Clarification of the molecular mechanism underlying the interaction of coal with CH4, CO2, and H2 O molecules is the basis for an in-depth understanding of the states of fluid in coal and fluid-induced coal swelling/c...Clarification of the molecular mechanism underlying the interaction of coal with CH4, CO2, and H2 O molecules is the basis for an in-depth understanding of the states of fluid in coal and fluid-induced coal swelling/contraction. In terms of instrumental analysis, molecular simulation technology based on molecular mechanics/dynamics and quantum chemistry is a powerful tool for revealing the relationship between the structure and properties of a substance and understanding the interaction mechanisms of physical-chemical systems. In this study, the giant canonical ensemble Monte Carlo（GCMC） and molecular dynamics（MD） methods were applied to investigate the adsorption behavior of a Yanzhou coal model（C222H185N3O17S5）. We explored the adsorption amounts of CH4, CO2, and H2 O onto Yanzhou coal, the adsorption conformation, and the impact of oxygen-containing functional groups. Furthermore, we revealed the different adsorption mechanisms of the three substances using isosteric heat of adsorption and energy change data.（1） The adsorption isotherms of the mono-component CH4, CO2, and H2 O were consistent with the Langmuir model, and their adsorption amounts showed an order of CH4CO2〉CH4. In addition, at higher temperatures, the isosteric heat of adsorption decreased; pressure had no significant effect on the heat of adsorption.（3） CH4 molecules displayed an aggregated distribution in the pores, whereas CO2 molecules were cross arranged in pairs. Regarding H2 O molecules, under the influence of hydrogen bonds, the O atom pointed to surrounding H2 O molecules or the H atoms of coal molecules in a regular pattern. The intermolecular distances of the three substances were 0.421, 0.553, and 0.290 nm, respectively. The radial distribution function（RDF） analysis showed that H2 O molecules were arranged in the most compact fashion, forming a tight molecular layer.（4） H2 O molecules showed a significantly stratified distribution around oxygen-containing functional groups on the coal surface, and the b展开更多
Cyclodextrin-modified graphene oxide nanosheets(denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spect...Cyclodextrin-modified graphene oxide nanosheets(denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and potentiometric acid-base titration. The characterization results indicated that CD was successfully grafted onto GO surfaces by forming a chemical bond. Mutual effects on the simultaneous removal of hexavalent uranium and humic acid by CD/GO from aqueous solution were investigated. The results indicated that U(VI) and humic acid(HA) sorption on CD/GO were greatly affected by pH and ionic strength. The presence of HA enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH, whereas the presence of U(VI) enhanced HA sorption. The surface adsorbed HA acted as a "bridge" between U(VI) and CD/GO, and formed strong inner-sphere surface complexes with U(VI). Sorption isotherms of U(VI) or HA on CD/GO could be well fitted by the Langmuir model. This work highlights that CD/GO can be used as a promising material in the enrichment of U(VI) and HA from wastewater in U(VI) and humic substances obtained by environmental pollution cleanup.展开更多
Batch experiments were conducted to investigate the behavior and mechanisms for the adsorption of Cd(Ⅱ) from aqueous solutions by tourmaline under acidic conditions. The results indicated that the adsorption of Cd(Ⅱ...Batch experiments were conducted to investigate the behavior and mechanisms for the adsorption of Cd(Ⅱ) from aqueous solutions by tourmaline under acidic conditions. The results indicated that the adsorption of Cd(Ⅱ) significantly depend on the adsorption time, temperature, and the initial concentration of the metal ion. Furthermore, tourmaline had a very good adsorption capacity for Cd(Ⅱ) in acidic, neutral and alkaline aqueous solutions. This good adsorption capacity is attributed to the observation that tourmaline can automatically adjust the pH values of acidic (except pH 2.0 and 3.0), neutral or alkaline aqueous solutions to 6.4. Specifically, the removal capacity for Cd(Ⅱ) was higher at strongly acidic pH values (in contrast to industrial wastewater pH values) compared to that obtained for other types of adsorbents. Furthermore, the results obtained in this study showed good fits to the Langmuir and Freundlich adsorption isotherms. However, the Langmuir model fit better than the Freundlich model. The maximum uptake of Cd(Ⅱ) by tourmaline was 31.77, 33.11 and 40.16 mg/g at pH 4.0 at 15, 25 and 35°C, respectively. Therefore, tourmaline is an effective adsorbent for the removal of Cd(Ⅱ) from acidic aqueous solutions. In addition, the kinetics for the Cd(Ⅱ) adsorption by tourmaline closely followed the pseudo-second-order model. The thermodynamic parameters indicated that adsorption was feasible, spontaneous, and endothermic. Furthermore, the pH variation after adsorption, ζ-potential, metal ions desorbed and released, and FT-IR analysis indicated that the physisorption and chemisorption mechanisms of tourmaline for heavy metals. These mechanisms included water that was automatically polarized by tourmaline, the ion exchange process, and electropolar adsorption. Among the mechanisms, the automatic polarization of water caused by tourmaline is a unique adsorption mechanism for tourmaline.展开更多
获得在酸碱介质中稳定性好、溶胀率小的壳聚糖/PVA微粒的基础上,探讨了时间、pH、温度等因素对壳聚糖/PVA微粒吸附Cr(Ⅵ)的影响,结果表明:温度与pH是影响吸附量最主要因素。在平均粒径为200μm,最适pH=3、28℃振荡240 m in其吸附量达200...获得在酸碱介质中稳定性好、溶胀率小的壳聚糖/PVA微粒的基础上,探讨了时间、pH、温度等因素对壳聚糖/PVA微粒吸附Cr(Ⅵ)的影响,结果表明:温度与pH是影响吸附量最主要因素。在平均粒径为200μm,最适pH=3、28℃振荡240 m in其吸附量达200 mg/g以上,吸附量随温度的升高而增大。通过计算不同温度下各热力学参数ΔG、ΔH和ΔS,证实该吸附为一自发的吸热过程。对实验数据运用相关数学模型拟合,得出等温吸附平衡符合Langmuir模型,吸附过程动力学更适合二级反应。展开更多
CO2 sorption and diffusion in coal are closely related to the occurrence of coal and gas outburst,geological sequestration of CO2 in coalbeds,and enhancing coalbed methane recovery by injecting CO2.Hence,it is signifi...CO2 sorption and diffusion in coal are closely related to the occurrence of coal and gas outburst,geological sequestration of CO2 in coalbeds,and enhancing coalbed methane recovery by injecting CO2.Hence,it is significant to investigate the sorption properties and diffusion models of CO2 in coal.Here we used a newly designed experimental apparatus at Peking University to investigate the sorption and diffusion properties of CO2 in natural coal samples from Dashucun Mine and Wutongzhuang Mine in Handan city,Hebei province,and Jinhuagong Mine in Datong city,Shanxi province,and obtained CO2 sorption isotherms and diffusivity models.The results indicate that,in a certain pressure range,CO2 sorption isotherms for the coal samples are consistent with the Langmuir model,which assumes that monolayer sorption occurs at the interface between coal matrix and CO2 molecules,and the sorption isotherms feature nonstandard hyperbolas in mathematics.At the same pressure and temperature,as the vitrinite content increases,coal adsorbs more CO2 molecules.The relation between the sorption capacity and the coal rank may be described as a "U-type" trend,and medium rank coal has the least sorption capacity.The bulk diffusivity of CO2 in coal is not constant;in the range of CO2 mass fraction greater than 1%,it increases roughly linearly with increasing mass fraction of CO2 adsorbed(or CO2 partial pressure) in coal.CO2 diffusivity in coal is approximately 10-4 to 10-2 mm2/s in magnitudes,and the diffusivity ranges in coal samples are 3×10-4 to 8×10-3 mm2/s from Dashucun Mine,2×10-4 to 4×10-3 mm2/s from Wutongzhuang Mine,and 2×10-4 to 4×10-3 mm2/s from Jinhuagong Mine.The results of the CO2 sorption and diffusion study can be applied to help predict and prevent coal and gas outburst as well as to evaluate the feasibility in geological sequestration of CO2 and to enhance coalbed methane recovery.展开更多
基金supported by National Natural Science Foundation of China(Grant Nos.41072116,41102092,41302127,41372165)Special Research Foundation for the Doctoral Program of Higher Education of China(Grant No.20091402110002)+1 种基金Science Project of Taiyuan city(Grant No.120247-27)outstanding funding innovative projects for the graduate students by Shanxi Province in 2010
文摘Clarification of the molecular mechanism underlying the interaction of coal with CH4, CO2, and H2 O molecules is the basis for an in-depth understanding of the states of fluid in coal and fluid-induced coal swelling/contraction. In terms of instrumental analysis, molecular simulation technology based on molecular mechanics/dynamics and quantum chemistry is a powerful tool for revealing the relationship between the structure and properties of a substance and understanding the interaction mechanisms of physical-chemical systems. In this study, the giant canonical ensemble Monte Carlo（GCMC） and molecular dynamics（MD） methods were applied to investigate the adsorption behavior of a Yanzhou coal model（C222H185N3O17S5）. We explored the adsorption amounts of CH4, CO2, and H2 O onto Yanzhou coal, the adsorption conformation, and the impact of oxygen-containing functional groups. Furthermore, we revealed the different adsorption mechanisms of the three substances using isosteric heat of adsorption and energy change data.（1） The adsorption isotherms of the mono-component CH4, CO2, and H2 O were consistent with the Langmuir model, and their adsorption amounts showed an order of CH4CO2〉CH4. In addition, at higher temperatures, the isosteric heat of adsorption decreased; pressure had no significant effect on the heat of adsorption.（3） CH4 molecules displayed an aggregated distribution in the pores, whereas CO2 molecules were cross arranged in pairs. Regarding H2 O molecules, under the influence of hydrogen bonds, the O atom pointed to surrounding H2 O molecules or the H atoms of coal molecules in a regular pattern. The intermolecular distances of the three substances were 0.421, 0.553, and 0.290 nm, respectively. The radial distribution function（RDF） analysis showed that H2 O molecules were arranged in the most compact fashion, forming a tight molecular layer.（4） H2 O molecules showed a significantly stratified distribution around oxygen-containing functional groups on the coal surface, and the b
基金supported by the National Natural Science Foundation of China(91326202,21375148,21207136,21225730)the Hefei Center for Physical Science and Technology(2012FXZY005)
文摘Cyclodextrin-modified graphene oxide nanosheets(denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and potentiometric acid-base titration. The characterization results indicated that CD was successfully grafted onto GO surfaces by forming a chemical bond. Mutual effects on the simultaneous removal of hexavalent uranium and humic acid by CD/GO from aqueous solution were investigated. The results indicated that U(VI) and humic acid(HA) sorption on CD/GO were greatly affected by pH and ionic strength. The presence of HA enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH, whereas the presence of U(VI) enhanced HA sorption. The surface adsorbed HA acted as a "bridge" between U(VI) and CD/GO, and formed strong inner-sphere surface complexes with U(VI). Sorption isotherms of U(VI) or HA on CD/GO could be well fitted by the Langmuir model. This work highlights that CD/GO can be used as a promising material in the enrichment of U(VI) and HA from wastewater in U(VI) and humic substances obtained by environmental pollution cleanup.
基金supported by the National Natural Science Foundation of China (20907024)the Fundamental Research Funds for the Central Universities
文摘Batch experiments were conducted to investigate the behavior and mechanisms for the adsorption of Cd(Ⅱ) from aqueous solutions by tourmaline under acidic conditions. The results indicated that the adsorption of Cd(Ⅱ) significantly depend on the adsorption time, temperature, and the initial concentration of the metal ion. Furthermore, tourmaline had a very good adsorption capacity for Cd(Ⅱ) in acidic, neutral and alkaline aqueous solutions. This good adsorption capacity is attributed to the observation that tourmaline can automatically adjust the pH values of acidic (except pH 2.0 and 3.0), neutral or alkaline aqueous solutions to 6.4. Specifically, the removal capacity for Cd(Ⅱ) was higher at strongly acidic pH values (in contrast to industrial wastewater pH values) compared to that obtained for other types of adsorbents. Furthermore, the results obtained in this study showed good fits to the Langmuir and Freundlich adsorption isotherms. However, the Langmuir model fit better than the Freundlich model. The maximum uptake of Cd(Ⅱ) by tourmaline was 31.77, 33.11 and 40.16 mg/g at pH 4.0 at 15, 25 and 35°C, respectively. Therefore, tourmaline is an effective adsorbent for the removal of Cd(Ⅱ) from acidic aqueous solutions. In addition, the kinetics for the Cd(Ⅱ) adsorption by tourmaline closely followed the pseudo-second-order model. The thermodynamic parameters indicated that adsorption was feasible, spontaneous, and endothermic. Furthermore, the pH variation after adsorption, ζ-potential, metal ions desorbed and released, and FT-IR analysis indicated that the physisorption and chemisorption mechanisms of tourmaline for heavy metals. These mechanisms included water that was automatically polarized by tourmaline, the ion exchange process, and electropolar adsorption. Among the mechanisms, the automatic polarization of water caused by tourmaline is a unique adsorption mechanism for tourmaline.
文摘获得在酸碱介质中稳定性好、溶胀率小的壳聚糖/PVA微粒的基础上,探讨了时间、pH、温度等因素对壳聚糖/PVA微粒吸附Cr(Ⅵ)的影响,结果表明:温度与pH是影响吸附量最主要因素。在平均粒径为200μm,最适pH=3、28℃振荡240 m in其吸附量达200 mg/g以上,吸附量随温度的升高而增大。通过计算不同温度下各热力学参数ΔG、ΔH和ΔS,证实该吸附为一自发的吸热过程。对实验数据运用相关数学模型拟合,得出等温吸附平衡符合Langmuir模型,吸附过程动力学更适合二级反应。
基金supported by Peking University (985 Program by Chinese Ministry of Education)the National Natural Science Foundation of China (Grant No.40640420141)
文摘CO2 sorption and diffusion in coal are closely related to the occurrence of coal and gas outburst,geological sequestration of CO2 in coalbeds,and enhancing coalbed methane recovery by injecting CO2.Hence,it is significant to investigate the sorption properties and diffusion models of CO2 in coal.Here we used a newly designed experimental apparatus at Peking University to investigate the sorption and diffusion properties of CO2 in natural coal samples from Dashucun Mine and Wutongzhuang Mine in Handan city,Hebei province,and Jinhuagong Mine in Datong city,Shanxi province,and obtained CO2 sorption isotherms and diffusivity models.The results indicate that,in a certain pressure range,CO2 sorption isotherms for the coal samples are consistent with the Langmuir model,which assumes that monolayer sorption occurs at the interface between coal matrix and CO2 molecules,and the sorption isotherms feature nonstandard hyperbolas in mathematics.At the same pressure and temperature,as the vitrinite content increases,coal adsorbs more CO2 molecules.The relation between the sorption capacity and the coal rank may be described as a "U-type" trend,and medium rank coal has the least sorption capacity.The bulk diffusivity of CO2 in coal is not constant;in the range of CO2 mass fraction greater than 1%,it increases roughly linearly with increasing mass fraction of CO2 adsorbed(or CO2 partial pressure) in coal.CO2 diffusivity in coal is approximately 10-4 to 10-2 mm2/s in magnitudes,and the diffusivity ranges in coal samples are 3×10-4 to 8×10-3 mm2/s from Dashucun Mine,2×10-4 to 4×10-3 mm2/s from Wutongzhuang Mine,and 2×10-4 to 4×10-3 mm2/s from Jinhuagong Mine.The results of the CO2 sorption and diffusion study can be applied to help predict and prevent coal and gas outburst as well as to evaluate the feasibility in geological sequestration of CO2 and to enhance coalbed methane recovery.
