The equations of the second and third order derivative curves of time with respect to potential for a reversible process in adsorption chronopotentiometry are derived and experimentally verified.
Amorphous carbon materials play a vital role in adsorbed natural gas(ANG) storage. One of the key issues in the more prevalent use of ANG is the limited adsorption capacity, which is primarily determined by the porosi...Amorphous carbon materials play a vital role in adsorbed natural gas(ANG) storage. One of the key issues in the more prevalent use of ANG is the limited adsorption capacity, which is primarily determined by the porosity and surface characteristics of porous materials. To identify suitable adsorbents, we need a reliable computational tool for pore characterization and, subsequently, quantitative prediction of the adsorption behavior. Within the framework of adsorption integral equation(AIE), the pore-size distribution(PSD) is sensitive to the adopted theoretical models and numerical algorithms through isotherm fitting. In recent years, the classical density functional theory(DFT) has emerged as a common choice to describe adsorption isotherms for AIE kernel construction. However,rarely considered is the accuracy of the mean-field approximation(MFA) commonly used in commercial software. In this work, we calibrate four versions of DFT methods with grand canonical Monte Carlo(GCMC) molecular simulation for the adsorption of CH_4 and CO_2 gas in slit pores at 298 K with the pore width varying from 0.65 to 5.00 nm and pressure from 0.2 to 2.0 MPa. It is found that a weighted-density approximation proposed by Yu(WDA-Yu) is more accurate than MFA and other non-local DFT methods. In combination with the trapezoid discretization of AIE, the WDA-Yu method provides a faithful representation of experimental data, with the accuracy and stability improved by 90.0% and 91.2%, respectively, in comparison with the corresponding results from MFA for fitting CO_2 isotherms. In particular, those distributions in the feature pore width range(FPWR)are proved more representative for the pore-size analysis. The new theoretical procedure for pore characterization has also been tested with the methane adsorption capacity in seven activated carbon samples.展开更多
The elementary mechanistic model of adsorption and sorption is based on a simple hypothesis： the adsorption sites are uniformly distnbuted on the surface of the pore walls in the adsorbent, the sorption sites are uni...The elementary mechanistic model of adsorption and sorption is based on a simple hypothesis： the adsorption sites are uniformly distnbuted on the surface of the pore walls in the adsorbent, the sorption sites are uniformly distributed in the volume of the polymer. In this first paper we will analyze the simple case where one solute molecule is only allowed to occupy a single adsorption or sorption site. A common elementary occupation law of the free sites is assumed： the differential increase of the number of the adsorbed/sorbed molecules is proportional to the differential increase of the activity of the solute and the concentration of the free （non-occupied） sites in the solid. The proportionality coefficient is called affinity coefficient depending on the solid/solute couple and on the temperature and independent of the concentration of the solute. In adsorption the concentration of the free sites is a surface concentration on the pore walls and in sorption it is expressed by the molarity. The simple monolayer adsorption law of Jovanovic is obtained： n = no（1 - e KP） where n is the number of moles adsorbed when the pressure is P. no is the total number of adsorption sites and K the affinity coefficient for adsorption. The sorption law writes： a = 1/k [Ф/1-Ф] ＋ 1-r/k In [1 ＋ 1/r Ф/1-Ф] where Ф, r and k hold respectively for the volume fraction of the solvent in the polymer, for the ratio of the molar volumes of the solvent to the elementary polymer chain containing one single adsorption site and for the sorption affinity coefficient. The confrontation of these equations to experimental isotherms is satisfactory in comparison with the classical Langmuir and Flory-Huggins equations： the best results are obtained for adsorption of vapors on a 5A zeolite and for all analyzed sorption results.展开更多
Natural gas, whose primary constituent is methane, has been considered a convincing alternative for the growth of the energy supply worldwide. Adsorbed natural gas （ANG）, the most promising methane storage method, h...Natural gas, whose primary constituent is methane, has been considered a convincing alternative for the growth of the energy supply worldwide. Adsorbed natural gas （ANG）, the most promising methane storage method, has been an active field of study in the past two decades. ANG constitutes a safe and low-cost way to store methane for natural gas vehicles at an acceptable energy density while working at substantially low pressures （3.5- 4.0 MPa）, allowing for conformable store tank. This work serves to review the state-of-the-art development reported in the scientific literature on adsorbents, adsorption theories, ANG conformable tanks, and related technolo- gies on ANG vehicles. Patent literature has also been searched and discussed. The review aims at illustrating both achievements and problems of the ANG technologies-based vehicles, as well as forecasting the development trends and critical issues to be resolved of these technologies.展开更多
Here we present a combined DFF and molecular dynamics study of uranyl （U（VI）） interaction mecha- nisms with the calcite （104） surface in aqueous solution. The roles of three anion ligands （CO2 , HCO3, OH ） and...Here we present a combined DFF and molecular dynamics study of uranyl （U（VI）） interaction mecha- nisms with the calcite （104） surface in aqueous solution. The roles of three anion ligands （CO2 , HCO3, OH ） and solvation effect in U（VI） interaction with calcite have been evaluated. According to our calculations, water adsorbed on the calcite （104） surface prefers to exist in molecular state rather than dis- sociative state. Energy analysis indicate that the positively charged uranyl species prefers to form surface complexes on the surface, while neutral uranyl species may bind with the surface via both surface complexing and ion exchange reactions of U（VI） → Ca（II）. In contrast, the negatively charged uranyl species prefer to interact with the surface via ion exchange reactions of U（VI）→ Ca（II）, and the one with UO2（CO3）2（H2O）^2- as the reactant becomes the most favorable one in energy. We also found that uranyl adsorption increases the hydrophilicability of the （104） surface to different extents, where the UO2（CO3）3Ca2 species contributes to the largest degree of energy changes （ 53 kcal/mol）. Our calcula- tions proved that the （104） surface also has the ability to immobilize U（VI） via either surface complexing or ion exchange mechanisms under different pH values.展开更多
文摘The equations of the second and third order derivative curves of time with respect to potential for a reversible process in adsorption chronopotentiometry are derived and experimentally verified.
基金Supported by the National Sci-Tech Support Plan(2015BAD21B05)China Scholarship Council(201408320127)
文摘Amorphous carbon materials play a vital role in adsorbed natural gas(ANG) storage. One of the key issues in the more prevalent use of ANG is the limited adsorption capacity, which is primarily determined by the porosity and surface characteristics of porous materials. To identify suitable adsorbents, we need a reliable computational tool for pore characterization and, subsequently, quantitative prediction of the adsorption behavior. Within the framework of adsorption integral equation(AIE), the pore-size distribution(PSD) is sensitive to the adopted theoretical models and numerical algorithms through isotherm fitting. In recent years, the classical density functional theory(DFT) has emerged as a common choice to describe adsorption isotherms for AIE kernel construction. However,rarely considered is the accuracy of the mean-field approximation(MFA) commonly used in commercial software. In this work, we calibrate four versions of DFT methods with grand canonical Monte Carlo(GCMC) molecular simulation for the adsorption of CH_4 and CO_2 gas in slit pores at 298 K with the pore width varying from 0.65 to 5.00 nm and pressure from 0.2 to 2.0 MPa. It is found that a weighted-density approximation proposed by Yu(WDA-Yu) is more accurate than MFA and other non-local DFT methods. In combination with the trapezoid discretization of AIE, the WDA-Yu method provides a faithful representation of experimental data, with the accuracy and stability improved by 90.0% and 91.2%, respectively, in comparison with the corresponding results from MFA for fitting CO_2 isotherms. In particular, those distributions in the feature pore width range(FPWR)are proved more representative for the pore-size analysis. The new theoretical procedure for pore characterization has also been tested with the methane adsorption capacity in seven activated carbon samples.
文摘The elementary mechanistic model of adsorption and sorption is based on a simple hypothesis： the adsorption sites are uniformly distnbuted on the surface of the pore walls in the adsorbent, the sorption sites are uniformly distributed in the volume of the polymer. In this first paper we will analyze the simple case where one solute molecule is only allowed to occupy a single adsorption or sorption site. A common elementary occupation law of the free sites is assumed： the differential increase of the number of the adsorbed/sorbed molecules is proportional to the differential increase of the activity of the solute and the concentration of the free （non-occupied） sites in the solid. The proportionality coefficient is called affinity coefficient depending on the solid/solute couple and on the temperature and independent of the concentration of the solute. In adsorption the concentration of the free sites is a surface concentration on the pore walls and in sorption it is expressed by the molarity. The simple monolayer adsorption law of Jovanovic is obtained： n = no（1 - e KP） where n is the number of moles adsorbed when the pressure is P. no is the total number of adsorption sites and K the affinity coefficient for adsorption. The sorption law writes： a = 1/k [Ф/1-Ф] ＋ 1-r/k In [1 ＋ 1/r Ф/1-Ф] where Ф, r and k hold respectively for the volume fraction of the solvent in the polymer, for the ratio of the molar volumes of the solvent to the elementary polymer chain containing one single adsorption site and for the sorption affinity coefficient. The confrontation of these equations to experimental isotherms is satisfactory in comparison with the classical Langmuir and Flory-Huggins equations： the best results are obtained for adsorption of vapors on a 5A zeolite and for all analyzed sorption results.
文摘Natural gas, whose primary constituent is methane, has been considered a convincing alternative for the growth of the energy supply worldwide. Adsorbed natural gas （ANG）, the most promising methane storage method, has been an active field of study in the past two decades. ANG constitutes a safe and low-cost way to store methane for natural gas vehicles at an acceptable energy density while working at substantially low pressures （3.5- 4.0 MPa）, allowing for conformable store tank. This work serves to review the state-of-the-art development reported in the scientific literature on adsorbents, adsorption theories, ANG conformable tanks, and related technolo- gies on ANG vehicles. Patent literature has also been searched and discussed. The review aims at illustrating both achievements and problems of the ANG technologies-based vehicles, as well as forecasting the development trends and critical issues to be resolved of these technologies.
基金supported by the National Natural Science Foundation of China (U1507116, 21471152, and 21477130)the Major Research Plan of Natural Science Foundation of China (91326202)The Science Challenge Project of China (JCKY2016212A504) is also acknowledged
文摘Here we present a combined DFF and molecular dynamics study of uranyl （U（VI）） interaction mecha- nisms with the calcite （104） surface in aqueous solution. The roles of three anion ligands （CO2 , HCO3, OH ） and solvation effect in U（VI） interaction with calcite have been evaluated. According to our calculations, water adsorbed on the calcite （104） surface prefers to exist in molecular state rather than dis- sociative state. Energy analysis indicate that the positively charged uranyl species prefers to form surface complexes on the surface, while neutral uranyl species may bind with the surface via both surface complexing and ion exchange reactions of U（VI） → Ca（II）. In contrast, the negatively charged uranyl species prefer to interact with the surface via ion exchange reactions of U（VI）→ Ca（II）, and the one with UO2（CO3）2（H2O）^2- as the reactant becomes the most favorable one in energy. We also found that uranyl adsorption increases the hydrophilicability of the （104） surface to different extents, where the UO2（CO3）3Ca2 species contributes to the largest degree of energy changes （ 53 kcal/mol）. Our calcula- tions proved that the （104） surface also has the ability to immobilize U（VI） via either surface complexing or ion exchange mechanisms under different pH values.
