Ha_MOF_A Review

Journal of Hazardous Materials 244 245 (2013) 444 456

Contents lists available at SciVerse ScienceDirect

Journal of Hazardous Materials

j our na l ho me p age: www.elsev ier .com/ locate / jhazmat

Review

Adsorptive removal of hazardous materials using metal-organic frameworks(MOFs)

Nazmul ADepartment of

h i g h l i g h t s

Metal-organic frameworks are veryeffective to remove hazardous mate-rials.

Mechanisms for adsorptive removalwith MOFs

MOFs are tial adsorment.

g r a p h i c a l a b s t r a c t

a r t i c l

Article history:Received 3 SepReceived in reAccepted 4 NoAvailable onlin

Key words:AdsorptionAdsorptive remHazardous maMetal-organicReview

Contents

1. Introd1.1. 1.2. 1.3. 1.4.

CorresponE-mail add

1 Fax: +82 5

0304-3894/$ http://dx.doi.o were summarized.surely regarded as poten-bents for clean environ-

e i n f o

tember 2012vised form 29 October 2012vember 2012e 13 November 2012

ovalterials

frameworks

a b s t r a c t

Efcient removal of hazardous materials from the environment has become an important issue froma biological and environmental standpoint. Adsorptive removal of toxic components from fuel, waste-water or air is one of the most attractive approaches for cleaning technologies. Recently, porous metal-organic framework (MOF) materials have been very promising in the adsorption/separation of variousliquids and gases due to their unique characteristics. This review summarizes the recent literatures onthe adsorptive removal of various hazardous compounds mainly from fuel, water, and air by virgin ormodied MOF materials. Possible interactions between the adsorbates and active adsorption sites of theMOFs will be also discussed to understand the adsorption mechanism. Most of the observed results canbe explained with the following mechanisms: (1) adsorption onto a coordinatively unsaturated site, (2)adsorption via acid-base interaction, (3) adsorption via -complex formation, (4) adsorption via hydrogenbonding, (5) adsorption via electrostatic interaction, and (6) adsorption based on the breathing propertiesof some MOFs and so on.

2012 Elsevier B.V. All rights reserved.

uction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445Common hazardous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445Adsorptive removal of hazardous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445Metal-organic frameworks (MOFs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446Purpose of this review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447

ding author. Tel.: +82 53 950 5341; fax: +82 53 950 6330.ress: [email protected] (S.H. Jhung).3 950 6330.

see front matter 2012 Elsevier B.V. All rights reserved.rg/10.1016/j.jhazmat.2012.11.011: A review

bedin Khan1, Zubair Hasan1, Sung Hwa Jhung

Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701, Republic of Korea

N.A. Khan et al. / Journal of Hazardous Materials 244 245 (2013) 444 456 445

2. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4472.1. Adsorptive removal of SCCs and NCCs from fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4472.2. Adsorptive removal of organic contaminants from waste water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4482.3. Adsorptive removal of heavy metal ions from efuent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4492.4. . . . . . .

3. Summ . . . . . .Ackno . . . . . Refer . . . . . .

1. Introdu

Presentllematic issureduce pollthe environenvironmen(VOCs), nitrcompoundsucts (PPCPsframeworksatile applibecause of ious pore aon. Therefoadsorption/with MOFs.liquids and

1.1. Commo

The mosenvironmensources; thanthropogelutants is prhand, the abustion, chematerials. Tnatural gas,emits huge the emissiolution are N[1,2]. Emissin the tropoVehicle-relabon contribworld is onetherefore, rgreat challechemicals itural, manuthe nitrogeAmerican Chas speciethe time-w[5]. Recentsuccessful tand odoroution [911].emitted frocommon haolics, xylensince they a

anic ing solineenerge amcounwarmerefoarmle, b

be le mosdely ustried adyesal ofe wal amtremPs ineven, fraglturaefunallh [2

ng ornal a

disperab), m

and cnd hions fcade

sorp

orpt for dangermfuentsent osp

ble sompAdsorptive removal of harmful gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .ary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .wledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

ences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

ction

y, environmental pollution is one of the most prob-es worldwide. There have been many trials both toution and to eliminate the polluting materials fromment. Common hazardous materials that exist in ourt are NOx, SOx, COx, H2S, volatile organic compoundsogen-containing compounds (NCCs), sulfur-containing

(SCCs), dyes, pharmaceuticals and personal care prod-), and so on. On the other hand, porous metal-organic

(MOF) materials are very interesting due to their ver-cations. MOFs are superior to other porous materialstheir high/tunable porosity, pore functionality, var-rchitectures/compositions, open metal sites, and sore, recently, extensive studies have been done on theseparation of various gaseous and liquid components

In this review, the adsorptive removal of various toxic gases using virgin or modied MOFs will be discussed.

n hazardous materials

t abundant hazardous components that exist in thet can be classied into two categories based on theirese are naturally occurring hazardous materials andnic. A considerable amount of naturally occurring pol-esent in the air, minerals, water, and soil. On the othernthropogenic pollutants generally originate from com-mical reactions or from the unsecured efuent of toxiche global energy demand is being supplied mainly by

coal, and crude oil. The burning of these energy sourcesamounts of toxic gases into the atmosphere. Generally,ns with the greatest concern for environmental air pol-Ox, SOx, CO2, VOCs, H2S, NH3, and other hydrocarbonsions of N2O, SO2, O3, and CH4 enlarge the ozone levelssphere and are also considered as greenhouse gases.ted pollutants like SO2, NO2, CO, CH4, and black car-ute to global warming [1]. The carbon balance of the

of the most important environmental issues currently;educing anthropogenic CO2 emissions has become ange for humanity. NH3, one of the most widely usedn laboratories and various industries including agricul-facturing, refrigeration, etc., is responsible partly forn containing pollutants in the atmosphere [35]. Theonference Governmental Industrial Hygienists (ACGIH)d the allowable NH3 concentration as up to 25 ppm aseighted average and 35 ppm as short-term exposurely, adsorption has been regarded as one of the most

Orgoccurroil, gasglobal of a huthat acglobal [2]. Ththese hexampshould

Theare witic indproducduced Removbecausa smaland ex

PPCwater meticsagricuin the occasioresearcfor livihormo

Theconsidper (Cu(Mn), tems ametal few de

1.2. Ad

Adsniqueswide rlow haadsorbadsorbthe atma suitathese cechniques for NH3 capture [58]. H2S, another toxics air pollutant has also been removed through sorp-

VOCs are chemicals with high vapor pressure, generallym solvents, resins, paints, adhesives, etc. [12,13]. Thezardous VOCs are benzene, naphthalene, toluene, phen-es, and so on. VOCs are considered hazardous materialsre harmful to the environment and human health.

bents. Baseand a porouical or chemadsorptive tive adsorpare generalpores of the . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453

compounds containing sulfur or nitrogen are naturallypecies that are present in fossil fuels and oils like crude, diesel, jet fuel, and heating oil. More than 85% of the

gy has originated from fossil fuels [14]. The combustionount of fossil fuel is the major source of toxic emissionst for the dangerous air pollution, greenhouse effect, anding as well as the harmful impact on living organisms

re, recently, it has become a great challenge to removeful compounds from crude oils before utilization. Forased on EU and US guidelines, the sulfur level in fuelsss than 10 ppmw and 15 ppmw, respectively [1,1517].t abundant pollutant of water is dye materials. Dyesused in the textile, leather, paper, painting, and plas-es. Around 100,000 commercially available dyes aret a rate of 7 105 tons per year [18] with 2% of the pro-

being discharged into aquatic systems as efuent [18]. these materials from waste water is very importantter quality is highly inuenced by color [18] and evenount of dye is highly visible and considered to be toxicely hazardous to aquatic living organisms [1820].clude a class of chemical contaminants that exist in

after these products are utilized for medicines, cos-rances, veterinary drugs, fungicides, disinfectants, andl practices [2123]. The presence of these kinds of PPCPsent of wastewater treatment plants, rivers, lakes andy, in groundwater, has been demonstrated by the recent4]. Moreover, it is reported that, a class of PPCPs is unsafeganisms and may cause endocrine disruptions changingctions [25,26].osal of heavy metal ions in processed water is still a

le amount. Some metals like lead (Pb), arsenic (As), cop-ercury (Hg), antimony (Sb), chromium (Cr), manganeseadmium (Cd) are signicantly toxic to ecological sys-uman beings [2731]. The recovery of those harmfulrom environment has been a global concern for the lasts [2731].

tive removal of hazardous materials

ion has been considered to be superior to other tech-econtamination in view of its comparatively low cost,

of applications, simplicity of design, easy operation,l secondary products and facile regeneration of the

. Adsorptive removal is based on the ability of a porousto selectively adsorb some specic compounds fromhere or renery streams. The compounds, which haveize and shape, can be removed via adsorption sinceounds have easy access to the pores of the solid sor-

d on the types of interactions between an adsorbates sorbent, the adsorption can be categorized as a phys-ical one [1,32]. Physical adsorption is usually called

adsorption, whereas chemical adsorption is called reac-tion. In the case of adsorptive removal, the adsorbatesly trapped with weak (van der Waals) forces inside the

solid adsorbents. Therefore, the adsorbent can be easily

446 N.A. Khan et al. / Journal of Hazardous Materials 244 245 (2013) 444 456

Fig. 1. Widely used porous sorbents: (a) activated carbon, (b) HY (FAU) zeolite, (c) MCM-41 and (d) MIL-101 (Cr).

regenerated by simple solvent exchange or some other physicaltreatments like calcination and sonication. On the other hand,reactive adsorption occurs through the formation of true chemi-cal bonds between the adsorbates and the adsorbent. Regenerationof the spent adsorbent is usually carried out with chemical treat-ments. The efciency of the adsorptive removal is determinedmainly by the adsorption capacity of the adsorbents, selectivityfor specic bents.

Various [3337], zeMOFs [14,1hazardous cpore geome[15,50,51]. tional groupand polyoxadsorbents through co interation techniqexchange, ibeen widely

1.3. Metal-

MOFs arion or a clulinker. The ands [52,53porous hybsince the insmall clustewas found twith a largelayers (2D),

Moreover, MOFs were further extended such as IRMOFs (Isoreticu-lar MOFs), MMOFs (microporous MOFs), PCPs (porous coordinationpolymers), and so on.

MOF materials have many advantages compared with zeolite-type materials. Zeolite-related inorganic hybrid materials need anorganic or inorganic template to form; however, in the case ofMOFs, a solvent is the main templating molecule [53,55]. Another

ant fF formed ones foangih thgth oo benent

intesy t

to mnic mver, tion/sorpy/biois [6Fs buas bf MOtion-ore sc gueently

for m thtry [y un

Source: Reprodcompounds, durability, and regenerability of the adsor-

porous adsorbents (Fig. 1) such as activated carbonsolites [18,3840], mesoporous materials [4144], and5,4548] have been studied for adsorptive removal ofompounds. For efcient adsorptive removal, porosity,try [46,49], and specic adsorption sites are requiredAdditionally, some active species like various func-s (acidic or basic), metal ions, metal oxides, metal salts,ometalates are usually incorporated into the porousfor selective adsorption of hazardous componentsmmon interactions like acid-base, -complexation,ction, and hydrogen bonding. Among the modica-ues, post synthetic modication, functionalization, ionmpregnation, and loading of porous adsorbents have

studied.

organic frameworks (MOFs)

e basically composed of two major components: a metalster of metal ions and an organic molecule called a

organic units are typically di-, tri-, or tetradendate lig-]. Some typical MOFs are shown in Fig. 2. In the past,rid frameworks were called coordination polymers [53]organic part contained either an isolated polyhedral orrs like in coordination chemistry. However, very soon ithat porous hybrid solids could possess inorganic partsr dimensionality which could give rise to chains (1D),

and even frameworks (3D) that were called MOFs [54].

importin MOare basadvanconly chin whicthe lencan alscompo

Theand eaporousinorgaMoreoadsorp[61], addelivercatalyson MOMOFs htions oadsorptheir pspeci

Recwidelyals frogeomenativelFig. 2. Structures of typical metal-organic frameworks. (a) MOFuced with permission from ref. [60]. Copyright 2012 American Chemical Society.eature is that most of the metal cations can participateation [53] compared with inorganic materials which

a few cations such as Si, Al, and P. MOFs have signicantr the formation of a series called isoreticular MOFs, byng the length of the ligands with the same metal speciese pore size of the corresponding frameworks depends onf the ligands [56,57]. Moreover, several analogous MOFs

prepared from identical ligands and different metallics [57].rest in MOF-type materials is due to the huge porosityunability of their pore size and shape from micro-esoporous scale by changing the connectivity of theoiety and the nature of the organic linkers [58,59].MOFs have many potential applications includingstorage of carbon dioxide [14,48,60], hydrogen storagetion of vapours [62], separation of chemicals [63], drugmedicine [64], polymerization [65], magnetism [66],7], luminescence [68], and so on. Not only researchest also the number of publications (per year) related toeen increased rapidly [45] because of potential applica-Fs in various elds. MOFs are promising materials forrelated applications because of the easy modication ofurfaces which leads to the selective adsorption of somest molecules having particular functional groups., MOF-type materials have also been investigatedthe adsorptive removal of various hazardous materi-e environment due to their huge porosity and pore6971]. Moreover, the central metals [7275], coordi-saturated sites (CUS or open metal sites) [7,74,7678],-5, (b) Cu-BTC and (c) CPO-27.


functionalized linkers [7,30,79,80], and loaded active species[4,81,82] have been employed successfully for some additionalinteractions between the adsorbates and MOF materials; thatmake MOFs superior to other porous adsorbents for efcientadsorptive ous host-gu[81,84], H-b[7,74,7678

1.4. Purpos

This revimon hazardliquid with teristics of particular hof central mtionalizatiointeractionsMoreover, amodynamicphenomena

2. Discussi

2.1. Adsorp

SCCs anrening anmercial useprotection aNCCs from explored toied a numbeadsorption superior tobon due to shown simiCu-BTC [92[93]), contrthan that focessful remoils by usinBTC adsorbs(304 K) whitype zeolitein terms othe surfacesynthesizedshowed thation of elecuptake withrich SCCs aof DBT frobenzene bythalate or MShi et al. [8gesting a stoxycarbideics like napadsorption

Khan et ics in the adMOFs such MIL stands

dsorption isotherms of SCCs over various MOFs: benzothiophene (top),thiophene (middle) and 4,6-dimethyldibenzothiophene (bottom).

eproduced with permission from ref. [90]. Copyright 2008 American Chem-ety.

ded that the central metal ions of MOFs play an impor-le in the adsorption of BT from liquid fuels. MIL-47 showedhest adsorption capacity and the fastest adsorption kinetics

the analogous MIL-53s because of the high acidity (Fig. 4).ore, an acid-base interaction (between the acidic MIL-47 andy basic BT) was suggested for the favorable adsorption. The

force of BT adsorptions over the adsorbents in that studye to an increased entropy change rather than an enthalpy. Moreover, introduction of an acidic component to porousals also results in a specic adsorption of slightly basicrough acid-base interactions [82,83]. Phosphotungstic acid

-loaded porous Cu-BTC was examined by Khan and Jhung understand the effect of PWAs on the adsorption/removal of

maximum adsorption capacity (Q0) increased with increas-A loading up to a W/Cu (wt/wt) ratio of 0.22 in PWA/Cu-BTCs,ng in an increase in the Q0 by 26% compared with the vir--BTC. Since there was no remarkable change in the surfaced pore volume for the virgin and PWA loaded Cu-BTCs, itggested that the improved Q0 over PWA/Cu-BTCs was duerable interactions like acidbase ones between the acidicremoval of hazardous compounds. Among the vari-est interactions, acid-base [72,82,83], -complexationonding [7,85] and coordination with open metal sites] play important roles in the preferred adsorption.

e of this review

ew will mainly focus on the adsorptive removal of com-ous materials that exist in the environment as gas or

widely studied porous MOFs. The advantageous charac-MOFs that play a key role in the adsorption/removal ofazardous compounds will be pointed out. The effectsetal ions, open metal sites, linkers, porosity, func-

n/modication of MOFs in adsorption, and the possible between adsorbate and adsorbent will be discussed.dsorption parameters like adsorption kinetics and ther-s will also be included to understand the adsorption.

on

tive removal of SCCs and NCCs from fuel

d NCCs are widely known contaminants in petroleumd in fuels. Removal of these compounds before com-

is extremely important because of environmentalnd catalyst poisoning issues. The removal of SCCs and

liquid fuels by adsorption using porous MOFs has been date [1,15,17,72,8184,8691]. Cychosz et al. [90] stud-r of MOFs having different pore sizes and shapes for theof various SCCs in model oils and found that MOFs are

other porous adsorbents like zeolites or activated car-the selectivity towards SCCs (Fig. 3). Peralta et al. haslarly that MOFs with CUSs (such as copper trimesate or] and nickel 2,5-dihydroxyterephthalate or CPO-27(Ni)ary to zeolites, exhibit stronger afnity for thiophener toluene [94]. Achmann et al. [17] also reported suc-oval of thiophene and tetrahydrothiophene from modelg Cu-BTC. Blanco-Brieva et al. [78] showed that Cu-

a considerable amount of DBT at ambient temperaturech was eight times higher than that of bench-marked Y-

or activated carbons. The higher uptake was explainedf a stronger interaction of the S-atom of DBT with

Cu2+ ions of the Cu-BTC framework. Park et al. [95] isostructural MOFs having N-substituted linkers, andt the uptake of SCCs was increased with the introduc-tron-decient linkers. The authors explained the high

an increased electronic interaction between electron-nd electron-decient linkers [95]. Selective adsorptionm solutions containing iso-octane, naphthalene and

Mo(CO)6 decomposed onto the surface of zinc tereph-OF-5 (Mo loadings up to 20 wt%) has been reported by7]. The breakthrough approached 0.5 mmol S g1 sug-rong afnity between DBT and the Mo carbides and/ors of the adsorbent. The high concentrations of aromat-hthalene and benzene caused the decrease in the sulfurcapacities.al. [72] studied adsorption kinetics and thermodynam-sorption of benzothiophene (BT) over three analogous

as metal terephthalates (MIL-53s(Al, Cr) and MIL-47(V); for the Material of Institut Lavoisier) [9698]. They

Fig. 3. Adibenzo

Source: Rical Soci

conclutant rothe higamongTherefslightldrivingwas duchangemateriSCCs th(PWA)[82] toBT. Theing PWresultigin Cuarea anwas suto favo


Fig. 4. Adsorption isotherms for benzothiophene adsorption over the MIL-47(V) andMIL-53s at 298 K [72].

PWA and slightly basic BT. Therefore, the acidity or basicity ofMOFs originates either from the central metals or from incorpo-rated specieacid-base in

It has bPt2+ have aformation complex-ba-complexature calcinAdditionalland SBA-15of SCCs th[102,103]. Kperformancinvolved reent condition-octane (Ftion capacitthat had thbetween ththe other habenecial eto V3+, Al3+

tion of Cu2+

metals of MOFs as well as their oxidation states are also importantin the various potential applications of MOFs. Moreover, Cu+-loaded iron terephthalate, MIL-100(Fe), was also evaluated by thesame group [84] as an efcient adsorbent for BT adsorption to inves-tigate the benecial effect of -complex formation. The Cu+ specieswas incorporated facilely onto the porous MIL-100(Fe) under mildcondition through a one-step synthesis of Cu2O (without selec-tive reduction of Cu2+ to Cu+ at about 923 K). Q0 increased withincreasing copper loading up to a Cu/Fe (wt/wt) ratio of 0.07 inCu+-loaded-MIL-100(Fe), resulting in an increase in the Q0 by 16%compared with the virgin MIL-100(Fe).

Compared to SCCs, very few reports have been published forthe adsorptive removal of NCCs with MOFs. In 2010, Nuzhdin et al.[89] used highly porous chromium terephthalate, MIL-101(Cr) toremove various NCCs from light cycle oil, and a maximum adsorp-tion capacity of 19.6 mg N g1 was reached. They attributed the highnitrogen adsorption capacity to the coordination of the NCCs onthe Cr3+ sites (CUS) of the MIL-101(Cr). They observed that the bet-ter the steric accessibility of the N atom of the substrate moleculewas, the higher the adsorptive performance of the MOF was. Amore detailed report was published by Maes et al. [106] in whichthey examined a series of MOFs for the adsorption of a mixture ofNCCs and SCCs from liquid fuel. Selective adsorption was observed

everal MOFs such as MIL-100s(Fe, Cr, Al) and MIL-101(Cr)e adsSAB

basetes sacid nce s Cu

detaodiftingL-10uinotion e of

sorp

eral al oflly, s might be involved in adsorbing compounds throughteractions.

een reported that metal ions like Cu+, Ag+, Pd2+ andn adsorption capability for SCCs through -complex[99101]. Yang and coworkers have developed -sed adsorbents for desulfurization [99]. In most cases,ation adsorbents have been prepared by high temper-ation of metal-ion-exchanged zeolitic materials [99].y, Cu2O-loaded porous materials like Al2O3, MCM-41,

have also been reported for the adsorptive removalrough -complex formation between Cu+ and SCCshan and Jhung [81] reported a remarkable adsorptivee for BT adsorption with CuCl2-loaded-MIL-47 whichducing Cu2+ to Cu+ (by the V3+ of the MIL-47) at ambi-n for an efcient -complex formation with SCCs in

ig. 5). The authors demonstrated that the high adsorp-y of CuCl2/MIL-47 (310 mg BT g1; 122% of CuIY [104]e highest capacity so far) was mainly due to a synergye reduced Cu+ ions (for -complexation) and MIL-47. Onnd, CuCl2-loaded-MIL-53s(Al and Cr) did not show anyffect of CuCl2 loading on BT adsorption [105]. Differentand Cr3+ were not efcient in the selective reduc-to Cu+; therefore, it can be assumed that the central

with sand thsons Hharderacid siLewis preferesuch aied theand mby grathe MIbasic qadsorpbecaus

2.2. Adwater

SevremovGeneraFig. 5. Adsorption mechanism (left) and adsorption isotherms (right) of benzothiophorption phenomena were nicely explained with Pear-(hard/soft acid/base) concept. According to this concept,s, such as NCCs, interact preferentially with hard Lewisuch as Fe3+, Cr3+, and Al3+ and also with intermediatesites. On the other hand, softer bases like SCCs have ato interact with intermediate or soft Lewis acid sites2+, Zn2+, Co2+, Ni2+, and Cu+. Ahmed et al. [83] stud-iled acid-base effect on adsorption of NCCs over virgined MIL-100(Cr). The MOF, MIL-100(Cr), was modied

compounds having acidity or basicity onto the CUS of0(Cr). It was observed that the adsorptive removal ofline was improved with an acid-grafted MOF; however,was severely decreased by a basic-group-grafted MOFacid-base interactions.

tive removal of organic contaminants from waste

virgin or modied MOFs have been tested for the various organic contaminants from waste water.pore structure [107], charge interaction between the

ene over virgin and CuCl2-loaded MIL-47(V) [81].


adsorbent and adsorbate [23,108,109], open metal sites [77] orthe breathing properties [110] of the MOFs have been reported asimportant parameters or mechanisms for adsorption. Haque andcoworkers [108] reported that MOF-235 (another phase of ironterephthaladyes (anionlene blue (MMO and MBand only 1activated calso much They also chighly depe[18,77,80,1bent decreadecreased atrary, the cincreases wAdsorptionand the enwith the adthe endotheaction betwthe interactelectrostatiby Hasan eand clobriMIL-101(Cradsorbents the order othe adsorptpore volumpH was proMIL-101(Cr

The opeof MIL-100(MG) [77]; in MG and treplacemenMG. The poin MG and Moreover, tmic processby an entro[107] synthusing cetyland the matics for liquthat all MBadsorbed oabout 110 mtion of phehas a charaof this breatwith increamal observpores, and of p-cresol adue to the dhaving a chaeffect in the

Functionadsorptive water throumodied toadsorb anio

interaction sites of anionic MO and functionalized MIL-101(Cr)adsorbents. The adsorption capacities and kinetic constants werein the order of activated carbon < MIL-101(Cr) < ethylenediamine-grafted MIL-101(Cr) (or ED-MIL-101(Cr)) < protonated

nediae adhe klargel conthanred wed bdom

dsorplarge

sorp

erowateothereen rvy med th0(Feith M

oxidtivelangepaci

pH. XPSlace y adster sr spa

foldtion n wa

of d shohere

the sy hig

on c surreoveovanall

only OFs

sorp

mfulCO, [57apo

nto apot ade 2entsen ha

on esily rte [111]) could be used for the removal of harmfulic dye methyl orange (MO) and cationic dye methy-B)) through adsorption. The adsorption capacities of

with MOF-235 were 477 and 187 mg g1, respectively,1 and 26 mg g1 for MO and MB, respectively, witharbon. The adsorption rates for the adsorptions werefaster with MOF-235 than with the activated carbon.onrmed that, the adsorption of MO and MB dyes wasndent on the pH of the solution similar to other reports09]. The density of the positive charge of the adsor-ses with increasing pH of the MO solution; therefore,dsorption was observed with increasing pH. On the con-oncentration of the negative charge of the adsorbentith increasing pH resulting in increased MB adsorption.

of MO and MB were spontaneous and endothermic,tropy (the driving force of the adsorption) increasessorption of MO and MB. The authors suggested thatrmic adsorptions occurred because of a stronger inter-een the pre-adsorbed water and the adsorbent thanion between the MO or MB and the adsorbent. Simplec interaction was also shown between PPCPs and MOFst al. [23] for the liquid phase adsorption of naproxenc acid. The adsorption capacities of two different MOFs,) and MIL-100(Fe) were compared with conventionalsuch as activated carbon. The efciency decreased inf MIL-101(Cr) > MIL-100(Fe) > activated carbon both forion rate and adsorption capacity. Large surface area ore was benecial for high adsorption, and low solutionven to be favorable for the adsorption of PPCPs over).n metal sites or coordinatively unsaturated sites (CUS)(Fe) were the active species to bind malachite greenwhereas, interaction between the Lewis base N(CH3)2he CUS (Lewis acid) of MIL-100(Fe) occurred due to thet of the water molecules by the Lewis base N(CH3)2 ofssibility of a interaction between the benzene ringsMIL-100(Fe) over the adsorption was also suggested.he adsorption of MG on MIL-100(Fe) was an endother-

and the driving force for the adsorption was controlledpy effect rather than an enthalpy change. Huang et al.esized hierarchically mesostructured MIL-101(Cr) bytrimethylammonium bromide (CTAB) as a surfactant,erial showed remarkably accelerated adsorption kinet-id phase adsorptive removal of MB. They observed

molecules with 30 ppm of initial concentration werento the hierarchically mesostructured MIL-101(Cr) inin. Maes et al. [110] reported the liquid phase adsorp-

nol from contaminated water over MIL-53(Cr) whichcteristic breathing property of the framework. Becausehing effect, a stepwise increase in the adsorbed amountsing concentrations of phenol was observed. This abnor-ation was explained with a sudden expansion of thenally allowed more phenol to be adsorbed. In the casedsorption, this effect was not observed which might beifference in polarity between phenol and p-cresol. MOFsracteristic breathing property also showed a noticeable

vapor phase adsorption of alkanes [112].alization of MOFs has also been reported for theremoval of charged liquid contaminants from wastegh electrostatic interactions. MIL-101(Cr) after being

have a positive charge has efciently been used tonic MO through charge interaction [80]. Fig. 6 shows the

ethyleand th[80]. Ttimes mentalarger compadesorbthe ranhigh aeffect (

2.3. Ad

Numwaste while have bof heareportMIL-10As5+ wof ironrespecwide rtion caat highductedtook pentiallthe ouinterioin a sixadsorpalizatiogroupsCu-BTCHg2+ wunder the vergroupsspeci

Mothe remAdditioto not tural M

2.4. Ad

HarCO2, MOFs gases/vtries igases/vefcienalso thadsorbbetwe

Hamand eamine-grafted MIL-101(Cr) (or PED-MIL-101(Cr)),sorption capacity of PED-MIL-101(Cr) was 194 mg g1

inetic constant over PED-MIL-101(Cr) was around 10r than that of the activated carbon under the experi-ditions. The number of desorbed water molecules was

that of the adsorbed MO molecules (MO is very bulkyith water; therefore, several water molecules may be

y the adsorption of one MO molecule); consequently,ness of the adsorption of MO increased. Therefore, thetion of PED-MIL-101(Cr) was explained by an entropy

positive S) [80].

tive removal of heavy metal ions from efuent

us techniques are available for metal recovery fromr. Many of these are established methods [113118],s are still in the experimental stages. Recently, MOFsegarded as robust adsorbents for the adsorptive removaletal ions from efuent [30,31,119]. Zhu et al. [31]

e removal of arsenic (As5+) from aqueous solutions over). According to that report, the adsorption capacity ofIL-100(Fe) was around 6 and 36 times higher than thate nanoparticles and commercial iron oxide powders,

y (Fig. 7). MIL-100(Fe) was able to absorb As5+ over a of pH (212). However, at a pH above 12, the adsorp-ty decreased drastically since MIL-100(Fe) is not stable

To shed light on the adsorption mechanism they con-, IR and TEM analysis and conrmed that the adsorptionvia formation of Fe-O-As bonds and As5+ was prefer-orbed onto the interior of the MIL-100(Fe) rather thanurface. As a result, porous MIL-100(Fe) provides moreces compared to Fe2O3 nanoparticles, which resulted

higher adsorption capacity. Ke et al. [30] reported Hg2+

from water over thiol functionalized Cu-BTC. Function-s done through coordination bonding between the thiolithioglycol and the CUS of Cu-BTC. Thiol functionalizedwed a very high adsorption capacity (714 mg g1) foras the virgin Cu-BTC showed no adsorption for Hg2+

ame experimental condition. The authors revealed thath adsorption of Hg2+ was due to the high density thiolthe inner surface of the porous MOFs having a hugeface area and a high density of adsorption sites.r, it has been suggested that MOFs can be utilized forl of metal ions with the ion-exchange of MOFs [120,121].y, in some cases, simple ion-exchange procedures leadmetal ions removal but also formation of a few isostruc-

[122,123].

tive removal of harmful gases

or toxic gases/vapors such as H2S, SO2, NH3,NO, benzene have been adsorbed over various,48,60,63,6971,7476,85,124152]. Most of these

rs are released as waste byproducts from various indus-the environment. Effective capture of these unsafers is very important for a clean environment. So far, forsorptive removal, not only the pore size/porosity but-OH, 2-O, open metal sites, and functional groups of

are all quite promising for some specic interactionszardous materials and the host adsorbents.t al. [75] did a comparative study of MOFs that are stableegenerable upon H2S sorption through pressure swing


hyl or

adsorption with 2-OHa closure ofing pressurstrong H2SconsequentinteractionsThe rst andMIL-53(Al) of H2S adsoThe maximto 13.12 andtively, at h

ous

Fig. 7. (a) Adsm/V = 5.0 g/L, T

Source: ReprodFig. 6. Proposed electrostatic interaction between met

processes. The polar H2S molecules interact strongly analog

of the inorganic chain of MIL-53s(Al, Cr), leading to

the pores at low pressure. Interestingly, with increas-e, the pores were reopened with the breaking of the. . .HO (on the metal site of MOFs) interactions, andly, all the pores were lled through weak host-guest

which resulted in steps in the adsorption isotherm. second steps began at 4.5, 118 kPa and 9.0, 210 kPa for

and MIL-53(Cr), respectively. The adsorption isothermsrption over the investigated MOFs are shown in Fig. 8.um adsorption capacities of H2S sorption were reached

11.77 mmol g1 for MIL-53(Al) and MIL-53(Cr), respec-igh pressure (1.6 MPa). On the other hand, MIL-47,

isotherm uand MIL-53suggested tMoreover, the large-pshaped adsto be irreve16.7 and 38tively. Partibetween thfor the irrevreported [8

orption isotherms and (b) linearized Langmuir isotherms for As5+ adsorption by MIL = 298 K).

uced with permission from ref. [31]. Copyright 2012 American Chemical Society.ange and adsorbents [80].

to MIL-53s but with no OH group, exhibits a type-I

pon H2S sorption. The adsorption capacities of MIL-47s(Al, Cr) at high pressure were similar; therefore, it washat the pores in MIL-53s reopened at high pressure.the authors also reported a huge uptake of H2S withores of MIL-100(Cr) and MIL-101(Cr) exhibiting type-Iorption isotherms; however, the adsorptions appearedrsible. The maximum adsorbed quantities at 2 MPa were.4 mmol g1 for MIL-100(Cr) and MIL-101(Cr), respec-al destruction of the framework or strong interactionse framework and the H2S molecules were suggestedersible adsorption phenomenon. Moreover, it was also5] that the adsorption of H2S preferentially occurs

-100 (Fe) gel, Fe2O3 nanoparticles and bulk Fe2O3 powders (pH 4,


Fig. 8. Excess adsorbed quantities of hydrogen sulde on MIL-53(Cr) (pink), MIL-53(Al) (blue), and MIL-53(Fe) (yellow) at 303.1 K at pressures up to 2.0 MPa. (Forinterpretationto the web ver

Source: Reprodical Society.

through theatom of thwhere H2S other basic ate group a[85].

A uorifrom 2,2-bihexahydratfor the adsoquite stableature and 1were 14.0%

The openas the activPetit and BCu-BTC or graphite oxunder ambcoordinatedof a new pand the MOMore than 1in the adscomposite (the adsorpt

new porosity created in the interface where the dispersive forceswere the strongest. Additionally, reactive adsorption was also sug-gested since the lone pair electron of NH3, H2S and NO2 coordinatesto the CUS of the MOFs and breaks the framework structure, andnally results in metal salts [125].

Britt et al. [7] demonstrated the potential applicability of sixMOFs, composed of a Zn4O(CO2)6 cluster linked by terephthalate(MOF-5), 2-amino terephthalate (IRMOF-3), benzene-1,3,5-tris(4-benzoate) (MOF-177), diacetylene-1,4-bis(4-benzoic acid) (IRMOF-62), Zn2O2(CO2)2 chains linked by 2,5-dihydroxyterephthalate(CPO-27) and Cu-BTC in the adsorption and separation of severalharmful gases or vapors including SO2, chlorine, NH3, benzene,ethylene oxide, tetrahydrothiophene, and the results were com-pared with BPL carbon. Fig. 9 shows the breakthrough curves of SO2and NH3 adsorption on various MOFs. Several factors such as theopen metal sites of CPO-27 (or M2(dobdc)(H2O)2; H4dobdc = 2,5-dihydroxyterephthalic acid) or Cu-BTC and the active adsorptionsite with particular functional groups (such as NH2 in IRMOF-3)were proven to play an important role in determining the dynamic

tion performance of these MOFs. For SO2 adsorption, CPO-27d thes 6 tition ecie

7. Onreatesinc

he prtive

breampality oowe3, CNg) i

akthsitescondas r

er stat veed bded tous ghe e of the references to color in this gure legend, the reader is referredsion of this article.)

uced with permission from ref. [75]. Copyright 2009 American Chem-

formation of the hydrogen bond between the 2-Oe V O V moiety in MIL-47 and the H2S molecules,acts as a hydrogen donor. Interaction of acidic H2S withcenters in MIL-47 such as the oxygens of the carboxyl-nd electrons of the benzene ring was also suggested

nated metal-organic framework (FMOF-2, obtaineds(4-carboxyphenyl)hexauoropropane and zinc nitratee) having breathing characteristics was also reportedrptive removal of toxic acidic gases [124]. FMOF-2 was

for the adsorption of SO2 and H2S. At room temper- bar, the calculated weight capacities for SO2 and H2S

and 8.3%, respectively, with FMOF-2. metal sites of MOFs have been reported several times

e sites for the adsorptive removal of various toxic gases.andosz [125] reported composites of MOFs (MOF-5,MIL-100(Fe)) and a graphitic compound (graphite oride, GO) for the adsorptive removal of NH3, H2S and NO2ient conditions. The open metal sites of porous MOFs

with the oxygen groups of GO led to the formationore space in the interface between the carbon layers

adsorpshoweity waadsorpzinc spCPO-2to or gfor Cl2NH3, tadsorpBeforeNH3 cocapabialso shing NHNi, or Mtal bremetal in dry bility wof watwas noadsorbconcluof vari

Dat

F units to form composites with distinct properties.2% (for NH3), 50% (for H2S) and 4% (for NO2) increases

orption capacity were observed using a GO/Cu-BTCcompared with the virgin Cu-BTC). The enhancement ofion capacities for the toxic gases was explained with the

Ba(CH3COOImpregnatiof Cu-BTC win the case perature, S

Fig. 9. Selected kinetic breakthrough curves of (A) SO2 and (B) NH best performance over the other MOFs and its capac-mes larger than that of the BPL carbon. This favorableis due to the presence of a highly reactive 5-coordinates along with the potentially reactive oxo group in the

the other hand, Cu-BTC showed a high efciency equalr than that of BPL carbon for all the gases tested excepte it does not naturally act as a ligand. In the case ofesence of the NH2 in IRMOF-3 sharply improves theperformance compared to the virgin IRMOF-1 or MOF-5.kthrough, IRMOF-3 adsorbed almost 71 times as muchred with BPL carbon, and this can be explained with thef NH3 to readily form hydrogen bonds. Glover et al. [74]d adsorptive removal of several harmful gases includ-Cl, SO2, and octane vapor using M-CPO-27 (M Zn, Co,

n both dry and humid conditions. Here, the experimen-rough results revealed that all these MOFs, with open, are capable of adsorbing the studied toxic gases onlyitions, while in humid conditions the adsorption capa-educed dramatically since the competitive adsorptionrted to dominate. The decrease in adsorption capacity

ry noticeable in the case of NH3 gas, i.e. ammonia wasoth in dry and humid conditions. Generally, it can behat water vapor has a negative effect on the adsorptionases over CPO-27 type materials.t al. [129] demonstrated adsorption of SO2 over)2 (or Ba(NO3)2 and BaCl2)-impregnated Cu-BTC.on led to small microcrystals of barium salts in the poreshile partial destruction of host structure was observed

of only BaCl2. The authors pointed out that at high tem-O2 uptake exceeded the stoichiometric capacity based

3 gases over various MOFs [7].


on the Ba2+ concentration. As a result, the excess SO2 uptake is dueto the contribution of chemical bonding between the metal cations(from the MOF) and SO2, which ultimately resulted in the forma-tion of Cu-sas a good hothe contrarduced isolanally Cu-sdisadvantag

Cu-BTC hCO2 molecustriking enhenhanced Cwork contametal sites interactionsenhancemeCO2 interacincreased wbe one posvapor on vaing open mhinders ads

The effeselectivity with a seriMg, Mn). Itthe CO2 upCPO-27(Mguptakes at The CO2 upother mem8.9 wt% CO2of CO2 per Mthat CPO-27capacity of increased ioto the highet al. reportsmall sized ing [13914synthesizedand showe[141].The Menhanced obvious to ealized MOFMoreover, and CO2 huptake witreported byin whichdiyl))tribenMOF-200 [1,3,5-triyl-tareas of 622400 mg g

other highlyon [70,134]uptakes, thto the total

CO is anBecause of ing CUS cousimulation bent for CO

Adsor

ctros (Cuanc

is ae/sepals h

ads adso

and TC w

solih vapium MIL-

andA-1Fig. 1ed thmol

gh ad-101

wat55] sed cydro

ium s succowo

ma

orptoth from liquid and gas phases; therefore, it has attractederable attention in both scientic research and commer-plications. The invention of new materials for adsorptiontions is indispensable interest and surely will be contin-rther. As a class of recently developed porous materials,ave already shown huge potential applications in gas/vaporuid phase adsorption/removal of hazardous materials suchs, NCCs, dyes, PPCPs, phenolics, SOx, NOx, VOCs and

Fs are superior to other porous sorbents in adsorptiveal of various toxic components because of their high sur-ea, various pore geometries, facile functionalization, ande porosities. The variety of central metals in the frame-f MOFs has led to a new strategy towards adsorption of

s hazardous compounds like SCCs, NCCs, CO2, SO2 and soulfates. Therefore, at low temperature, Cu-BTC behavedst material to possess highly dispersed barium salts. Ony, at high temperatures, Cu-BTC decomposed and pro-ted Cu species that acted as SOx storage sites formingulfates. Irreversible SOx storage, however, is the maine of barium salts-impregnated Cu-BTC materials.as been widely studied for the selective adsorption ofles [14,60,132,133,136]. Yazaydn et al. [135] showedancements in the abilities to capture CO2 as well asO2 selectivity over N2 and CH4 with a Cu-BTC frame-ining 4 wt% water molecules coordinated to the openof the framework. It was suggested that the Coulombic

between water and CO2 are mostly responsible for thent in CO2 adsorption while the quadrupole moment ofts with the electric eld gradient of the sorbent, which ishen water occupies the copper open metal site. It mayitive example of water; however, the effects of waterrious adsorptive performances with other MOFs hav-etal sites require further studies because water usuallyorptions.ct of the metal center on the adsorption capacity andof CO2 adsorption was studied by Dietzel et al. [136]es of isostructural MOFs M-CPO-27s (M Ni, Co, Zn,

was reported that at 298 K and high pressure (50 bar),takes were 51 wt% for CPO-27(Ni) and 63 wt% for). Caskey et al. [73] showed 30.6 and 35.2 wt% CO21 atm with CPO-27(Co) and CPO-27(Mg), respectively.take of CPO-27(Mg) is much higher than that of anyber of the series [73,136,137]. CPO-27(Mg) takes up tobefore breakthrough, corresponding to 0.44 moleculesg ion at low pressure [137]. Thus, it is quite optimistic(Mg) represents a major advance in the CO2 separationMOFs. The end-on coordination mode for CO2, with thenic character of the Mg2+ O interaction, was subjected

adsorption capacity of CPO-27(Mg) [73,137,138]. Ahned the improved CO2 adsorption with high quality andadsorbents obtained by sonication or microwave heat-1]. Small and homogeneous particles of CPO-27(Mg)

via sonication adsorbed 350 mg g1 of CO2 at 298 Kd high isosteric heat of adsorption (4222 kJ mol1)OFs having amine functionalized linkers showed

afnity towards CO2 [60,70,79,132,142146]. It isxpect enhanced CO2 adsorption with amine function-s through the acid-base or electrostatic interactions.strong interaction between the amino functionalityas also been reported [143,144]. A remarkable CO2h MOFs that have an ultrahigh surface area was

Furukawa et al. [69]. MOF-210 [Zn4O(BTE)4/3(BPDC) BTE: 4,4,4-(benzene-1,3,5-triyl-tris(ethyne-2,1-zoate and BPDC: biphenyl-4,4-terephthalate] andZn4O(BBC)2(H2O)3 in which BBC: 4,4,4-(benzene-ris(benzene-4,1-diyl))tribenzoate] having BET surface40 and 4530 m2 g1, respectively, were able to uptake1 of CO2 at 50 bar which exceeds the uptake values of

porous MOFs like MOF-177 and MIL-101(Cr)c, and so. It was assumed that unlike hydrogen and methanee uptake capacities for excess CO2 are directly relatedpore volume of the highly porous MOFs.other toxic gas that is present in the environment.its strong binding ability with metal sites, MOFs hav-ld adsorb CO selectively over other gases. A molecularstudy revealed that Cu-BTC was quite a selective adsor-

over H2 and N2 at 298 K [76]. It was suggested that

Fig. 10.

the eleCu-BTCperform

NOremovmaterigas viametric(1 bar)of Cu-Bporous

Botchrom[152]. phase,than SBtively (exceed(12.4 mthis hiof MILtion in[1531activattional hchromof VOCLi and

3. Sum

Adsrials bconsidcial apapplicaued fuMOFs hand liqas SCCso on.

MOremovface artunablwork ovariouption isotherms of benzene over various adsorbents at 303 K [144].

tatic interaction between the partial charge of CUS of2+ sites) and the CO dipole dominated the adsorptivee.nother gas molecule which has great interest toarate for environmental applications. A number of MOFave been employed successfully to adsorb/separate theorption [131,148151]. Xiao et al. reported the gravi-rption of NO on the open metal sites of Cu-BTC at 196 Kfound that around 9 mmol of NO was adsorbed over 1 ghich was signicantly higher than any other reported

ds for the adsorption of NO [148].or phase and liquid phase adsorption of benzene over

terephthalate, MIL-101(Cr), was studied by Jhung et al.101(Cr) adsorbed 16.7 mmol g1 of benzene in vapor

this value was almost 5.5, 8.7 and two times larger5, H-ZSM-5 and a commercial activated carbon, respec-0). The adsorption capacity of MIL-101(Cr) for benzenee adsorption capacity of pitch-based activated carbon

g1) with a large surface area of 26003600 m2 g1, andsorption capacity was explained by the high porosity(Cr). Moreover, in the case of liquid phase adsorp-er, MIL-101(Cr) synthesized by microwave irradiationhowed better performance compared to a commercialarbon and one MIL-101(Cr) synthesized by conven-thermal techniques [152]. The potential applications of

terephthalate, MIL-101(Cr), in vapor phase adsorptionh as ethyl acetate and p-xylene were also conrmed byrkers [71,156,157].

ry

ion plays a signicant role in removing hazardous mate-


f haza

on throughunsaturatedused succescompoundsproperties hazardous Moreover, iinto MOFs dous toxic coformation, tions betweadsorbates of anionic oMOF materof MOFs infor the efunusual brquite interelike CO2, H2hazardous m

This revpotential adtions/removMOFs matefunctionalizmaterials. Tmost powe

Acknowled

The authImteaz Ahmwoo Jeon acontributio

ic Sciatione and

ncesScheme 1. Important mechanisms for the adsorption o

specic interactions. For example, the coordinatively metal sites (or open metal sites) of MOFs have beensfully to bind (or coordinate) various polarizable toxic

like SCCs, NCCs, CO2, CO, H2S, NH3 and SO2. Acid-baseof MOFs showed a dominant role in the adsorption ofcontaminants having opposite acidic-basic properties.ncorporation of active acidic/basic species and metals

by BasFoundScienc

Refereramatically improves the adsorption capacity for vari-mpounds through acid-base interaction and -complexrespectively. Sometimes simple electrostatic interac-en MOF materials and its counter anionic or cationicare also believed to play a dominating role in adsorptionr cationic dyes, PPCPs over different MOFs or modiedials. The hydrogen bonding between 2-OH or 2-Oorganic chain and guest molecules has been suggestedcient adsorptive removal of hazardous materials. Theeathing behavior of porous MOFs such as MIL-53s issting for pressure swing adsorption of polar moleculesS and SO2. Important mechanisms for the adsorption ofaterials over MOFs are summarized in Scheme 1.

iew reveals that MOFs are undoubtedly regarded assorbents in the eld of liquid and gas phase adsorp-als. Moreover, the versatility in the characteristics ofrials can be imparted through simple modications orations that allow for a widespread applicability of theseherefore, in future studies MOFs might be one of therful adsorbents for a green environment.

gements

ors would like to express their sincere thanks to Mr.ed, Enamul Haque, In Joong Kang, Jong Won Jun, Jae-nd Miss Eun Young Park for their sincere efforts andns for this review article. This research was supported

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7.

Adsorptive removal of hazardous materials using metal-organic frameworks (MOFs): A review1 Introduction1.1 Common hazardous materials1.2 Adsorptive removal of hazardous materials1.3 Metal-organic frameworks (MOFs)1.4 Purpose of this review

2 Discussion2.1 Adsorptive removal of SCCs and NCCs from fuel2.2 Adsorptive removal of organic contaminants from waste water2.3 Adsorptive removal of heavy metal ions from effluent2.4 Adsorptive removal of harmful gases

3 SummaryAcknowledgementsReferences

Ha_MOF_A Review

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