Pore-Space-Partition-Enabled Exceptional Ethane Uptake and Ethane-Selective Ethane–Ethylene Separation

Yang, Huajun; Wang, Yanxiang; Krishna, Rajamani; Jia, Xiaoxia; Wang, Yong; Hong, Anh N.; Dang, Candy; Castillo, Henry E.; Bu, Xianhui; Feng, Pingyun

doi:10.1021/jacs.9b12924

Title: Pore-Space-Partition-Enabled Exceptional Ethane Uptake and Ethane-Selective Ethane–Ethylene Separation

Journal Article · Mon Jan 27 00:00:00 UTC 2020 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b12924 · OSTI ID:1599639

^[1]; Wang, Yanxiang ^[2];

^[3]; Jia, Xiaoxia ^[2];

^[2];

^[2]; Dang, Candy ^[4]; Castillo, Henry E. ^[4];

^[4];

^[2]

California State Univ. (CalState), Long Beach, CA (United States); Univ. of California, Riverside, CA (United States); UC Riverside
Univ. of California, Riverside, CA (United States)
Univ. of Amsterdam (Netherlands)
California State Univ. (CalState), Long Beach, CA (United States)

A modell material for C₂H₆/C₂H₄ separation would simultaneously have the highest C₂H₆ uptake capacity and the highest C₂H₆/C₂H₄ selectivity. But such material is elusive. A benchmark material for ethane-selective C₂H₆/C₂H₄ separation is peroxo-functionalized MOF-74-Fe that exhibits the best known separation performance due to its high C₂H₆/C₂H₄ selectivity (4.4), although its C₂H₆ uptake capacity is moderate (74.3 cm³/g). Here, we report a family of pore-space-partitioned crystalline porous materials (CPMs) with exceptional C₂H₆ uptake capacity and C₂H₆/C₂H₄ separation potential (i.e., C₂H₄ recovered from the mixture) despite their moderate C₂H₆/C₂H₄ selectivity (up to 1.75). The ethane uptake capacity as high as 166.8 cm³/g at 1 atm and 298 K, more than twice that of peroxo-MOF-74-Fe, was previously achieved even though the isosteric heat of adsorption (21.9–30.4 kJ/mol) for these CPMs is as low as about one-third of that for peroxo-MOF-74-Fe (66.8 kJ/mol). While the overall C₂H₆/C₂H₄ separation potentials have not yet surpassed peroxo-MOF-74-Fe, these robust CPMs exhibit outstanding properties including high thermal stability (up to 450 °C) and aqueous stability, low regeneration energy, and a high degree of chemical and geometrical tunability within the same isoreticular framework.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of California, Riverside, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0010596

OSTI ID:: 1599639

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 5 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (51)

Stable Metal-Organic Frameworks: Design, Synthesis, and Applications Yuan, Shuai; Feng, Liang; Wang, Kecheng Advanced Materials, Vol. 30, Issue 37 https://doi.org/10.1002/adma.201704303	journal	February 2018
Metal-Organic Frameworks for Separation Zhao, Xiang; Wang, Yanxiang; Li, Dong-Sheng Advanced Materials, Vol. 30, Issue 37 https://doi.org/10.1002/adma.201705189	journal	March 2018
Tailor-Made Microporous Metal-Organic Frameworks for the Full Separation of Propane from Propylene Through Selective Size Exclusion Wang, Hao; Dong, Xinglong; Colombo, Valentina Advanced Materials, Vol. 30, Issue 49 https://doi.org/10.1002/adma.201805088	journal	October 2018
Simultaneous Trapping of C ₂ H ₂ and C ₂ H ₆ from a Ternary Mixture of C ₂ H ₂ /C ₂ H ₄ /C ₂ H ₆ in a Robust Metal–Organic Framework for the Purification of C ₂ H ₄ Hao, Hong‐Guo; Zhao, Yun‐Feng; Chen, Di‐Ming Angewandte Chemie, Vol. 130, Issue 49 https://doi.org/10.1002/ange.201809884	journal	October 2018
Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite-Type Zeolitic Imidazolate Frameworks Nguyen, Nhung T. T.; Furukawa, Hiroyasu; Gándara, Felipe Angewandte Chemie International Edition, Vol. 53, Issue 40 https://doi.org/10.1002/anie.201403980	journal	July 2014
Exploration of porous metal–organic frameworks for gas separation and purification Lin, Rui-Biao; Xiang, Shengchang; Xing, Huabin Coordination Chemistry Reviews, Vol. 378 https://doi.org/10.1016/j.ccr.2017.09.027	journal	January 2019
Titanium-based metal–organic frameworks for photocatalytic applications Zhu, Jianjun; Li, Pei-Zhou; Guo, Wenhan Coordination Chemistry Reviews, Vol. 359 https://doi.org/10.1016/j.ccr.2017.12.013	journal	March 2018
Ethane selective adsorbent Ni(bdc)(ted)0.5 with high uptake and its significance in adsorption separation of ethane and ethylene Liang, Wanwen; Xu, Feng; Zhou, Xin Chemical Engineering Science, Vol. 148 https://doi.org/10.1016/j.ces.2016.04.016	journal	July 2016
An ethane-trapping MOF PCN-250 for highly selective adsorption of ethane over ethylene Chen, Yongwei; Qiao, Zhiwei; Wu, Houxiao Chemical Engineering Science, Vol. 175 https://doi.org/10.1016/j.ces.2017.09.032	journal	January 2018
Olefins from conventional and heavy feedstocks: Energy use in steam cracking and alternative processes Ren, T.; Patel, M.; Blok, K. Energy, Vol. 31, Issue 4 https://doi.org/10.1016/j.energy.2005.04.001	journal	March 2006
Metal–organic frameworks: Structures and functional applications Jiao, Long; Seow, Joanne Yen Ru; Skinner, William Scott Materials Today, Vol. 27 https://doi.org/10.1016/j.mattod.2018.10.038	journal	July 2019
Methodologies for screening and selection of crystalline microporous materials in mixture separations Krishna, Rajamani Separation and Purification Technology, Vol. 194 https://doi.org/10.1016/j.seppur.2017.11.056	journal	April 2018
Metal–Organic Frameworks as Platforms for Functional Materials Cui, Yuanjing; Li, Bin; He, Huajun Accounts of Chemical Research, Vol. 49, Issue 3 https://doi.org/10.1021/acs.accounts.5b00530	journal	February 2016
Pore Space Partition in Metal–Organic Frameworks Zhai, Quan-Guo; Bu, Xianhui; Zhao, Xiang Accounts of Chemical Research, Vol. 50, Issue 2 https://doi.org/10.1021/acs.accounts.6b00526	journal	January 2017
Bimetallic Metal–Organic Frameworks for Gas Storage and Separation Yang, Xinchun; Xu, Qiang Crystal Growth & Design, Vol. 17, Issue 4 https://doi.org/10.1021/acs.cgd.7b00166	journal	March 2017
Highly Adsorptive Separation of Ethane/Ethylene by An Ethane-Selective MOF MIL-142A Chen, Yongwei; Wu, Houxiao; Lv, Daofei Industrial & Engineering Chemistry Research, Vol. 57, Issue 11 https://doi.org/10.1021/acs.iecr.7b05260	journal	March 2018
Enhancement of Ethane Selectivity in Ethane–Ethylene Mixtures by Perfluoro Groups in Zr-Based Metal-Organic Frameworks Pires, João; Fernandes, Joana; Dedecker, Kevin ACS Applied Materials & Interfaces, Vol. 11, Issue 30 https://doi.org/10.1021/acsami.9b07115	journal	July 2019
Grand Challenges and Future Opportunities for Metal–Organic Frameworks Hendon, Christopher H.; Rieth, Adam J.; Korzyński, Maciej D. ACS Central Science, Vol. 3, Issue 6 https://doi.org/10.1021/acscentsci.7b00197	journal	June 2017
Ethane Selective IRMOF-8 and Its Significance in Ethane–Ethylene Separation by Adsorption Pires, João; Pinto, Moisés L.; Saini, Vipin K. ACS Applied Materials & Interfaces, Vol. 6, Issue 15 https://doi.org/10.1021/am502686g	journal	July 2014
Metal–Organic Frameworks for Separations Li, Jian-Rong; Sculley, Julian; Zhou, Hong-Cai Chemical Reviews, Vol. 112, Issue 2, p. 869-932 https://doi.org/10.1021/cr200190s	journal	September 2011
Metal-Organic Frameworks Based on Trigonal Prismatic Building Blocks and the New “acs” Topology Sudik, Andrea C.; Côté, Adrien P.; Yaghi, Omar M. Inorganic Chemistry, Vol. 44, Issue 9, p. 2998-3000 https://doi.org/10.1021/ic050064g	journal	May 2005
Pore Space Partition and Charge Separation in Cage-within-Cage Indium−Organic Frameworks with High CO ₂ Uptake Zheng, Shou-Tian; Bu, Julia T.; Li, Yufei Journal of the American Chemical Society, Vol. 132, Issue 48 https://doi.org/10.1021/ja106903p	journal	December 2010
Ethane/Ethene Separation Turned on Its Head: Selective Ethane Adsorption on the Metal−Organic Framework ZIF-7 through a Gate-Opening Mechanism Gücüyener, Canan; van den Bergh, Johan; Gascon, Jorge Journal of the American Chemical Society, Vol. 132, Issue 50 https://doi.org/10.1021/ja1089765	journal	December 2010
Selective Binding of O ₂ over N ₂ in a Redox–Active Metal–Organic Framework with Open Iron(II) Coordination Sites Bloch, Eric D.; Murray, Leslie J.; Queen, Wendy L. Journal of the American Chemical Society, Vol. 133, Issue 37 https://doi.org/10.1021/ja205976v	journal	September 2011
How Linker’s Modification Controls Swelling Properties of Highly Flexible Iron(III) Dicarboxylates MIL-88 Horcajada, Patricia; Salles, Fabrice; Wuttke, Stefan Journal of the American Chemical Society, Vol. 133, Issue 44 https://doi.org/10.1021/ja206936e	journal	November 2011
Introduction of π-Complexation into Porous Aromatic Framework for Highly Selective Adsorption of Ethylene over Ethane Li, Baiyan; Zhang, Yiming; Krishna, Rajamani Journal of the American Chemical Society, Vol. 136, Issue 24 https://doi.org/10.1021/ja502119z	journal	June 2014
Pore Space Partition by Symmetry-Matching Regulated Ligand Insertion and Dramatic Tuning on Carbon Dioxide Uptake Zhao, Xiang; Bu, Xianhui; Zhai, Quan-Guo Journal of the American Chemical Society, Vol. 137, Issue 4 https://doi.org/10.1021/ja512137t	journal	January 2015
Boosting Ethane/Ethylene Separation within Isoreticular Ultramicroporous Metal–Organic Frameworks Lin, Rui-Biao; Wu, Hui; Li, Libo Journal of the American Chemical Society, Vol. 140, Issue 40 https://doi.org/10.1021/jacs.8b07563	journal	September 2018
A Robust Ethane-Trapping Metal–Organic Framework with a High Capacity for Ethylene Purification Qazvini, Omid T.; Babarao, Ravichandar; Shi, Zhao-Lin Journal of the American Chemical Society, Vol. 141, Issue 12 https://doi.org/10.1021/jacs.9b00913	journal	March 2019
Seven chemical separations to change the world Sholl, David S.; Lively, Ryan P. Nature, Vol. 532, Issue 7600 https://doi.org/10.1038/532435a	journal	April 2016
The chemistry of metal–organic frameworks for CO2 capture, regeneration and conversion Trickett, Christopher A.; Helal, Aasif; Al-Maythalony, Bassem A. Nature Reviews Materials, Vol. 2, Issue 8 https://doi.org/10.1038/natrevmats.2017.45	journal	July 2017
Highly controlled acetylene accommodation in a metal–organic microporous material Matsuda, Ryotaro; Kitaura, Ryo; Kitagawa, Susumu Nature, Vol. 436, Issue 7048 https://doi.org/10.1038/nature03852	journal	July 2005
Porous materials with optimal adsorption thermodynamics and kinetics for CO₂ separation Nugent, Patrick; Belmabkhout, Youssef; Burd, Stephen D. Nature, Vol. 495, Issue 7439, p. 80-84 https://doi.org/10.1038/nature11893	journal	February 2013
Supramolecular binding and separation of hydrocarbons within a functionalized porous metal–organic framework Yang, Sihai; Ramirez-Cuesta, Anibal J.; Newby, Ruth Nature Chemistry, Vol. 7, Issue 2 https://doi.org/10.1038/nchem.2114	journal	December 2014
Efficient purification of ethene by an ethane-trapping metal-organic framework Liao, Pei-Qin; Zhang, Wei-Xiong; Zhang, Jie-Peng Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9697	journal	October 2015
A phase transformable ultrastable titanium-carboxylate framework for photoconduction Wang, Sujing; Kitao, Takashi; Guillou, Nathalie Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04034-w	journal	April 2018
Molecular sieving of ethylene from ethane using a rigid metal–organic framework Lin, Rui-Biao; Li, Libo; Zhou, Hao-Long Nature Materials, Vol. 17, Issue 12 https://doi.org/10.1038/s41563-018-0206-2	journal	November 2018
Titanium coordination compounds: from discrete metal complexes to metal–organic frameworks Assi, Hala; Mouchaham, Georges; Steunou, Nathalie Chemical Society Reviews, Vol. 46, Issue 11 https://doi.org/10.1039/C7CS00001D	journal	January 2017
Gas/vapour separation using ultra-microporous metal–organic frameworks: insights into the structure/separation relationship Adil, Karim; Belmabkhout, Youssef; Pillai, Renjith S. Chemical Society Reviews, Vol. 46, Issue 11 https://doi.org/10.1039/C7CS00153C	journal	January 2017
Screening metal–organic frameworks for mixture separations in fixed-bed adsorbers using a combined selectivity/capacity metric Krishna, Rajamani RSC Advances, Vol. 7, Issue 57 https://doi.org/10.1039/C7RA07363A	journal	January 2017
Pore environment engineering in metal–organic frameworks for efficient ethane/ethylene separation Wang, Xun; Niu, Zheng; Al-Enizi, Abdullah M. Journal of Materials Chemistry A, Vol. 7, Issue 22 https://doi.org/10.1039/C9TA02822F	journal	January 2019
Hydrogen adsorption in the metal–organic frameworks Fe2(dobdc) and Fe2(O2)(dobdc) Queen, Wendy L.; Bloch, Eric D.; Brown, Craig M. Dalton Transactions, Vol. 41, Issue 14 https://doi.org/10.1039/c2dt12138g	journal	January 2012
Metal–organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons He, Yabing; Krishna, Rajamani; Chen, Banglin Energy & Environmental Science, Vol. 5, Issue 10 https://doi.org/10.1039/c2ee22858k	journal	January 2012
Role of Solvent-Host Interactions That Lead to Very Large Swelling of Hybrid Frameworks Serre, C.; Mellot-Draznieks, C.; Surble, S. Science, Vol. 315, Issue 5820 https://doi.org/10.1126/science.1137975	journal	March 2007
Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites Bloch, E. D.; Queen, W. L.; Krishna, R. Science, Vol. 335, Issue 6076, p. 1606-1610 https://doi.org/10.1126/science.1217544	journal	March 2012
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene Cui, X.; Chen, K.; Xing, H. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf2458	journal	May 2016
A metal-organic framework-based splitter for separating propylene from propane Cadiau, A.; Adil, K.; Bhatt, P. M. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf6323	journal	July 2016
Molecular sieves for gas separation Lin, J. Y. S. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aag2267	journal	July 2016
Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites Li, Libo; Lin, Rui-Biao; Krishna, Rajamani Science, Vol. 362, Issue 6413 https://doi.org/10.1126/science.aat0586	journal	October 2018
Synergistic sorbent separation for one-step ethylene purification from a four-component mixture Chen, Kai-Jie; Madden, David G.; Mukherjee, Soumya Science, Vol. 366, Issue 6462 https://doi.org/10.1126/science.aax8666	journal	October 2019

Cited By (3)

Two Co-based MOFs assembled from an amine-functionalized pyridinecarboxylate ligand: inorganic acid-directed structural variety and gas adsorption properties Jiang, Zhenzhen; Zhou, Ping; Xu, Tingting CrystEngComm https://doi.org/10.1039/d0ce00475h	journal	January 2020
Structural diversity of metal–organic frameworks based on a chalcone dicarboxylic acid ligand Xu, Hao; Zeng, Xianghua; Pan, Wei Dalton Transactions, Vol. 49, Issue 18 https://doi.org/10.1039/d0dt00654h	journal	January 2020
Immobilization of N -oxide functionality into NbO-type MOFs for significantly enhanced C ₂ H ₂ /CH ₄ and CO ₂ /CH ₄ separations Xu, Tingting; Fan, Lihui; Jiang, Zhenzhen Dalton Transactions https://doi.org/10.1039/d0dt01081b	journal	January 2020

Linked Research (7)

Similar Records

A Strategy for Constructing Pore-Space-Partitioned MOFs with High Uptake Capacity for C₂ Hydrocarbons and CO₂

Journal Article · Wed Aug 26 00:00:00 UTC 2020 · Angewandte Chemie (International Edition) · OSTI ID:1755101

Wang, Yong; Jia, Xiaoxia; Yang, Huajun; +6 more

Tunable Metal–Organic Frameworks Based on 8-Connected Metal Trimers for High Ethane Uptake

Journal Article · Tue Aug 25 00:00:00 UTC 2020 · Small · OSTI ID:1755103

Lei, Xiao‐Wu; Yang, Huajun; Wang, Yanxiang; +5 more

A Strategy for Constructing Pore‐Space‐Partitioned MOFs with High Uptake Capacity for C ₂ Hydrocarbons and CO ₂

Journal Article · Wed Aug 26 00:00:00 UTC 2020 · Angewandte Chemie · OSTI ID:1651161