Effect of Pore Topology and Accessibility on Gas Adsorption Capacity in Zeolitic−Imidazolate Frameworks: Bringing Molecular Simulation Close to Experiment

2011 ◽  
Vol 115 (16) ◽  
pp. 8126-8135 ◽  
Author(s):  
Ravichandar Babarao ◽  
Sheng Dai ◽  
De-en Jiang
Keyword(s):  
Adsorption Capacity ◽  
Molecular Simulation ◽  
Gas Adsorption ◽  
Zeolitic Imidazolate Frameworks

Influence of intramolecular interactions on carbon dioxide gas adsorption capacity in Mesoporous Imine polymers

2018 ◽  
Author(s):  
Jaya Prakash Madda ◽  
Pilli Govindaiah ◽  
Sushant Kumar Jena ◽  
Sabbhavat Krishna ◽  
Rupak Kishor
Keyword(s):  
Carbon Dioxide ◽  
Adsorption Capacity ◽  
Density Functional ◽  
Gas Adsorption ◽  
Ambient Pressure ◽  
Condensation Reaction ◽  
Intramolecular Interactions ◽  
Carbon Dioxide Adsorption ◽  
Nitrogen Gas ◽  
Adsorption Characteristic

<p>Covalent organic Imine polymers with intrinsic meso-porosity were synthesized by condensation reaction between 4,4-diamino diphenyl methane and (para/meta/ortho)-phthaladehyde. Even though these polymers were synthesized from precursors of bis-bis covalent link mode, the bulk materials were micrometer size particles with intrinsic mesoporous enables nitrogen as well as carbon dioxide adsorption in the void spaces. These polymers were showed stability up to 260<sup>o</sup> centigrade. Nitrogen gas adsorption capacity up to 250 cc/g in the ambient pressure was observed with type III adsorption characteristic nature. Carbon dioxide adsorption experiments reveal the possible terminal amine functional group to carbamate with CO<sub>2</sub> gas molecule to the polymers. One of the imine polymers, COP-3 showed more carbon dioxide sorption capacity and isosteric heat of adsorption (Q<sub>st</sub>) than COP-1 and COP-2 at 273 K even though COP-3 had lower porosity for nitrogen gas than COP-1 and COP-2. We explained the trends in gas adsorption capacities and Qst values as a consequence of the intra molecular interactions confirmed by Density Functional Theory computational experiments on small molecular fragments.</p>

Influence of Metal Substitution on the Pressure-Induced Phase Change in Flexible Zeolitic Imidazolate Frameworks

2018 ◽  
Author(s):  
C. Michael McGuirk ◽  
Tomče Runčevski ◽  
Julia Oktawiec ◽  
Ari Turkiewicz ◽  
mercedes K. taylor ◽  
...  
Keyword(s):  
Phase Change ◽  
Single Crystal ◽  
Gas Adsorption ◽  
High Capacity ◽  
Phase Changes ◽  
Zeolitic Imidazolate Frameworks ◽  
Metal Substitution ◽  
Heat Management ◽  
Metal Organic ◽  
First Time

<p>Metal–organic frameworks that display step-shaped adsorption profiles arising from discrete pressure-induced phase changes are promising materials for applications in both high-capacity gas storage and energy-efficient gas separations. The thorough investigation of such materials through chemical diversification, gas adsorption measurements, and <i>in situ </i>structural characterization is therefore crucial for broadening their utility. We examine a series of isoreticular, flexible zeolitic imidazolate frameworks (ZIFs) of the type M(bim)<sub>2</sub> (SOD; M = Zn<sup> </sup>(ZIF-7), Co (ZIF-9), Cd (CdIF-13); bim<sup>–</sup> = benzimidazolate), and elucidate the effects of metal substitution on the pressure-responsive phase changes and the resulting CO<sub>2</sub> and CH<sub>4</sub> step positions, pre-step uptakes, and step capacities. Using ZIF-7 as a benchmark, we reexamine the poorly understood structural transition responsible for its adsorption steps and, through high-pressure adsorption measurements, verify that it displays a step in its CH<sub>4 </sub>adsorption isotherms. The ZIF-9 material is shown to undergo an analogous phase change, yielding adsorption steps for CO<sub>2</sub> and CH<sub>4</sub> with similar profiles and capacities to ZIF-7, but with shifted threshold pressures. Further, the Cd<sup>2+</sup> analogue CdIF-13 is reported here for the first time, and shown to display adsorption behavior distinct from both ZIF-7 and ZIF-9, with negligible pre-step adsorption, a ~50% increase in CO<sub>2</sub> and CH<sub>4</sub> capacity, and dramatically higher threshold adsorption pressures. Remarkably, a single-crystal-to-single-crystal phase change to a pore-gated phase is also achieved with CdIF-13, providing insight into the phase change that yields step-shaped adsorption in these flexible ZIFs. Finally, we show that the endothermic phase change of these frameworks provides intrinsic heat management during gas adsorption. </p>

scholarly journals Molecular simulation of gases competitive adsorption in lignite and analysis of original CO desorption

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Jing Zhang ◽  
Jiren Wang ◽  
Chunhua Zhang ◽  
Zongxiang Li ◽  
Jinchao Zhu ◽  
...  
Keyword(s):  
Adsorption Capacity ◽  
Molecular Simulation ◽  
Competitive Adsorption ◽  
Air Leakage ◽  
Adsorption Characteristics ◽  
Adsorption Sites ◽  
Simulation Based ◽  
Lignite Coal ◽  
Model C ◽  
Grand Canonical

AbstractTo study the adsorption characteristics of CO, CO2, N2, O2, and their binary-components in lignite coal, reveal the influence of CO2 or N2 injection and air leakage on the desorption of CO in goafs, a lignite model (C206H206N2O44) was established, and the supercell structure was optimized under temperatures of 288.15–318.15 K for molecular simulation. Based on molecular dynamics, the Grand Canonical Monte Carlo method was used to simulate the adsorption characteristics and the Langmuir equation was used to fit the adsorption isotherms of gases. The results show that for single-components, the order of adsorption capacity is CO2 > CO > O2 > N2. For binary-components, the competitive adsorption capacities of CO2 and CO are approximate. In the low-pressure zone, the competitive adsorption capacity of CO2 is stronger than that of CO, and the CO is stronger than N2 or O2. From the simulation, it can be seen that CO2, N2 or O2 will occupy adsorption sites, causing CO desorption. Therefore, to prevent the desorption of the original CO in the goaf, it is not suitable to use CO2 or N2 injection for fire prevention, and the air leakage at the working faces need to be controlled.

scholarly journals Changes in Pore Structure of Coal Caused by CS2 Treatment and Its Methane Adsorption Response

Geofluids ◽  
2018 ◽  
Vol 2018 ◽  
pp. 1-11 ◽  
Author(s):  
Run Chen ◽  
Yong Qin ◽  
Pengfei Zhang ◽  
Youyang Wang
Keyword(s):  
Pore Structure ◽  
Adsorption Capacity ◽  
Gas Adsorption ◽  
Recovery Process ◽  
Micropore Volume ◽  
Methane Adsorption ◽  
Coal Bed ◽  
Methane Recovery ◽  
Before And After ◽  
Key Issues

The pore structure and gas adsorption are two key issues that affect the coal bed methane recovery process significantly. To change pore structure and gas adsorption, 5 coals with different ranks were treated by CS2 for 3 h using a Soxhlet extractor under ultrasonic oscillation conditions; the evolutions of pore structure and methane adsorption were examined using a high-pressure mercury intrusion porosimeter (MIP) with an AutoPore IV 9310 series mercury instrument. The results show that the cumulative pore volume and specific surface area (SSA) were increased after CS2 treatment, and the incremental micropore volume and SSA were increased and decreased before and after Ro,max=1.3%, respectively; the incremental big pore (greater than 10 nm in diameter) volumes were increased and SSA was decreased for all coals, and pore connectivity was improved. Methane adsorption capacity on coal before and after Ro,max=1.3% also was increased and decreased, respectively. There is a positive correlation between the changes in the micropore SSA and the Langmuir volume. It confirms that the changes in pore structure and methane adsorption capacity due to CS2 treatment are controlled by the rank, and the change in methane adsorption is impacted by the change of micropore SSA and suggests that the changes in pore structure are better for gas migration; the alteration in methane adsorption capacity is worse and better for methane recovery before and after Ro,max=1.3%. A conceptual mechanism of pore structure is proposed to explain methane adsorption capacity on CS2 treated coal around the Ro,max=1.3%.

scholarly journals Geologic characterization of a lower Cambrian marine shale: Implications for shale gas potential in northwestern Hunan, South China

2018 ◽  
Vol 6 (3) ◽  
pp. T635-T647 ◽  
Author(s):  
Zhenghui Xiao ◽  
Jisong Liu ◽  
Jingqiang Tan ◽  
Rongfeng Yang ◽  
Jason Hilton ◽  
...  
Keyword(s):  
Adsorption Capacity ◽  
South China ◽  
Lower Cambrian ◽  
Gas Adsorption ◽  
Vitrinite Reflectance ◽  
Mean Value ◽  
Hunan Province ◽  
Quartz Content ◽  
Gas Potential

We have investigated the geologic features of the lower Cambrian-aged Niutitang Shale in the northwestern Hunan province of South China. Our results indicate that the Niutitang Shale has abundant and highly mature algal kerogen with total organic carbon (TOC) content ranging from 0.6% to 18.2%. The equivalent vitrinite reflectance (equal-Ro) value is between 2.5% and 4.3%. Mineral constituents are dominated by quartz and clay. The average quartz content (62.8%) is much higher than that of clay minerals (26.1%), and this suggests a high brittleness index. Organic-matter pores, interparticle pores, intraparticle pores, interlaminated fractures, and structural fractures are all well developed. The porosity ranges from 0.6% to 8.8%, with an average of 4.8%, whereas the permeability varies from 0.0018 to [Formula: see text] (microdarcy) (averaging [Formula: see text]). The porosity of TOC- and clay-rich shale samples is generally higher than that of quartz-rich shale samples. The gas adsorption capacity of the Niutitang Shale varies from 2.26 to [Formula: see text], with a mean value of [Formula: see text]. The TOC content appears to significantly influence gas adsorption capacity. In general, TOC-rich samples exhibit a much higher adsorption capacity than TOC-poor samples.

scholarly journals Experimental Analysis of Pore Structure and Fractal Characteristics of Soft and Hard Coals With Same Coalification

2021 ◽  
Author(s):  
Barkat Ullah ◽  
Yuanping Cheng ◽  
Liang Wang ◽  
Weihua Yang ◽  
Izhar Mithal Jiskani ◽  
...  
Keyword(s):  
Pore Structure ◽  
Adsorption Capacity ◽  
Gas Adsorption ◽  
Hysteresis Loops ◽  
Control Measures ◽  
Practical Significance ◽  
Coal Bed ◽  
Hard Coal ◽  
Pore Surface ◽  
Soft Coal

Abstract Accurate and quantitative investigation of the physical structure and fractal geometry of coal has important theoretical and practical significance for coal bed methane and the prevention of dynamic disasters such as coal and gas outbursts. This study investigates the pore structure and fractural characteristics of soft and hard coals using nitrogen and carbon dioxide (N2/CO2) adsorption. Coal samples from Pingdingshan Mine in Henan province of China were collected and pulverized to the required size (0.2-0.25mm). N2/CO2 adsorption tests were performed to evaluate the pore size distribution (PSD), specific surface area (SSA), and pore volume (PV). The pore structure was characterized based on fractural theory. The results unveiled that the strength of coal has a significant influence on pore structure and fracture dimensions. The obvious N2-adsorption isotherms of the coals were verified as Type IV (A) and Type II. The shape of the hysteresis loops indicates the presence of slit-shaped pores. There are significant differences in SSA and PV between both coals. The soft coal showed larger SSA and PV than hard coal that shows consistency with adsorption capacity. The fractal dimensions of soft coal are respectively larger than that of hard coal. The greater the value of D1 (complexity of pore surface) of soft coal is, the larger the pore surface roughness and gas adsorption capacity is. The results enable us to conclude that the characterization of pores and fractures of soft and hard coals is different, tending to different adsorption/desorption characteristics and outburst sensitivity. In this regard, results provide a reference for formulating corresponding coal and gas outburst prevention and control measures.

scholarly journals Molecular Simulation of Shale Gas Adsorption and Diffusion in Clay Nanopores

Computation ◽  
2015 ◽  
Vol 3 (4) ◽  
pp. 687-700 ◽  
Author(s):  
Hongguang Sui ◽  
Jun Yao ◽  
Lei Zhang
Keyword(s):  
Molecular Simulation ◽  
Shale Gas ◽  
Gas Adsorption ◽  
And Diffusion

scholarly journals The binary gas sorption in the bituminous coal of the Huaibei Coalfield in China

2018 ◽  
Vol 36 (9-10) ◽  
pp. 1612-1628 ◽  
Author(s):  
Lei Zhang ◽  
Zhiwei Ye ◽  
Mingxue Li ◽  
Cun Zhang ◽  
Qingsheng Bai ◽  
...  
Keyword(s):  
Adsorption Capacity ◽  
Sorption Capacity ◽  
Bituminous Coal ◽  
Gas Adsorption ◽  
Langmuir Equation ◽  
Separation Coefficient ◽  
Gas Sorption ◽  
Langmuir Adsorption ◽  
Gas Molecules ◽  
Huaibei Coalfield

Knowledge of the gas sorption characteristics of a coal not only helps to explain the mechanism of enhanced coalbed methane recovery but also provides an important basis for simultaneous coal and gas extraction. In consequence, the pure and binary gas excess sorption capacity of methane, carbon dioxide, and nitrogen of bituminous coal samples derived from the Xutuan Coal Mine in Huaibei coalfield, in Anhui Province in China, was measured using the volumetric method. The fitting analysis of the pure gas Langmuir adsorption model was carried out. The binary gas excess sorption measurement showed that the final sorption capacity of bituminous samples was the same no matter what the gas adsorption order of competitive adsorption and displacement adsorption. Hence, coal gas adsorption is physical adsorption, i.e. the different adsorption and desorption process of gas molecules does not affect the final adsorption amount of coal to each component of gas. Using the fitting parameters obtained by the Langmuir equation, the extended Langmuir equation was used to predict the adsorption capacity for each component of the binary gas. The comparison between predicted adsorption capacity and measured adsorption capacity showed that the extended Langmuir equation can better describe the trend of the adsorption isotherm curves of a binary gas under different pressures. The separation coefficient and displacement coefficient were defined from Langmuir adsorption theory. The separation coefficient involves the proportion of each component in the free phase and the proportion of each component in the adsorption phase. The displacement coefficient involves the displacement ability of gas molecules at adsorption sites by free gas molecules.

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