Gas Storage and Diffusion through Nanocages and Windows in Porous Metal-Organic Framework Cu-2(2,3,5,6-tetramethylbenzene-1,4-diisophthalate)(H2O)(2)

doi:10.1021/cm403697m

	Gas Storage and Diffusion through Nanocages and Windows in Porous Metal-Organic Framework Cu-2(2,3,5,6-tetramethylbenzene-1,4-diisophthalate)(H2O)(2)
	Li, Liangjun1 ; Bell, Jon G.2; Tang, Sifu3 ; Lv, Xiaoxia 3; Wang, Chao3 ; Xing, Yanlong3 ; Zhao, Xuebo 1,3; Thomas, K. Mark 2
	2014-08-26
发表期刊	CHEMISTRY OF MATERIALS
卷号	26 期号:16 页码:4679-4695
摘要	A novel nanoporous metal organic framework NPC-4 with excellent thermal stability was assembled from 2,3,5,6-tetramethylbenzene-1,4-diisophthalate (TMBDI) and the paddle-wheel secondary building unit (Cu-2(COO)(4)). The porous structure comprises a single type of nanoscale cage (16 angstrom diameter) interconnected by windows (5.2 X 6.3 angstrom), which give a high pore volume. CH4 (195-290 K), CO2 (198-303 K), N-2 (77 K), and H-2 (77 K) adsorption isotherms were studied for pressures up to 20 bar. NPC-4 exhibits excellent methane and carbon dioxide storage capacities on a volume basis with very high adsorbate densities, under ambient conditions. Isobars were investigated to establish the relationship for adsorption capacities over a range of storage temperatures. The isosteric enthalpies of adsorption for both CH4 and CO2 adsorption did not vary significantly with amount adsorbed and were similar to 15 and similar to 25 kJ mol(-1), respectively. The adsorption/desorption kinetics for CH4 and CO2 were investigated and activation energies, enthalpies of activation, and diffusion parameters determined using various kinetic models. The activation energies for adsorption obtained over a range of uptakes from the stretched exponential kinetic model were 5.1-6.3 kJ mol(-1) (2-13.5 mmol g(-1)) for CO2 and 2.7-5.6 kJ mol(-1) (2-9 mmol g(-1)) for CH4. The activation energies for surface barriers and diffusion along pores for both CH4 and CO2 adsorption obtained from a combined barrier resistance diffusion model did not vary markedly with amount adsorbed and were <9 kJ mol(-1). Comparison of kinetic and thermodynamic parameters for CH4 and CO2 indicates that a surface barrier is rate determining at high uptakes, while intrapartide diffusion involving diffusion through pores, consisting of narrow windows interconnecting with nanocages, being rate determining at very low uptakes. The faster CH4 intraparticle adsorption kinetics compared with CO2 for NPC-4 was attributed to faster surface diffusion due to the lower isosteric enthalpy of adsorption for CH4.
文章类型	Article
WOS标题词	Science & Technology ; Physical Sciences ; Technology
DOI	10.1021/cm403697m
关键词[WOS]	HIGH-CAPACITY HYDROGEN ; HIGH METHANE UPTAKE ; CARBON-DIOXIDE ; PORE-SIZE ; DIELECTRIC-RELAXATION ; ADSORPTION-KINETICS ; SELECTIVE SORPTION ; MOLECULAR-DYNAMICS ; NEUTRON-SCATTERING ; SMALL HYDROCARBONS
收录类别	SCI
语种	英语
WOS研究方向	Chemistry ; Materials Science
WOS类目	Chemistry, Physical ; Materials Science, Multidisciplinary
WOS记录号	WOS:000340992900004
引用统计
文献类型	期刊论文
条目标识符	http://ir.qibebt.ac.cn/handle/337004/6371
专题	储氢及新型纳孔材料团队（过去）
作者单位	1.China Univ Petr East China, Inst Unconvent Hydrocarbon & New Energy Sources, Qingdao 266580, Shandong, Peoples R China 2.Newcastle Univ, Sch Chem Engn & Adv Mat, Wolfson Northern Carbon Reduct Labs, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England 3.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Qingdao 266101, Shandong, Peoples R China
推荐引用方式 GB/T 7714	Li, Liangjun,Bell, Jon G.,Tang, Sifu,et al. Gas Storage and Diffusion through Nanocages and Windows in Porous Metal-Organic Framework Cu-2(2,3,5,6-tetramethylbenzene-1,4-diisophthalate)(H2O)(2)[J]. CHEMISTRY OF MATERIALS,2014,26(16):4679-4695.
APA	Li, Liangjun.,Bell, Jon G..,Tang, Sifu.,Lv, Xiaoxia.,Wang, Chao.,...&Thomas, K. Mark.(2014).Gas Storage and Diffusion through Nanocages and Windows in Porous Metal-Organic Framework Cu-2(2,3,5,6-tetramethylbenzene-1,4-diisophthalate)(H2O)(2).CHEMISTRY OF MATERIALS,26(16),4679-4695.
MLA	Li, Liangjun,et al."Gas Storage and Diffusion through Nanocages and Windows in Porous Metal-Organic Framework Cu-2(2,3,5,6-tetramethylbenzene-1,4-diisophthalate)(H2O)(2)".CHEMISTRY OF MATERIALS 26.16(2014):4679-4695.