Synthesis of Macro-Mesostructured γ-Al_2O_3 with Large Pore Volume and High Surface Area by a Facile Secondary Reforming Method

Through improving the aging process during synthesis of the support, γ-Al2O3 with large pore volume and high surface area was synthesized by a facile secondary reforming method. The synthesis parameters, such as the reaction temperature, the first aging temperature and the second aging temperature, were investigated. The textural properties of γ-Al2O3 were characterized by means of N2 adsorption-desorption isotherms, X-ray powder diffractometry （XRD）, scanning electron microscopy （SEM）, Fourier transform infrared （FTIR） spectroscopy and thermogravimetry （TG）. The experimental results indicated that AACH and amorphous A1OOH were the precursors of alumina, which were formed via precipitation from solutions after reaction of aluminum sulphate with ammonium hydrogen carbonate. The precursor nanocrystallites grew and re-assembled during the secondary reforming process, which resulted in an increased pore size and pore volume and a decreased bulk density. The as-synthesized γ-Al2O3 materials featured meso/macroporosity, large pore volume （2.175 cm^3/g）, high surface area （237.8 m^2/g）, and low bulk density （0.284 g/mL）.

Volume and Surface Distribution Heterogeneity of Nano-pore in Coal Samples by CO2 and N2 Adsorption Experiments

In this paper,the heterogeneity of adsorption pores in middle and high rank coal samples were analyzed by using low temperature N2 and CO2 adsorption technology and fractal theory.The following results were achieved.1)According to the results of volume and surface fractal dimension,meso-pores can be classified into Mep-1,Mep-2,and Mep-3,respectively.Micro-pore can be classified into Mip-1,Mip-2,and Mip-3,respectively.2)Pore types play an important role in affecting the heterogeneity of meso-pores.The volume heterogeneity(VHY)of Mep-1 is simpler than that of Mep-2 and Mep-3 in type A samples.However,the VHY of Mep-1 becomes gradually larger than that of Mep-2 and Mep-3 from type A to type B and C.The VHY of open pore in the same diameter is higher than that of semi-open or closed pore.Meanwhile,the surface heterogeneity(SHY)of types A and B samples is significantly larger than that of type C,the SHY of semi-open or closed pores is more complicated than that of open pores.3)Coal rank mainly affects the heterogeneity of micro-pores.The heterogeneity of type A is always smaller than that of type B and C.The VHY of Mip-1 is more complicated than that of Mip-2 and Mip-3 in the same samples,and the sensitivity of the VHY of Mip-1 and Mip-2 to the degree of coal rank is smaller than that of Mip-3.Meanwhile,the SHY of Mip-1 and Mip-2 is simpler than that of Mip-3 in the same sample,the SHY of micro-pores remains stable as the pore size decreases,and the affect of coalification level on SHY decreases with the decrease in pore diameter.Full-scale fractal characterization has enabled quantitative characterization of adsorption pore properties and provided useful information with regards to the similarity of pore features in different coal reservoirs.

Determination of the Real Surface Area of Palladium Electrode

Four methods, including voltammetric measurement of double layer capacitance, surface oxides reduction, under potential deposition of Cu and carbon monoxide （CO） stripping have been applied to evaluate the real surface area of a polycrystalline Pd （pc-Pd） electrode. The results reveal that the second and third methods lead to consistent results with deviations below 5%. And from the determined double layer capacitance and CO stripping charge, it is deduced that the double layer capacity unit area is 23.1±0.4μF/cm2 and the saturated CO adlayer should be ca. 0.66 ML in order to ensure that the real surface area as determined is consistent with the other two techniques. The applicability as well as the attentions when applying these techniques for the determination of the real surface area of pc-Pd electrodes have been discussed.

Characteristics of phosphorus adsorption by sediment mineral matrices with different particle sizes

The particle size of sediment is one of the main factors that influence the phosphorus physical adsorption on sediment. In order to eliminate the effect of other components of sediment on the phosphorus physical adsorption, the sediment mineral matrices were obtained by removing inorganic matter, metal oxides, and organic matter from natural sediments, which were collected from the Nantong reach of the Yangtze River. The results show that an exponential relationship exists between the median particle size （Ds0） and specific surface area （Sg） of the sediment mineral matrices, and the fine sediment mineral matrix sample has a larger specific surface area and pore volume than the coarse sediment particles. The kinetic equations were used to describe the phosphorus adsorption process of the sediment mineral matrices, including the Elovich equation, quasi-first-order adsorption kinetic equation, and quasi-second-order adsorption kinetic equation. The results show that the quasi-second-order adsorption kinetic equation has the best fitting effect. Using the mass conservation and Langmuir adsorption kinetic equations, a formula was deduced to calculate the equilibrium adsorption capacity of the sediment mineral matrices. The results of this study show that the phosphorus adsorption capacity decreases with the increase of Ds0, indicating that the specific surface area and pore volume are the main factors in determining the phosphorus adsorption capacity of the sediment mineral matrices. This study will help understand the important role of sediment in the transformation of phosphorus in aquatic environments.

BET Surface Area and Porous Structure of Fullerenes and Fullerene Soots

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New Method for Calculating Slit-Shaped Pore Size In Solids from Adsorption Isotherm

Assuming the pores in a porous solid to be slit-shaped,according to the principle of surface chemical thermody-namics,an equation for the calculation of pore size fromthe desorption branch of the isotherm of physical adsorp-tion of nitrogen on the porous solid at liquid nitrogentemperature is derived.The calculation results obtainedby different methods,namely,the classical method,BBmethod and the method of this paper,are compared.Comparison shows that the pore sizes d_T and d_H calculat-ed by the method of this paper and BB method respec-tively are larger than the pore size d_c calculated by theclassical method in the range 0【p/p_s【1;d_T】d_Hatp/p_s【0.71 and d_H】d_T at p/p_s】0.71;The results byBB method and the method of this paper tend to be thesame as that by the classical method while p/p_s ap-proaches 1.

Modeling Enhanced Adsorption of Explosive Molecules on a Hydroxylated Graphene Pore

The possibility of a graphene bilayer nanosensor for the detection of explosive molecules was modeled using computational chemistry. A pore was designed on a graphene bilayer structure with three strategically placed perimeter hydroxyl (OH) groups built around the edge of an indented, two-dimensional hexagonal pore. This hydroxylated pore and models of various explosive molecules were optimized using MM2 molecular mechanics parameters. Values were calculated for the molecule-surface interaction energy (binding energy), E, for 22 explosive molecules on a flat graphene bilayer and on the specially designed hydroxylated pore within the bilayer. The molecule-surface binding energy for trinitrotoluene (TNT) increased from 17.9 kcal/mol on the flat graphene bilayer to 42.3 kcal/mol on the hydroxylated pore. Due to the common functionality of nitro groups that exist on many explosive molecules, the other explosive molecules studied gave similar enhancements based on the specific hydrogen bonding interactions formed within the pore. Each of the 22 explosive adsorbate molecules showed increased molecule-surface interaction on the bilayer hydroxylated pore as compared to the flat bilayer. For the 22 molecules, the average E for the flat graphite surface was 15.8 kcal/mol and for the hydroxylated pore E was 33.8 kcal/mol. An enhancement of adsorption should make a detection device more sensitive. Nanosensors based on a modified graphene surface may be useful for detecting extremely low concentrations of explosive molecules or explosive signature molecules.

Microstructure and its influence on CH_4 adsorption behavior of deep coal

In this paper we investigate the influence of microstructure on the CH4 adsorption behavior of deep coal. The coal microstructure is characterized by N2 adsorption at 77 K, scanning electron microscopy （SEM）, Raman spectroscopy, and Fourier transform infrared spectroscopy （FT-IR）. The CH4 adsorptions are measured at 298 K at pressures up to 5.0 MPa by the the volumetric method and fitted by the Langmuir model. The results show that the Langmuir model fits well with the experimental data, and there is a positive correlation with surface area, pore volume, ID/IG, and CH4 adsorption capacity. The burial depth also affects the methane adsorption capacity of the samples.

A comparative study of the pore characteristics and phenol adsorption performance of activated carbons prepared from oil-palm shell wastes by steam and combined steam-chemical activation

Oil-palm shell wastes were successfully converted into useful activated carbons in a systematic and novel approach by optimizing the pyrolysis conditions and subsequent steam activation conditions to maximize the BET surface area.The optimal activation conditions were a steam flow rate of 1.13 kg/h,hold time of 1.5 h and temperature of 950℃,yielding BET areas of 1432.94 and 1382.95 m^(2)/g for nitrogen-pyrolyzed and vacuumpyrolyzed chars,respectively.In steam-chemical activation,one-step activation of oil-palm shell in steam with potassium carbonate(K_(2)CO_(3)),sodium carbonate(Na_(2)CO_(3))or potassium chloride(KCl)was conducted,resulting in BET area output order of shell/K_(2)CO_(3)(710.56 m^(2)/g)>shell/KCl(498.55 m^(2)/g)>shell(366.7 m^(2)/g)>shell/Na_(2)CO_(3)(326.62 m^(2)/g).This study reported the first use of KCl and Na_(2)CO_(3)as chemical reagents in one-step steam-chemical activation of biomass.KCl-activated carbon exhibited retardation of tar formation property,resulting in better pore development than pure steam activated carbon.Phenol adsorption of activated carbon is not only a function of the BET surface area but also the type of pyrolysis used prior to physical activation.Activated carbon(BET area of 1192.29 m^(2)/g)pyrolyzed under vacuum could adsorb 87%more phenol than that pyrolyzed in nitrogen flow which had a higher BET area of 1432.94 m^(2)/g.Phenol adsorption capacities of activated carbons are:shell pyrolyzed under vacuum(275.5 mg/g)>shell pyrolyzed in N_(2)flow(147.1 mg/g)>shell/K_(2)CO_(3)(145.7 mg/g)>shell without pyrolysis(12.1 mg/g).These activated carbons would be highly suitable in industry processes to remove phenolic contaminants.

Removal of Safranin-O from Aqueous Solution by Adsorption onto Kaolinite Clay

In this study, Natural Raw Kaolinite (NRK) clay was used as an adsorbent for the investigation of the adsorption kinetics, isotherms and thermodynamic parameters of a cationic dye Safranine-O, also known as Basic Red 2 (BR2) from aqueous solution. The effects of pH, temperature, initial dye concentration and contact time on the adsorption capacity were evaluated and the adsorbent was characterized by XRD, BET and FTIR. The pseudo-first-order, pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The experimental data fitted very well with the pseudo-second-order kinetic model and also followed intraparticle diffusion model revealing that diffusion is not only the rate-controlling step. The Langmuir Freundlich and Dubinin-Radushkevic adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were also determined. The Langmuir model agrees with experimental data well. The activation energy, change of Gibbs free energy, enthalpy and entropy of adsorption were also evaluated for the adsorption of BR2 onto NRK.

Removal of Dyes from Wastewater by Adsorption onto Activated Carbon: Mini Review

Nowadays, wastewater from dyeing industries became a challenging issue in the world. Researchers have reported several techniques to treat those effluents based on their projects. Adsorption is the most common method because of cheap, simple and effective method. In this work, activated carbon was used for dye adsorption purpose. This adsorbent has high surface area and high porosity to remove dye. This review highlighted some important results of the last few years regarding the use of activated carbon in wastewater treatment. Research findings supported that adsorption process is spontaneous in nature. Adsorption data confirmed Langmuir model, indicating the chemisorption occurred.

Experimental Adsorption and Modelisation of CO<SUB>2</SUB>on Adsorbents Collected from Elborma Field in South Tunisia

In order to select the best adsorbant for CO2 sequestration, this study deals the interaction between clay, Triassic sandstone and Jurassic evaporate and CO2. These materials have been used as sorbents. To choose the adequate geological layers for sequestration and with minimum risk of leakage, adsorbent characterizations were investigated using X-ray diffraction, SEM and surface area analysis, structural and textural shapes of these materials have been investigated too. The elution chromatography in gaseous phase has been employed to determine the adsorption isotherms of adsorbed CO2 for each adsorbent. Then, the treatment of the experimental data allowed us to compare each CO2/adsorbent couple. The adsorption isotherms were modeled using the Langmir and Freundlich models. A thermodynamic comparison between the different adsorbents will also be provided. Experimental results show that clay and Triassic sandstone have the highest rate of adsorption amount. It has been also found that the Langmuir model is the most appropriate one to describe the phenomenon of CO2 adsorption on clay. However, for the other adsorbents (i.e. Triassic sandstone and Jurassic evaporates) the two-models are adequate.

Comparative Study of the Adsorption and Desorption Behavior of Single and Multi-Ring Aromatics in Sediment Fractions

The sorption behaviour of benzene, toluene, ethyl benzene, xylene and naphthalene using clay and sand sediments under ambient conditions is examined in this study. Experimental results showed that, the time taken to attain adsorption equilibrium for naphthalene, and BTEX were 28, 30, 30, 32, 28 hrs and 20, 22, 22, 24, 22 hrs while the desorption equilibrium time were 10, 13, 12, 15, 12 hrs and 9, 9, 9, 11, 10 hrs in clay and sand respectively. All of the naphthalene, and BTEX were adsorbed at the different equilibrium times, using clay while the amount of naphthalene and BTEX adsorbed by sand, at different equilibrium times were 117, 121, 127, 123 and 134 mg. Following the results of the adsorption/desorption experiments, quantitative measurements showed that sand exhibited higher affinity for the solute as retained more chemicals (as high as between 58% - 66%) within it pores while nearly all the chemicals adsorbed by the clay were released at the attainment of equilibrium. The implication of this is that occlusion within the sand particles may likely be the resultant effect of continued sand-chemicals contact. The amount of contaminant solute adsorbed and desorbed affirmed that clay has a better capacity to retain naphthalene and BTEX than sand and this may not be unrelated to its large surface area, high porosity and higher hydraulic conductivity for the solutes arising from its good binding sites (small pore sizes) that tend to hold the adsorbates to its particles.

Better Refined Adsorption Isotherm than BET Equation

During studying the heat capacity of metals and brightening more than the original Lena’s image, the temperature increasing term obtained in binomial expansion is transformed into the adsorption increasing term and thereafter we have derived the total adsorption rate equation with it. In the first layer the quantization does not occur and from 2nd layer to nth layer the quantization occurs. So as to get the total adsorption rate equation we add the quantized terms of the second to nth layers to the non-quantized term of the first layer. All terms are based on the unit surface sites. Instead of the unit surface sites, the new adsorption site term appears in the denominator of the adsorption equation. Hence the adsorption equations come out much better than BET equation. The surface area is also calculated through the integration of the adsorption isotherm equation excluding the first layer adsorption equation from the inflection point to the wanted relative pressure.

Real-time pore structure evolution difference between deep and shallow coal during gas adsorption:A study based on synchrotron radiation small-angle X-ray scattering

Coal seam CO_(2) sequestration is an important option to address global warming.A better knowledge on coal pore structure evolution during gas adsorption can provide guidance for coal seams CO_(2) seques-tration.However,few investigations on the pore structure evolution differences between the deep and shallow coal were conducted during gas adsorption.In this study,based on the real-time synchrotron radiation small-angle X-ray scattering(SAXS)observation,the average pore diameter and pore surface fractal dimension evolution differences between deep and shallow coal were investigated from the as-pects of coal compositions and stress history.Two types of coal deformation(inner-swelling and outer-swelling)coexist during gas adsorption.Coal compositions have significant impact on the dominance of deformation type.The dominance of inner-swelling in deep coal is induced by the higher ash contents,and there is the decrease of average pore diameter during gas adsorption.The impact of stress-history(burial depth)on adsorption-induced deformation is more prominent than that of gas adsorption ca-pacity.In deep coal,the surface fractal dimension evolution presents a negative correlation with the evolution of pore diameters.In shallow coal,the surface fractal dimension evolution presents a Langmuir-type correlation with the adsorption time.

Microfluidic synthesis of thiourea modified chitosan microsphere of high specific surface area for heavy metal wastewater treatment

An improved biosorbent of thiourea modified chitosan microsphere（TMCM） with high specific surface,favorable mechanical strength and excellent adsorption performance had been synthesized via microfluidic technology. Polyethylene glycol was used as a significant component added in aqueous solution of chitosan to produce such microspheres through droplets forming, chemical crosslinking and pores creating. For the improvement of adsorption capacity, thiourea was considered as an excellent choice in increasing amino functional group by graft modification. The SEM, FTIR and EDS were employed to detect distinct features of TMCM. Copper（Ⅱ） was used to test the adsorption performance of TMCM. The experimental results indicated that TMCM exhibited higher adsorption capacity（q_e= 60.6 mg g_（-1）） and faster adsorption rate than that non-modified chitosan microsphere（NMCM）.The adsorption kinetic was described well by the pseudo-second order kinetic model, which suggested that chemical adsorption along with electrons transferring was dominant in adsorption process.

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 ...

Homogeneous Zr and Ti co-doped SBA-15 with high specific surface area:preparation,characterization and application

A facile synthesis procedure is proposed to prepare homogeneous Zr and Ti co-doped SBA-15(Zr-Ti-SBA-15)with high specific surface area of 876.0m2 g−1.Based on“masking mechanism”from tanning,lactic acid was used as masking agent to obtain the uniform distribution of Zr and Ti species in the SBA-15 framework.The obtained materials were characterized by powder X-ray diffraction(XRD),nitrogen adsorption-desorption isotherms,scanning electron microscope(SEM),transmission electron microscope(TEM)and X-ray photoelectron(XPS).The results reveal that in mesoporous materials,the presence of lactic acid gives rise to the uniform distribution of Zr and Ti species.The adsorption equilibrium and kinetic studies of Zr-Ti-SBA-15 materials show that the adsorption process conforms to the Langmuir isotherm and pseudo-second-order kinetic model,respectively.Regenerational experiments show that the Zr-Ti-SBA-15 displays a significant adsorption ability for methylene blue(MB)(up to 291.6 mg/g),along with good reusability,indicating promising potentials of commercialization.Methodologically,this work provides a wide range of possibilities for further development of SBA-15 based on bimetallic and sewage disposal.

Characterization of Organic-Rich Shales for Petroleum Exploration & Exploitation: A Review-Part 1: Bulk Properties, Multi-Scale Geometry and Gas Adsorption

Shales, the most abundant of sedimentary rocks, are valued as the source-rocks and seals to porous petroleum reservoirs. Over the past-twenty years, organic-rich shales have also emerged as valuable petroleum systems （reservoir, seal, and source rocks contained in the same for- mation）. As such they have become primary targets for petroleum exploration and exploitation. This Part 1 of a three-part review addresses the bulk properties, multi-scale geometry and gas adsorption characteristics of these diverse and complex rocks. Shales display extremely low permeability, and their porosity is also low, but multi-scale. Characterizing the geometry and interconnectivity of the pore-structure frameworks with the natural-fracture networks within shales is essential for establish- ing their petroleum exploitation potential. Organic-rich shales typically contain two distinct types of porosity： matrix porosity and fracture porosity. In addition to inter-granular porosity, the matrix po- rosity includes two types of mineral-hosted porosity： inorganic-mineral-hosted porosity （1P）; and, organic-matter-hosted （within the kerogen） porosity （OP）. Whereas, the fracture porosity and per- meability is crucial for petroleum production from shales, it is within the OP where, typically, much of the in-situ oil and gas resources resides, and from where it needs to be mobilized. OP increases signifi- cantly as shales become more thermally mature （i.e., within the gas generation zones）, and plays a key role in the ultimate recovery from shale-gas systems. Shales＇ methane sorption capacities （MSC） tends to be positively correlated with their total organic carbon content （TOC）, thermal maturation, and mi- cropore volume. Clay minerals also significantly influence key physical properties of shale related to fluid flow （permeability） and response to stress （fracability） that determine their prospectivity for pe- troleum exploitation. Clay minerals can also adsorb gas, some much better than others. The surface area of the pore structure of shales can be positively or negatively correlated with TOC content, de- pending upon mineralogy and thermal maturity, and can influence its gas adsorption capacity. Part 2 of this three-part review considers, in a separate article, the geochemistry and thermal maturity cha- racteristics of shale; whereas Part 3, addresses the geomechanical attributes of shales, including their complex wettability, adsorption, water imbibition and ＂fracability＂ characteristics. The objectives of this Part 1 of the review is to identify important distinguishing characteristics related to the bulk properties of the most-prospective, petroleum-rich shales.

Characterization of Compactness of Rust Layers on Weathering Steels by an Adsorption/Dehydration Test of Ethanol

A new method for evaluating the compactness of rust layers on steels has been proposed in the present study. The method includes adsorption and dehydration process of anhydrous ethanol. The protective ability of rust layers can be qualitatively reflected by the adsorption/dehydration rates. The specific surface area and porosity of rust layers can be calculated by a quantitative model. The results from the present method are consistent with electrochemical tests, N2 adsorption and X-ray diffraction analysis. The method characterizes the compactness of rust layers rather than that of corrosion products removed from the metal surfaces, which is generally practiced in classic N2 adsorption method. Furthermore, the method can reflect the compactness of inner rust layers, to which N2 adsorption is unavailable. The method provides a new approach for the study of rust layers.