Immobilization of the Polar Group into an Ultramicroporous Metal–Organic Framework Enabling Benchmark Inverse Selective CO2/C2H2 Separation with Record C2H2 Production DOI

Shan‐Qing Yang,

Rajamani Krishna, Hongwei Chen

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(25), P. 13901 - 13911

Published: June 13, 2023

One-step harvest of high-purity light hydrocarbons without the desorption process represents an advanced and highly efficient strategy for purification target substances. The separation acetylene (C2H2) from carbon dioxide (CO2) by CO2-selective adsorbents are urgently demanded yet very challenging owing to their similar physicochemical properties. Here, we employ pore chemistry adjust environment immobilizing polar groups into ultramicroporous metal-organic framework (MOF), achieving one-step manufacture C2H2 CO2/C2H2 mixtures. Embedding methyl prototype stable MOF (Zn-ox-trz) not only changes but also improves discrimination guest molecules. methyl-functionalized Zn-ox-mtz thus exhibits benchmark reverse uptake ratio 12.6 (123.32/9.79 cm3 cm-3) exceptionally high equimolar selectivity 1064.9 at ambient conditions. Molecular simulations reveal that synergetic effect confinement surfaces decorated with provides recognition CO2 molecules through multiple van der Waals interactions. column breakthrough experiments suggest dramatically achieved capacity mixture a record productivity 2091 mmol kg-1, surpassing all reported so far. In addition, excellent chemical stability under different pH values aqueous solutions (pH = 1-12). Moreover, inverse selective performance showcase its promising application as splitter industrial manufacture. This work paves way developing reverse-selective gas process.

Language: Английский

Isoreticular chemistry within metal–organic frameworks for gas storage and separation DOI
Weidong Fan,

Xiurong Zhang,

Zixi Kang

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 443, P. 213968 - 213968

Published: May 13, 2021

Language: Английский

Citations

433
Postsynthetic Modification: An Enabling Technology for the Advancement of Metal–Organic Frameworks DOI Creative Commons
Mark Kalaj, Seth M. Cohen

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(7), P. 1046 - 1057

Published: July 2, 2020

Metal–organic frameworks (MOFs) are a class of porous materials with immense chemical tunability derived from their organic and inorganic building blocks. Presynthetic approaches have been used to construct tailor-made MOFs, but rather restricted functional group scope limited by the typical MOF solvothermal synthesis conditions. Postsynthetic modification (PSM) MOFs has matured into an alternative strategy broaden MOFs. PSM many incarnations, two main avenues include (1) covalent PSM, in which linkers modified reagent resulting new groups, (2) coordinative where molecules containing metal ligating groups introduced onto secondary units (SBUs) MOF. These methods evolved simple efforts modifying demonstrate proof-of-concept, becoming key synthetic tools for advancing range emerging applications, including selective gas sorption, catalysis, drug delivery. Moreover, both create hierarchal MOF-based liquids, other unusual materials. This Outlook highlights recent reports that extended some seminal contributed advancement our view on future directions field.

Language: Английский

Citations

419
Selective capture of carbon dioxide from hydrocarbons using a metal-organic framework DOI Creative Commons
Omid T. Qazvini, Ravichandar Babarao, Shane G. Telfer

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Jan. 8, 2021

Abstract Efficient and sustainable methods for carbon dioxide capture are highly sought after. Mature technologies involve chemical reactions that absorb CO 2, but they have many drawbacks. Energy-efficient alternatives may be realised by porous physisorbents with void spaces complementary in size electrostatic potential to molecular 2 . Here, we present a robust, recyclable inexpensive adsorbent termed MUF-16. This metal-organic framework captures high affinity its one-dimensional channels, as determined adsorption isotherms, X-ray crystallography density-functional theory calculations. Its low other competing gases delivers selectivity the of over methane, acetylene, ethylene, ethane, propylene propane. For equimolar mixtures /CH 4 /C H , is 6690 510, respectively. Breakthrough gas separations under dynamic conditions benefit from short time lags elution weakly-adsorbed component deliver high-purity hydrocarbon products, including pure methane acetylene.

Language: Английский

Citations

268
Fine pore engineering in a series of isoreticular metal-organic frameworks for efficient C2H2/CO2 separation DOI Creative Commons
Jun Wang, Yan Zhang, Yun Su

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Jan. 11, 2022

The separation of C2H2/CO2 is not only industrially important for acetylene purification but also scientifically challenging owing to their high similarities in physical properties and molecular sizes. Ultramicroporous metal-organic frameworks (MOFs) can exhibit a pore confinement effect differentiate gas molecules similar size. Herein, we report the fine-tuning sizes sub-nanometer scale on series isoreticular MOFs that realize highly efficient separation. subtle structural differences lead remarkable adsorption performances enhancement. Among four MOF analogs, by integrating appropriate size specific binding sites, [Cu(dps)2(SiF6)] (SIFSIX-dps-Cu, SIFSIX = SiF62-, dps 4.4'-dipyridylsulfide, termed as NCU-100) exhibits highest C2H2 uptake capacity selectivity. At room temperature, space SIFSIX-dps-Cu significantly inhibits CO2 takes up large amount (4.57 mmol g-1), resulting IAST selectivity 1787 multiple host-guest interactions both inter- intralayer cavities are further revealed dispersion-corrected density functional theory grand canonical Monte Carlo simulations. Dynamic breakthrough experiments show clean with working 2.48 g-1.

Language: Английский

Citations

244
Supramolecular control of MOF pore properties for the tailored guest adsorption/separation applications DOI
Dan Wu,

Peng-Feng Zhang,

Guo‐Ping Yang

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 434, P. 213709 - 213709

Published: Feb. 11, 2021

Language: Английский

Citations

219
Progress and potential of metal-organic frameworks (MOFs) for gas storage and separation: A review DOI
Tao Jia, Yifan Gu, Fengting Li

et al.

Journal of environmental chemical engineering, Journal Year: 2022, Volume and Issue: 10(5), P. 108300 - 108300

Published: July 20, 2022

Language: Английский

Citations

216
Benchmark C2H2/CO2Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry DOI
Ling Zhang, Ke Jiang, Lifeng Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(29), P. 15995 - 16002

Published: May 12, 2021

Abstract Separation of acetylene from carbon dioxide remains a daunting challenge because their very similar molecular sizes and physical properties. We herein report the first example using copper(I)‐alkynyl chemistry within an ultra‐microporous MOF (Cu I @UiO‐66‐(COOH) 2 ) to achieve ultrahigh C H /CO separation selectivity. The anchored Cu ions on pore surfaces can specifically strongly interact with molecule through π‐complexation thus rapidly adsorb large amount at low‐pressure region, while effectively reduce CO uptake due small sizes. This material exhibits record high selectivity 185 ambient conditions, significantly higher than previous benchmark ZJU‐74a (36.5) ATC‐Cu (53.6). Theoretical calculations reveal that unique between mainly contributes ultra‐strong binding affinity exceptional performance was evidenced by breakthrough experiments for gas mixtures. work suggests new perspective functionalizing MOFs highly selective over .

Language: Английский

Citations

193
Fluorinated metal–organic frameworks for gas separation DOI
Abtin Ebadi Amooghin, Hamidreza Sanaeepur, Rafael Luque

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(17), P. 7427 - 7508

Published: Jan. 1, 2022

Fluorinated metal-organic frameworks (F-MOFs) as fast-growing porous materials have revolutionized the field of gas separation due to their tunable pore apertures, appealing chemical features, and excellent stability. A deep understanding structure-performance relationships is critical for synthesis development new F-MOFs. This review has focused on several strategies precise design F-MOFs with structures tuned specific purposes. First, basic principles concepts well structure, modification structure property are studied. Then, applications in adsorption membrane discussed. detailed account capabilities various gases governing provided. In addition, exceptional characteristics highly stable engineered size put into perspective fabricate selective membranes separation. Systematic analysis position revealed that benchmark most challenging separations. The outlook future directions science engineering challenges highlighted tackle issues overcoming trade-off between capacity/permeability selectivity a serious move towards industrialization.

Language: Английский

Citations

174
Integrating the Pillared-Layer Strategy and Pore-Space Partition Method to Construct Multicomponent MOFs for C2H2/CO2 Separation DOI
Lizhen Liu, Zizhu Yao,

Yingxiang Ye

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(20), P. 9258 - 9266

Published: April 25, 2020

Introducing multiclusters and multiligands (mm) in a well-defined array will greatly increase the diversity of metal-organic frameworks (MOFs). Here, series porous mm-MOFs constructed from pillared-layer pore-space partition (PL-PSP) have been achieved. FJU-6 with {Co3}-cluster-based sheets {Co6}-cluster-based pillars exhibits new (3,9,12)-connected llz topology. By using substituted analogues ligands metal ions, seven isoreticular (FJU-6-X, X = PTB, TATB, Me-INA, F-INA, NDC, BrBDC, Ni) synthesized adjustable BET surface areas ranging 731 to 1306 m2/g as well adsorption capacity CO2 increasing by 77%. The C2H2/CO2 mixture can be effectively separated breakthrough experiments fixed bed filled solid FJU-6-TATB at ambient temperature. In all, integrating strategy partitioning is effective constructing multivariate environments for optimization gas separation.

Language: Английский

Citations

173
Precise Pore Space Partitions Combined with High‐Density Hydrogen‐Bonding Acceptors within Metal–Organic Frameworks for Highly Efficient Acetylene Storage and Separation DOI
Yingying Xue,

Xiao‐Ying Bai,

Jing Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(18), P. 10122 - 10128

Published: Feb. 5, 2021

Abstract The high storage capacity versus selectivity trade‐off barrier presents a daunting challenge to practical application as an acetylene (C 2 H ) adsorbent. A structure–performance relationship screening for sixty‐two high‐performance metal–organic framework adsorbents reveals that moderate pore size distribution around 5.0–7.5 Å is critical fulfill this task. precise space partition approach was involved 1D hexagonal channels of typical MIL‐88 architecture into finite segments with sizes varying from 4.5 (SNNU‐26) 6.4 (SNNU‐27), 7.1 (SNNU‐28), and 8.1 (SNNU‐29). Coupled bare tetrazole N sites (6 or 12 within one cage) high‐density H‐bonding acceptors C , the target MOFs offer good combination /CO adsorption uptake in addition stability. optimized SNNU‐27‐Fe material demonstrates 182.4 cm 3 g −1 extraordinary dynamic breakthrough time up 91 min under ambient conditions.

Language: Английский

Citations

169