Review Potential of metal–organic frameworks for adsorptive separation of industrially and environmentally relevant liquid mixtures Soumya Mukherjee a,1 , Aamod V. Desai a,1 , Sujit K. Ghosh a,b,⇑ a Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhabha Road, Pashan, Pune 411008, India b Centre for Energy Science, IISER Pune, Pune 411008, India article info Article history: Received 28 November 2017 Accepted 5 April 2018 Keywords: Metal–organic frameworks Chemical functionalization Adsorption Separation abstract Metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are defined as crystalline, open, coordination network architectures with potential voids. They have drawn momentous attention across several crossroads of material chemistry since their discovery, owing to an exciting plethora of application-oriented footprints left by this class of supramolecular network solids. The unmatched aspect of tunable coordination nanospace arising from the countless choice of pre-functionalized organic struts pertaining to varying lengths alongside multivariate coordination geometries/oxidation states of the metal nodes, bestows a distinct chemical tailorability facet to this class of porous materials. Amidst the two-decade long attention dedicated to the adsorption–governed purification of gases, the MOF literature has substantially expanded its horizon into the manifestation of industrially relevant liquid mixtures’ adsorptive separation–driven purification. Such chemical separation phenomena categorically encompasses high importance to the manufacturing and processing industry sectors, apart from the fundamental scientific pursuit of discovering novel physicochemical principles. Aimed at the energy- economic preparation of pure industrial feedstocks and their consequent usage as end products, structure–property correlations pursued in the alleys of coordination chemistry has led to major advancements in a number of critical separation frontiers, inclusive of biofuels (alcohol/water), diverse hydrocarbon mixtures, and chiral species. This comprehensive review summarizes the topical develop- ments accrued in the field of MOF based liquid mixtures’ adsorptive separation phenomena, structure– selectivity relationships as well as the associated plausible mechanisms substantiating such behavior. Ó 2018 Elsevier B.V. All rights reserved. Contents 1. Introduction .......................................................................................................... 83 2. Evaluation of MOFs adsorbents exhibiting liquid mixture separation ............................................................ 86 2.1. Separation of linear/branched alkane hydrocarbons (C 5 –C 6 –C 7 ) ........................................................... 86 2.2. Separation of cyclic C 6 isomers (benzene/cyclohexane) .................................................................. 89 2.3. Separation of cyclic C 8 isomers (styrene/ethyl benzene, and xylene isomers) ................................................ 95 https://doi.org/10.1016/j.ccr.2018.04.001 0010-8545/Ó 2018 Elsevier B.V. All rights reserved. Abbreviations: MOF, metal–organic framework; PCP, porous coordination polymer; PSA, pressure swing adsorption; TSA, temperature swing adsorption; VSA, vacuum swing adsorption; EPA, United States Environmental Protection Agency; EEA, European Environment Agency; SMB, simulated moving bed; Q st , isosteric heat of adsorption; MFOF, metal–fluoride–organic framework; MBB, molecular building block; CP, coordination polymer; CB, carbon black; UMC, unsaturated metal center; HUM, hybrid ultramicroporous material; IAST, ideal adsorbed solution theory; S ads , selectivity of adsorption/adsorption selectivity; CID, coordination polymer with interdigitated structure; Hip, isophthalic acid; bpy, 4,4 0 -bipyridine; pcu, primitive cubic; GC, gas chromatography; dabco, 1,4-diazabicyclo[2,2,2]octane; bdp, 1,4-benzenedipyrazolate; Bz, benzene; Cy, cyclohexane; Tl, toluene; BTEX, mixtures of benzene, toluene, ethyl benzene and xylene isomers.; nC 6 or n-Hex, n-hexane; FAU, Faujasite; BTC, 1,3,5- benzenetricarboxylate or trimesate; BPz, 3,3 0 ,5,5 0 -tetramethyl-4,4 0 -bipyrazole; % RH, relative humidity; m, min; HK, Horvath Kawazoe; BTB, 1,3,5-benzenetrisbenzate; ZIFs, zeolitic imidazolate frameworks; BET, Brunauer–Emmett–Teller; QCM, quartz crystal microbalance; Im, imidazole. ⇑ Corresponding author at: Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhabha Road, Pashan, Pune 411008, India. E-mail address: sghosh@iiserpune.ac.in (S.K. Ghosh). 1 These authors have contributed equally. Coordination Chemistry Reviews 367 (2018) 82–126 Contents lists available at ScienceDirect Coordination Chemistry Reviews journal homepage: www.elsevier.com/locate/ccr