Direct Synthesis of Amine-functionalized Mesoporous Silica for CO_2 Adsorption

Amine-functionalized mesoporous silica was prepared by using lauric acid and N-stearoyl-l-glutamic acid as structure directing agents via the S-N+-I- mechanism and applied to CO2 adsorption at room temperature. With γ-aminopropyltriethoxysilane as co-structure directing agent and due to the direct electrostatic interaction with anionic surfactant, most of the amino groups were uniformly distributed at the inner surface of pores and the per- formance was stable. The amine-functionalized mesoporous silica was characterized by Fourier transform infrared spectrometer, X-ray diffraction, nitrogen physisorption and thermogravimetric analysis. The CO2 adsorption capacity was measured by digital recording balance. At the room temperature and under the atmospheric pressure, the adsorption capacity of LAA-AMS-0.2 for CO2 and N2 is 1.40 mmol·g-1 and 0.03 mmol·g-1, respectively, indicating high separation coefficient of CO2/N2.

Controllable fabrication of carbon aerogels

Nano-pore carbon aerogels were prepared by the sol-gel polymerization of resorcinol (1,3-dihydroxybenzene)(C6H4(OH)2) with formaldehyde (HCHO) in a slightly basic aqueous solution, followed by super-critical drying under liquid carbon dioxide as super-critical media and carbonization at 700 ℃ under N2 gas atmosphere. The key of the work is to fabricate carbon aerogels with controllable nano-pore structure, which means extremely high surface area and sharp pore size distribution. Aiming to investigate the effects of preparation conditions on the gelation process, the bulk density, and the physical and chemical structure of the resultant carbon aerogels, the molar ratio of R/C (resorcinol to catalyst) and the amount of distilled water were varied, consequently two different sets of samples, with series of R/C ratio and RF/W (Resorcinol-Formaldehyde to water, or the content of reactant) ratio, were prepared. The result of N2 adsorption/desorption experiment at 77 K shows that the pore sizes decreasing from 11.4 down to 2.2 nm with the increasing of the molar ratio of R/C from 100 to 400, and/or, the pore sizes decreasing from 3.8 down to 1.6 nm with the increasing of reactant content from 0.4 to 0.6.

Nanoscale Pore Characteristics of the Upper Permian Mudrocks from a Transitional Environment in and around Eastern Sichuan Basin, China

Nanoscale pore characteristics of the Upper Permian Longtan transitional mudrocks and their equivalent strata Wujiaping Formation marine mudrocks in and around the eastern Sichuan Basin was investigated using field emission scanning electron microscopy(FE-SEM)and low-pressure N2 adsorption experiments.The results indicate that the Upper Permian mudrock is at a mature stage with total organic carbon(TOC)values ranging between 0.47%and 12.3%.The Longtan mudrocks mainly contain vitrinite,and their mineral composition is primarily clay.In contrast,the Wujiaping mudrocks are dominated by sapropelinite and solid bitumen,and their mineral compositions are mainly quartz and a notably high amount of pyrite.The FE-SEM reveals that clay mineral pores and microcracks are the common pore types in the Longtan mudrocks.The specific surface area and pore volume depend on the clay content but are negatively correlated with the TOC.The generation of nanometer pores in the Longtan mudrocks is caused by high clay mineral contents.Meanwhile,the Wujiaping mudrock mainly contains OM pores,and the pore parameters are positively correlated with the TOC.The OM pore development exhibits remarkable differences in the Longtan and Wujiaping mudrocks,which might be related to their sedimentary facies and maceral fractions.Vitrinite and inertinite appear as discrete particles in these mudrocks and cannot generate pores during thermal maturation.Sapropelinite often contains many secondary pores,and solid bitumen with large particles,usually with several pores,is not the major contributor to the pore system of the investigated mudrock.

Preparation and characterization of carbon nano-sheet powders

Carbon nanosheet films were deposited on A1 substrates by using plasma assisted chemical vapor deposition （PACVD） technique. And after being peeled off from A1 substrates, carbon nanosheet powders （CNSPs） were obtained. In Raman spectrum of carbon film, there was a strong and broadened peak at about 1,580 cm^-1, indicating a carbon diamond-like film. Atomic force microscope image showed that the carbon diamond-like film had a grain size less than 100 nm, and its surface roughness Ra was 17.95 nm in an area of 5×5 μm^2. The CNSPs were irregular sheets with curly edges and a length of several micrometers to several hundreds of micrometers. The BET surface area of CNSPs was 6.66 m^2/g with no micro-pore present, which was confirmed by N2 adsorption-desorption characterization. In the adsorption testing, when the relative pressure p/po was higher than 0.3, the adsorption behavior did not follow the Langmuir equation. The addition of CNSPs to carbon black （catalyst support） could improve hydrodesulfurization performance of carbon supported Ni-W catalysts for diesel oil.

Influence of Drying Methods on Fractal Geometric Characteristics of Mesoporous Silica Aerogels

Chemical modification/ambient drying method and freeze drying method were introduced to research the synthesis of mesoporous silica aerogels. By analyzing N2 gas adsorption/desorption isotherms, the fractal geometric characteristics of gels were focused. The overall surface fractal dimensions were determined by analyzing N2 gas adsorption branch and a Frenkel-Halsey-Hill （FHH） equation was empolyed to determine surface fractal dimension Df It is found that, during ambient drying process, VTMCS/VWetgel ratio plays a crucial role in the changes of geometric feature, the key point is 50%, when the ratio is lower, and surface roughness increases with the ratio, when it exceeds 50%, the surface is almost unaffected by the modification. While freeze drying always tends to get larger Df freeze drying process could cause a rough surface of the gels. Compared with traditional porosity and specific surface area analyses, fractal geometry may be expected to be favorable for mesoporous structural analyses of materials.

A comparative study of drying techniques on the morphology of porous silica gels synthesized via sol-gel process

The effect of drying techniques on the microstructure,morphology and pore structure of porous silica gels was studied in the paper.The gels were prepared by using sol-gel process and different drying routes:freeze-drying (FD),low pressure drying (LPD),high temperature drying (HTD) and chemical modification & ambient drying (CMD) techniques.Observation under pore distribution and structural properties showed that CMD technique leads to homogenous mesoporous silica material with specific surface area of 745 m2/g,and the average pore size around 20 nm,while LPD and HTD result in loosely packed particles with non-isotropic aggregation pattern.The specific surface areas of LPD and HTD samples are 419 and 513 m2/g respectively,and the pore size distribution of the samples are observed distributing widely in range of 10-100 nm.Freeze drying method is a new but prospective way to prepare mesoporous silica.The specific area of FD sample is around 500 m2/g.By the comparison for the properties of the gels,this paper wants to induce a further interest in finding a proper method to synthesize the porous silica gels for low price use.

Experimental and density functional theory study of the adsorption of N_2O on ion-exchanged ZSM-5: Part II. The adsorption of N_2O on main-group ion-exchanged ZSM-5

The adsorption and desorption of N 2 O on main-group ion-exchanged ZSM-5 was studied using temperature-programmed desorption （TPD） and density functional theory （DFT） calculations. TPD experiments were carried out to determine the desorbed temperature T max corresponding to the maximum mass intensity of N 2 O desorption peak and adsorption capacity of N 2 O on metal-ion-exchanged ZSM- 5s. The results indicated that T max followed a sequence of Ba 2＋ Ca 2＋ Cs ＋ K ＋ Na ＋ Mg 2＋ and the amount of adsorbed N 2 O on main-group metal cation followed a sequence of Ba 2＋ Mg 2＋ Ca 2＋ Na ＋ K ＋ Cs ＋ . The DFT calculations were performed to obtain the adsorption energy （E ads ）, which represents the strength of the interaction between metal cations and the N-end or O-end of N 2 O. The calculation results showed that the N-end of the N 2 O molecule was favorably adsorbed on ion-exchanged ZSM-5, except for Cs-ZSM-5. For alkali metal cations, the E ads of N 2 O on cations followed the order which was the same to that of T max ： Cs ＋ K ＋ Na ＋ . The calculated and experimental results consistently showed that the adsorption performances of alkaline-earth metal cations were better than those of alkali metal cations.

Pore Size Distribution of Clayey Soils and Its Correlation with Soil Organic Matter

Soil pore size distribution(PSD) directly influences soil physical,chemical,and biological properties,and further knowledge of soil PSD is very helpful for understanding soil functions and processes.In this study,PSD of three clayey soils collected from the topsoil(0-20 cm) of Vertisols in Northern China was analyzed using the N_2 adsorption(NA) and mercury intrusion porosimetry(MIP) methods.The effect of soil organic matter(SOM) on the PSD of clayey soils was also evaluated.The differential curves of pore volume of clayey soils by the NA method exhibited that the pores with diameter < 0.01 μm accounted for more than 50%in the pore size range of 0.001 to 0.1 μm.The differential pore curves of clayey soils by the MIP method exhibited three distinct peaks in pore size range of 60 to 100,0.3 to 0.4 and 0.009 to 0.012 μm,respectively.In the three clayey soils,the ultramicropores(5-0.1μm) were determined to be the main pore class(on average 35.5%),followed by macropores(> 75 μm,31.4%),cryptopores(0.1-0.007μm,16.0%),micropores(30-5 μm,9.7%) and mesopores(75-30 μm,7.3%).The SOM greatly affected the pore structure and PSD of aggregates in clayey soils.In particular,SOM removal reduced the volume and porosity of 5-100 μm pores while increased those of <5 μm pores in the 5-2 and 2-0.25 mm aggregates of clayey soils.The increase in the volume and porosity of < 5 μm pores may be attributed to the disaggregation and partial emptying of small pores caused by the destruction of SOM.

Relationship between surface area and crystal size of pure and doped cerium oxides

Pure and Zr, La or Pr-doped cerium oxides were characterised by transmission electron microscopy (TEM), N2 adsorption-desorption at –196 oC and X-ray diffraction (XRD). For crystal sizes calculation, the Scherrer and Williamson-Hall equations were compared, and the relationship between surface area and crystal size was critically discussed. It was demonstrated that the Williamson-Hall equation must be used instead of the Scherrer equation to calculate crystal sizes, since the latter equation underestimated ...

Porous zinc(Ⅱ)-organic framework with potential open metal sites:Synthesis,structure and property

Reaction of Zn(NO3)2.6H2O with 5-(isonicotinamido) isophthalic acid(H2INAIP) in N,N-dimethylformamide(DMF) affords a new three-dimensional(3D) coordination polymer {[Zn(INAIP)(DMF)].0.5DMF.4H2O}n(1).The X-ray crystallographic structural analysis reveals that complex 1 is a 3D porous framework containing a potential open metal site inside the pores.Topology analysis confirms that complex 1 is a two-fold interpenetrated(10,3)-b net with both metal ion and ligand acting as 3-connecting nodes.The thermal stability,variable temperature X-ray diffraction pattern and N2 adsorption property of the complex are investigated.

Studies on Natural CXN Zeolite: Modification, Framework De-alumination and Ion-exchange

A natural CXN zeolite (stilbite, type code-STI) discovered in China was modified with +4NH exchange by using ammonium salt and calcinations (procedure I), or with +4NH exchange followed by treatment with acid (procedure II). The coordination state of Si and Al atoms in the framework, the property of ion exchange, and the adsorption of the H-STI zeolite samples prepared by different modification procedure were investigated with XRD, EDX, 29Si and 27Al MAS NMR, Ag+ ion exchange and N2 adsorption. The results of the investigations indicate that different procedure of the modification made variety on the distribution of the framework Si atoms and Al atoms, the content of non-framework aluminum, and the blocking channels and the shielding effect to the positions of the exchangeable cations. The H-STI zeolite prepared by the procedure II possesses high ion exchange capacity, open and perfect pore system, and high thermal stability.