Enhanced uptake and selectivity of CO(2) adsorption in a hydrostable metal-organic frameworks via incorporating methylol and methyl groups.

A new methylol and methyl functionalized metal-organic frameworks (MOFs) QI-Cu has been designed and synthesized. As a variant of NOTT-101, this material exhibits excellent CO2 uptake capacities at ambient temperature and pressure, as well as high CH4 uptake capacities. The CO2 uptake for QI-Cu is high, up to 4.56 mmol g(-1) at 1 bar and 293 K, which is top-ranked among MOFs for CO2 adsorption and significantly larger than the nonfunctionalized NOTT-101 of 3.93 mmol g(-1). The enhanced isosteric heat values of CO2 and CH4 adsorption were also obtained for this linker functionalized MOFs. From the single-component adsorption isotherms, multicomponent adsorption was predicted using the ideal adsorbed solution theory (IAST). QI-Cu shows an improvement in adsorptive selectivity of CO2 over CH4 and N2 below 1 bar. The incorporation of methylol and methyl groups also greatly improves the hydrostability of the whole framework.

[1]  S. Han,et al.  Diamine-functionalized metal-organic framework: Exceptionally high CO 2 capacities from ambient air and flue gas, ultrafast CO2 uptake rate, and adsorption mechanism , 2014 .

[2]  Hong‐Cai Zhou,et al.  Tuning the Moisture and Thermal Stability of Metal–Organic Frameworks through Incorporation of Pendant Hydrophobic Groups , 2013 .

[3]  W. Zhou,et al.  A series of metal–organic frameworks with high methane uptake and an empirical equation for predicting methane storage capacity , 2013 .

[4]  Tony Pham,et al.  A robust molecular porous material with high CO2 uptake and selectivity. , 2013, Journal of the American Chemical Society.

[5]  Krista S. Walton,et al.  Molecular-level insight into unusual low pressure CO2 affinity in pillared metal-organic frameworks. , 2013, Journal of the American Chemical Society.

[6]  V. Valtchev,et al.  Tailored Crystalline Microporous Materials by Post‐Synthesis Modification , 2013 .

[7]  Stephen D. Burd,et al.  Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation , 2013, Nature.

[8]  Perla B. Balbuena,et al.  Porous materials with pre-designed single-molecule traps for CO2 selective adsorption , 2013, Nature Communications.

[9]  C. Malliakas,et al.  A straight forward route for the development of metal-organic frameworks functionalized with aromatic -OH groups: synthesis, characterization, and gas (N2, Ar, H2, CO2, CH4, NH3) sorption properties. , 2013, Inorganic chemistry.

[10]  V. Valtchev,et al.  Tailored crystalline microporous materials by post-synthesis modification. , 2013, Chemical Society reviews.

[11]  Jinhee Park,et al.  Introduction of functionalized mesopores to metal-organic frameworks via metal-ligand-fragment coassembly. , 2012, Journal of the American Chemical Society.

[12]  A. J. Blake,et al.  Selectivity and direct visualization of carbon dioxide and sulfur dioxide in a decorated porous host. , 2012, Nature chemistry.

[13]  Omar K Farha,et al.  Metal-organic framework materials with ultrahigh surface areas: is the sky the limit? , 2012, Journal of the American Chemical Society.

[14]  Hong‐Cai Zhou,et al.  Pore surface engineering with controlled loadings of functional groups via click chemistry in highly stable metal-organic frameworks. , 2012, Journal of the American Chemical Society.

[15]  R. Krishna,et al.  Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions , 2012, Nature Communications.

[16]  Daryl R. Brown,et al.  Progress in Adsorption‐Based CO2 Capture by Metal—Organic Frameworks , 2012 .

[17]  J. F. Stoddart,et al.  Large-Pore Apertures in a Series of Metal-Organic Frameworks , 2012, Science.

[18]  Jun Liu,et al.  Progress in adsorption-based CO2 capture by metal-organic frameworks. , 2012, Chemical Society reviews.

[19]  Kenji Sumida,et al.  Carbon dioxide capture in metal-organic frameworks. , 2012, Chemical reviews.

[20]  A. Samanta,et al.  Post-Combustion CO2 Capture Using Solid Sorbents: A Review , 2012 .

[21]  J. Long,et al.  Introduction to metal-organic frameworks. , 2012, Chemical reviews.

[22]  C. Wilmer,et al.  Large-scale screening of hypothetical metal-organic frameworks. , 2012, Nature chemistry.

[23]  D. Zhao,et al.  Three-dimensional pillar-layered copper(II) metal-organic framework with immobilized functional OH groups on pore surfaces for highly selective CO2/CH4 and C2H2/CH4 gas sorption at room temperature. , 2011, Inorganic chemistry.

[24]  Randall Q. Snurr,et al.  Ultrahigh Porosity in Metal-Organic Frameworks , 2010, Science.

[25]  Wei Zhou,et al.  Metal-organic frameworks with exceptionally high methane uptake: where and how is methane stored? , 2010, Chemistry.

[26]  M. Pinto,et al.  Comparison of Methods to Obtain Micropore Size Distributions of Carbonaceous Materials from CO2 Adsorption Based on the Dubinin−Radushkevich Isotherm , 2010 .

[27]  Christian J. Doonan,et al.  Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks , 2010, Science.

[28]  Christopher W. Jones,et al.  Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources , 2010 .

[29]  A. Spek,et al.  Electrocatalytic CO2 Conversion to Oxalate by a Copper Complex , 2010, Science.

[30]  Randall Q Snurr,et al.  Screening of metal-organic frameworks for carbon dioxide capture from flue gas using a combined experimental and modeling approach. , 2009, Journal of the American Chemical Society.

[31]  R. Stuart Haszeldine,et al.  Carbon Capture and Storage: How Green Can Black Be? , 2009, Science.

[32]  Gary T. Rochelle,et al.  Amine Scrubbing for CO2 Capture , 2009, Science.

[33]  N. Meinshausen,et al.  Warming caused by cumulative carbon emissions towards the trillionth tonne , 2009, Nature.

[34]  Hong-Cai Zhou,et al.  Selective gas adsorption and separation in metal-organic frameworks. , 2009, Chemical Society reviews.

[35]  Freek Kapteijn,et al.  An amine-functionalized MIL-53 metal-organic framework with large separation power for CO2 and CH4. , 2009, Journal of the American Chemical Society.

[36]  Randall Q. Snurr,et al.  Enhanced CO2 Adsorption in Metal-Organic Frameworks via Occupation of Open-Metal Sites by Coordinated Water Molecules , 2009 .

[37]  Alexander J. Blake,et al.  High capacity hydrogen adsorption in Cu(II) tetracarboxylate framework materials: the role of pore size, ligand functionalization, and exposed metal sites. , 2009, Journal of the American Chemical Society.

[38]  C. Grimes,et al.  and Water Vapor to Hydrocarbon Fuels , 2009 .

[39]  A. Matzger,et al.  Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores. , 2008, Journal of the American Chemical Society.

[40]  Michael O'Keeffe,et al.  High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture , 2008, Science.

[41]  David B. Stephenson,et al.  A Changing Climate for Prediction , 2007, Science.

[42]  A. J. Blake,et al.  High H2 adsorption by coordination-framework materials. , 2006, Angewandte Chemie.

[43]  A. Fletcher,et al.  Hydrogen adsorption on functionalized nanoporous activated carbons. , 2005, The journal of physical chemistry. B.

[44]  Michael O'Keeffe,et al.  Reticular synthesis and the design of new materials , 2003, Nature.

[45]  Anthony L. Spek,et al.  Journal of , 1993 .

[46]  P. Carrott,et al.  Evaluation of the Stoeckli method for the estimation of micropore size distributions of activated charcoal cloths , 1999 .

[47]  P. van der Sluis,et al.  BYPASS: an effective method for the refinement of crystal structures containing disordered solvent regions , 1990 .

[48]  Alan L. Myers,et al.  Thermodynamics of mixed‐gas adsorption , 1965 .

[49]  E. Teller,et al.  ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS , 1938 .