is obtained in one- and two-dimensional lattices and compared with Monte Carlo simulation. In addition, the BET approach is used to analyze these isotherms and to estimate the monolayer volume. In all cases, the application of the BET equation leads to an underestimate of the true monolayer capacity. However, significant compensation effects were observed for heterogeneous surfaces and attractive lateral interactions.     

Transition bidimensionnelle du premier ordre; cas du xénon adsorbé sur la face (0001) du graphite

Submonolayer adsorption isotherms of xenon condensed on the (0001) face of graphite are measured between 85°K and 102°K by Auger electron spectroscopy. A two-dimensional phase change 2D gas ? 2D solid is emphasized. The solid phase is characterized by low energy electron diffraction. It is a two-dimensional crystal in epitaxy on the graphite. The analysis of the adsorption isotherms measured with a sensivity of $\text{1}\text{500}$ of monolayer, i.e. 10¹⁰ atoms, allows to determine the integral heat of adsorption at the two-dimensional phase change (5.5 ± 0.1 kcal mole^?1). We also deduced from our measurements, the binding energy of an individual atom of xenon on the (0001) face of graphite, the heat and the entropy of fusion of the two-dimensional crystal.     

Phase transitions in physisorbed films on cadmium (0001): comparison with graphite (0001)

Physical adsorption of simple molecules has been studied experimentally on cadmium (0001). Adsorption isotherms of Kr and CF₄ at 77.3 K show a first-order phase transition in the first layer, characteristic of adsorption on uniform substrates.

The nature of the phase transition on cadmium (0001) in the first layer is investigated for Kr and CF₄ by a thermodynamic approach in comparison with results obtained earlier on graphite (0001).

From the comparison between the two uniform substrates, we show that (1) cadmium (0001) has a less attractive force field than graphite (0001); and (2) like graphite (0001), cadmium (0001) is a very uniform surface suitable for studying two-dimensional phases according to the Gibbsian formulation.     

Preparation of activated carbons previously treated with sulfuric acid: A study of their adsorption capacity in solution

In the present work, cedar wood has been used as raw material for the preparation of activated carbons. The influence of a previous treatment with sulfuric acid on the textural properties of the carbonized and activated samples has been investigated. Finally, the adsorption capacity of para-nitrophenol in aqueous solution has been studied and the corresponding adsorption isotherms have been fitted to Langmuir's equation. The experimental results indicate that the previous dehydration of the raw material with sulfuric acid gives rise to an improvement in the porous texture and adsorption capacity of the activated carbons.     

Excess surface work—A modelless way of getting surface energies and specific surface areas directly from sorption isotherms

Sorption isotherms can be easily transformed into excess surface work (ESW) isotherms, computed as the product of the adsorbed amount and the change in chemical potential. Plotted against the amount adsorbed at least one minimum is yield. Thermodynamically ESW is the sum of the surface free energy and the isobaric isothermal work of sorption. Therefore, ESW is not a model, instead it is just another way of presenting an isotherm. From the amount adsorbed in the first minimum one can obtain a specific surface area similar to the BET surface area. The depth of the ESW in the minimum gives a sorption energy, which corresponds approximately to the loss of degrees of freedom of the sorptive. In this contribution the ESW plots of various sorption isotherms on highly ordered alumina with cylindrical pores of 25 nm width and mesoporous SBA 15 will be presented and discussed.     

Hydrogen adsorption in microporous alkali-doped carbons (activated carbon and single wall nanotubes)

Adsorption of hydrogen gas was tested in microporous doped carbons: activated carbon (1600 m²/g) and single wall carbon nanotubes (SWNTs). The isotherms of adsorption of LiC₁₈ and KC₂₄ doped microporous activated carbons were determined in the range [0–30 bar] at room temperature and 77 K. The chemisorption ratio observed at room temperature increases with increasing the alkali/carbon rate. The isotherm profiles of doped activated carbon at 77 K show no clear enhancement of the sorption ratio compared to the raw activated carbon.The adsorption sites of potassium doped SWNTs with closed end were determined by neutron diffraction experiment using deuterium gas. The K-doped SWNTs were found only slightly intercalated by K ions so that empty cavities are preserved in between the tubes. At room temperature, the chemisorption of deuterium was not observed in doped SWNTs bundles, but only in the KC₈ graphite intercalation compound impurities. At low temperature, the isotherms analysis and neutron diffraction experiments have shown that D₂ molecules are physisorbed in the free interstitial voids in between the tubes within the bundles.     

New insights into the adsorption isotherm interpretation by a coupled molecular simulation—experimental procedure

We present here Grand Canonical Monte Carlo (GCMC) simulation results of nitrogen adsorption at 77 K on a crude model of activated carbon. The material is modeled as slit-like pores of different widths, with smooth surfaces. The individual adsorption isotherms serve as the basis to check the success and limitations of the assumptions made when using the BET model to characterize adsorbent materials, in particular to calculate the monolayer capacity and the C parameter. As done in our previous work with several experimental adsorption isotherms, different linearizations of the BET equation are used. The aim of this work is to quantify, using statistical mechanics tools, the changes in the C factor with surface coverage, showing that C is an intrinsically energetic meaningful quantity. The amount of molecules adsorbed at each pressure is calculated in the first and subsequent layers. We also keep track of the adsorbent-adsorbate and adsorbate-adsorbate energy along the simulations. The C factor is obtained following two different routes: as directly derived from the BET equation, once the monolayer capacity is known, and from the heat of adsorption obtained directly from the simulations. Results from simulations confirm the changes in the C values with surface coverage. In addition, molecular simulations provide independent and consistent ways of calculating the monolayer capacity.     

A new isotherm equation for multilayer adsorption on heterogeneous surfaces yielding the Dubinin-Radushkevich isotherm in the submonolayer region

The Cerofolini procedure for obtaining multilayer adsorption isotherms on heterogeneous surfaces is generalized, to take into account the full form of the BET equation as the local adsorption isotherm.