Water Contaminant Elimination Based on MetalâOrganic

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Perspective

Water contaminants elimination based on Metal#Organic Frameworks and perspective on their industrial applications Xiang Li, Bo Wang, Yuhua Cao, Shuang Zhao, Hang Wang, Xiao Feng, Junwen Zhou, and Xiaojie Ma ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b05751 • Publication Date (Web): 24 Jan 2019 Downloaded from http://pubs.acs.org on January 25, 2019

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ACS Sustainable Chemistry & Engineering

Water contaminants elimination based on Metal‒Organic Frameworks and perspective on their industrial applications

Xiang Li,† Bo Wang,*‡ Yuhua Cao,‡ Shuang Zhao,‡ Hang Wang,‡ Xiao Feng,‡ Junwen Zhou,‡ Xiaojie Ma‡ †Advanced

Research Institute of Multidisciplinary Science, Beijing Institute of

Technology,

5 South Zhongguancun Street, Haidian District, Beijing 100081 (P. R.

China) ‡

School of Chemistry and Chemical Engineering, Beijing Institute of Technology, 5

South Zhongguancun Street, Haidian District, Beijing 100081 (P. R. China)

*Corresponding author: Bo Wang; E-mail: [email protected];

Abstract Nowadays, one of the most challenging sustainability issues faced by the society is the safety of water resource. Water pollution caused by hazardous contaminants (e.g. heavy metal ions, emerging contaminants, organic dyes) is a serious issue because of acute toxicities and carcinogenic nature of the pollutants. With the advent of material engineering, unprecedented technical advances have been achieved through diverse technologies in recent decades, including photocatalytic oxidation, photo-Fenton, electron Fenton, adsorption and separation. However, the applications of these technologies have suffered from several limitations, such as the uncompleted degradation efficiency, high energy consumption, narrow pH range for application etc. Metal-organic frameworks (MOFs) have aroused increasing studies in gas storage, separation, sensing, water/air purification and catalysis. The effectiveness of the 1 ACS Paragon Plus Environment

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above applications has been extensively recognized. In recent years, these highly ordered and porous crystalline structures have been recognized as a potential alternative to overcome the technical limitations in the area of water pollution control. This perspective article reports recent progress in the applications of MOFs in the field of environmental pollutants elimination, including the adsorption, advanced oxidation processes (AOPs) heterogeneous Fenton-like reactions and MOF-based membranes for pollutants filtration. Keywords: Metal-Organic Frameworks (MOFs); Environmental contaminants; Adsorption; Advanced Oxidation; Industrial applications Introduction Only 2.5 percent of water on the earth is fresh, making it crucial to use the water effectively and smartly. Nowadays, in both developing and industrialized nations, a growing number of contaminants are entering the water supplies from human activity, including traditional chemicals such as heavy metals, organic compounds and even contaminants of emerging concern (CECs). It is well known that the traditional toxic pollutants (e.g. heavy metal cations and oxyanions) can cause a serious threat to human health and ecosystem.1-5 The toxic heavy metals such as Pb2+, Cu2+, Cd2+, Hg2+ and Cr2O7 2‒ are difficult to degrade. Furthermore, there is a class of micropollutants with trace concentrations (e.g. ng/L or μg/L) which could be carcinogenic or highly toxic such as pharmaceuticals and personal care products (PPCPs), endocrine disrupters

compounds

perfluorooctanoate (PFOA)

(EDCs), 6-9.

perfluorooctanesulfonate

(PFOS)

and

Over the past decades, unprecedented remediation

strategies (including adsorption, separation processing, bioremediation and Fenton like reaction etc.) have been developed with the advent of material engineering.10-14 However, the current technologies are facing the technical limitations such as inefficiency, high energy requirements, and operational problems.5,15 Among all the technologies, adsorption process has become one of the most favored methods for 2 ACS Paragon Plus Environment

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removing toxic contaminants from wastewater.16,17 Common adsorbents, including activated carbon, zeolites and natural fiber usually suffer from low adsorption capacities, poor selective sorption and unsatisfactory regeneration ability. A lot of advanced adsorbents have been developed to overcome these disadvantages, such as the nanostructure metal oxides, carbon nanotubes and porous graphene etc.18 Another common applied technology is advanced oxidation process, apart from the typical oxidation process; the recent decades have brought an increasing interest in technologies based on the application of free radicals, such as hydroxyl radicals, which is one of the most reactive free radicals and one of the strongest oxidants (E0= 2.33 v). The Fenton process has attracted considerable attention in the field of water treatment. Following the pioneering practical application of Fenton reaction for degradation pollutants in the 1930s, the Fenton reaction and its derivative technologies, such as electron-Fenton, photo-Fenton, have been extensively studied.12,19 The traditional Fenton reactions suffer from some drawbacks, such as the acid pH regulation (pH 2.8~3.5), sludge generation and the loss of the catalyst in the effluents. In order to overcome these drawbacks, heterogeneous Fenton-like process with a wide range of materials used as solid catalysis or metal support has been reported. The development of new type of catalysts with low cost, high activity and good chemical stability is crucial and challenging. Among all the current technologies, the application of polymeric membranes for pollutants elimination may lead to the development of the next-generation reusable and portable water purification process. The membrane techniques are cost-effective and technically feasible which can be better alternatives for the traditional water treatment systems since their high efficiency in removal of pollutants meets the high environmental standards.20 Studies have shown that membranes filtration and adsorption processes are very effective to remove trace amounts of pollutants such as heavy metals, anionic phosphates and nitrates and organic pollutants.16,17,21,22 For example, nanofiltration membrane has been proved that could effectively remove emerging contaminants which are hardly 3 ACS Paragon Plus Environment


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eliminated during conventional secondary wastewater treatment process. Also, high chemical oxygen demand (COD), TSS (Total Suspended Solids) and color removal efficiency has been achieved.23,24 In recent years, highly ordered structural and porous crystal, metal organic framework (MOFs) materials attracted great attention due to their wide applications. This novel material is of great interest due to their versatile applications. MOFs are superior to other porous materials because of the high/tunable porosity, pore functionality, various pore compositions and open metal sites etc. It has been recognized as a promising alternative to conventional porous materials and nano-based materials for environmental applications. MOF is a type of porous materials composed of metal ions as nodes and organic linkers forming crystalline structures. Pioneering work has been done by Yaghi25 and others.26 MOFs have some advantages compared to traditional porous materials in terms of highly tunable porosity, designable pore functionality, pore architectures and large amounts of unsaturated metal sites. Some typical porous coordination frameworks are shown in Figure 1.27 The variety of MOFs topologies and tunable chemical functionalities make MOFs attractive for a wide range of applications such as adsorption/storage of carbon dioxide28-30, hydrogen storage31, adsorption of vapors32, separation of chemicals33, drug

delivery/biomedicine34,

polymerization35,

magnetism36,

catalysis37

and

luminescence38. Owning to the prosperity of the research activities on the MOFs, many reviews have been published focusing on a variety of topics related to the preparation and applications of MOF based materials.39-52 In recent years, the emergence of water-stable MOFs largely boosted the applications of MOFs in aqueous environments. ZIF family, MIL family and some zirconium and pyrazolated based MOFs already demonstrated satisfactory water stability. Here this perspective article will emphasize on the applications of MOFs to reduce common hazardous materials from water. Here, three main strategies of using MOFs to control pollution will be discussed. The first one is using MOFs as absorbents for removal of toxic 4 ACS Paragon Plus Environment

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materials from environment via adsorption. The second one is using MOFs to catalyze the degradation of hazardous materials. At last, we discussed the fabrication of MOF-based membrane for filtering hazardous compounds. The performances, mechanisms and advantages of the state-of-the-art MOF-based pollution control method following each strategy will be reported.

Figure 1. The 3D structures of representative porous coordination frameworks.27 Reprinted with permission from Ref. [27], Copyright 2008. The Royal Society of Chemistry.

Adsorption Technology Adsorption technology plays a significant role in removing hazardous materials from water. Compared with other pollution control methods, adsorption method has some unique advantages including low cost, ease of design and recyclability of the adsorbents. The adsorptions could be categorized into physical adsorption and chemical adsorption based on the interactions between adsorbents and adsorbates.53,54 During physical adsorption, the adsorbates are generally captured by Van der Waals forces and adsorbed into the pore structures of the adsorbents. On the other hand, during chemical adsorption, the adsorbates are adsorbed to the adsorbent through 5 ACS Paragon Plus Environment


chemical bonds leading to a much stronger interaction than physical adsorption. Due to the high specific surface area, controllable pore structure and various functional groups, MOFs have been used as a high performance adsorbent to remove hazardous compounds such as heavy metals, organic compounds and toxic gases28,55-62 through interactions like hydrogen bonding, π–complexation, acid-base interaction and π-π interaction (Figure 2). The central metals, open metal sites, functionalized linkers, and loaded active species of MOFs could be designed for enhanced adsorption between the adsorbates and MOFs. Here we summarized some representative works demonstrating superior advantages or performances of MOF absorbents in terms of adsorption capacity, equilibrium time, selectivity, regenerability and cost effectivity.

Figure 2. Schematic illustration of different adsorption mechanisms over MOFs.63 Reprinted with permission from Ref. [63], Copyright 2012, Elsevier.

Metal Ions. The heavy metal pollution of wastewater is a serious environmental issue directly related to human health and other life forms along the food chains. Heavy metals in industrial wastewater include lead, chromium, mercury, uranium, 6 ACS Paragon Plus Environment

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selenium, zinc, arsenic, cadmium, silver, gold, and nickel. Among them, lead, cadmium, mercury and arsenic exposure are the main threat to human health which has been regularly reviewed by international bodies such as the World Health Organization (WHO). They may damage central nervous function, lungs, kidneys, liver and bones which may increase the risk of some cancers16. Numerous efforts have been done to remove heavy metal ions from wastewater. Some of them are established methods.64-67 Recently, MOFs have been found to be promising adsorbents for the adsorptive removal of heavy metal ions from solution. Table 1 summarizes representative researches and compares the advantages and disadvantages of MOFs. Methylthio groups (‒SCH3) were first introduced into MOFs structure to removal Hg(II) by Xu and coworkers.68 Many other functional groups have been introduced to capture Hg(II) based on strong Hg‒S or Hg‒N interaction. Ke and co-workers69 used thiol functionalized Cu-BTC to adsorb Hg2+ from water. The thiol functionalized Cu-BTC had an adsorption capacity of Hg2+ as high as 714 mg g−1. The high adsorption capacity of Hg2+ resulted from binding to the large amount of thiol groups. The equilibrium time was reported to be 120 min. No data about reusability was reported. A 3D bioMOF was reported to have an absorption capacity of 900 mg g-1, which was the highest one so far.70 However, approximate 200 min was required to reach equilibrium. Sulfur-functionalized MOF FJI-H12 was found to have the best overall performance.71 It has a relative satisfactory adsorption capacity of 439.8 mg g-1 and a relative short equilibrium time of less than 50 min. Furthermore, FJI-H12 could selectively adsorb Hg2+ over Mn2+, Ba2+, Ni2+ and Cd2+. More importantly, FJI-H12 could be synthesized in large‒scale with low cost, very mild conditions and could be recycled for reusing (only one day immersing of FJIH12–Hg in the KSCN solution at ambient temperature), which is vitally important for practical applications. On the other hand, this work presents the first continuous and fast removal of Hg(II) using column, a 20 ppm Hg solution in 50 mL water could be completely purified

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by this column at a flow rate of 2 mL/min. This implies the practicality of such materials for wastewater treatment in industry. Table 1. Summary of advantages and disadvantages of published MOFs in removing metal ions Target

MOFs

Advantages

Disadvantages

good capacity of 110 mg g-1, As5+

MIL-100(Fe)72

long equilibrium time of selective, reusable, wide range of pH

1h

2-12 good capacity of 115/143.6 mg g-1, As5+/

CoFe2O4@MIL-10

short equilibrium time of 2 min,

As3+

0(Fe)73

selective,

non-reusable

wide pH range of 4-10 As5+

UiO-6674

high capacity of 303.4 mg g-1, selective good capacity of

Cr2O72-

MOR-1-HA

240‒280 mg g-1, short

equilibrium time of 3 min, wide pH range, selective, reusable, low cost good capacity of

Cr2O72-

MOR-2

194 mg g-1, short

equilibrium time of 1 min, wide pH range, reusable, low cost

Cr2O72-

Hg2+

long equilibrium time of 48 h, unknown reusability long-term stability is unknown

long-term stability is unknown

Fe-gallic acid

ultrahigh capacity of 1709.2 mg g-1,

limited reusable, long

MOFs75

selective

equilibrium time of 72 h

[CU3(BTC)2]n69

high capacity of 714.29 mg g-1

long equilibrium time of 2 h, unknown reusability long equilibrium time of

Hg2+

3D

bioMOF70

high capacity of 900 mg

g-1

200 min, unknown reusability

good capacity of 439.8 mg g-1, short Hg2+

FJI-H1271

equilibrium time of 50 min, selective, wide pH range (3-7), reusable, low cost

U6+

U6+

Carboxyl-function

good capacity of 314 mg g-1, good

alized MIL-10176

equilibrium time of 2 h, selective

MIL-101-DETA77


Limited reusable

good capacity of 350 mg g-1, good

Limited reusable, narrow

equilibrium time of 1.5 h, selective

pH range 4.5-5.5


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Fe3O4@ZIF-878

U6+

High capacity of 523.5 mg g-1, good equilibrium time of 2 h, selective

U6+

HKUST79

Pb6+

Tb-MOF80

Pb6+

HKUST81

High capacity of 787.4 mg g-1, short equilibrium time of 1 h, selective High capacity of 547 mg g-1, short equilibrium time of 1 h, selective High capacity of 787.4 mg g-1, short equilibrium time of 1 h, selective

Limited reusable

Non-reusable

Non-reusable

Non-reusable

MIL family MOFs ((MIL stands for Material Institute Lavoisier) were found to be effective absorbents to remove arsenic ions. MIL-100(Fe) was reported that it could remove arsenic (As5+) from wastewater.72 MIL-100(Fe) could adsorb As5+ with 6 folds higher adsorption capacity compared to commercial iron oxide powders (50 nm Fe2O3 nanoparticle). It was found that the Fe‒O‒As bond is the reason of the As5+ adsorption. Arsenic ions absorbed onto the interior of the Fe–BTC polymer instead of on the outer surface. Yang et al.73 synthesized a core-shell and mesoporous CoFe2O4@MIL-100(Fe) hybrid magnetic nanoparticles (MNPs) for adsorptive removal of AS (III) and AS (V) which exhibits the best performance to date. The Fe‒O‒As inner-sphere complex mechanism was formed on MOFs surface through hydroxyl substitution. It is noted that an excellent anti-interference capacity was confirmed by using the electrostatic repulsion interaction and size exclusion effect of the MIL-100(Fe) shell. The maximum adsorption capacities were 114.8 mg g-1 and 143 mg g-1 for As (III) and As (V), respectively. The adsorption kinetic is very fast that 0.1 mg L-1 arsenic ions could be adsorbed in 2 min. In addition, this MOF could work over a wide range of pH 4‒10 and could selectively capture arsenic ions over various oxyanions. The data about the reusability has not been reported yet. Additionally, UiO‒66 was reported to have a highest adsorption capacity of 303.4 mg g-1 among all reported MOFs.74 This capacity is much higher than that of currently available adsorbents (5‒280 mg/g, generally less than 100 mg/g). Surface functional 9 ACS Paragon Plus Environment


groups (hydroxyl group and benzenedicarboxylate ligand) and highly porous crystalline structure containing zirconium oxide clusters provide a large contact area and plenty of active sites in unit space. The formation of Zr‒O‒As coordination bond accelerates the adsorption process. But it has a low equilibrium time of 48 h. Also, no data of reusability was reported. Uranium, mainly existed in the form UO22+ in aqueous solutions, is radioactive and highly toxic species released from unclear facilities. Carboxyl-functionalized MIL-101 was applied to remove U (VI) via adsorption.76 The adsorption capacity could reach 314 mg g-1 with 2 h equilibrium time. MIL-101-DETA has a similar performance that could adsorb U (VI) with a capacity of 350 mg g-1 and equilibrium time of 1.5 h.77 However, the working pH range for MIL-101-DETA is very narrow (4.5-5.5). Fe3O4@ZIF-8 has an adsorption capacity of 523.5 mg g-1 on U (VI) and an equilibrium time of 2 h.78 These three MOFs have only limited reusability. HKUST was found to have the highest adsorption capacity (787.4 mg g-1) and fastest equilibrium time (less than 1 h) among all the reported MOFs, but it could not be reused.79 A great number of oxygen atoms in carboxyl groups of HKUST-1 provided coordination sites for uranium species. In addition, although the framework was electrical neutral, partial negative charges localized on the carboxylate units. Under near-neutral condition when uranium are present in the form of positive ions (UO2 (OH)

+

and UO22+), adsorption properties of HKUST-1 were supposed to be

determined also by electrostatic interaction. It is worthy to note that so far no investigation about the stability of MOFs under radiation were conducted which is critical for the practical application of MOFs to the radioactive wastewater. Chromium ions in the form of oxyanions (CrO42‒, Cr2O72‒ or HCrO4‒) and cations (Cr3+) are harmful when released into the environment. Niu et al. recently reported an exceptional 1D Fe–gallic acid MOF showing an adsorption capacity for Cr2O72- ions as high as 1709.2 mg g-1.75 This ultrahigh uptake capacity was attributed to the large amount of active sites of the Fe–gallic acid MOF. This MOF also demonstrated 10 ACS Paragon Plus Environment

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excellent selectivity of Cr2O72- over several types of anions and metal cations. Furthermore, this MOF is highly stable in strong acidic (pH= 2) and alkaline (pH= 11) resulting to an unchanged performance over a broad pH range (3.0–9.0). However, it takes about 72 h to reach equilibrium and the MOF could not be reused which are the limitations. MOR-1-HA82 and MOR-283 were reported to have faster kinetics. MOR-1-HA and MOR-2 could reach an adsorption capacity of 240‒280 mg g-1 and 194 mg g-1 within 3 min and 1 min, respectively. Furthermore, these two MOFs could also work in a wide range of pH values and be regenerated. Tan et al.80 synthesized a nanotube-like Tb-based MOF and studied its adsorption property toward Pb2+. The Tb-MOFs demonstrated excellent adsorption capacity of Pb2+ (547 mg g-1). The XPS analysis revealed that the innersphere complexation between nitrogenous groups of Tb-MOFs and Pb2+ is the reason of the ultrahigh adsorption capacity. Yu et al.81 developed a Zn (II)-based MOF functionalized with Ogroup for the removal of Pb2+ via adsorption. An extraordinary adsorption capacity of Pb2+ (616.61 mg g-1) was achieved attributing to the electrostatic attraction and coordination interaction between the sufficient exposed O‒ groups and Pb2+. In addition, this MOF could selectively capture Pb2+ over background ions (Ca2+ or Mg 2+)

with a high efficiency of more than 99%. Organic Contaminants. Recently, various MOFs have been studied for the

adsorptive removal of organic contaminants such as organic dyes, pharmaceuticals and personal care products (PPCPs), perfluorooctanoic acid (PFOA) and bisphenol A (BPA) from wastewater. Table 2 summarizes the advantages and disadvantages of MOFs in adsorbing organic contaminants for comparison. Table 2 Summary of advantages and disadvantages of published MOFs in removing various organic pollutants Target

MOFs

Advantages


Disadvantages


good capacity of ~160 mg g-1, naproxen

long equilibrium time of 4 h (same with

reusable

MIL‒101‒OH84

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activated carbon), narrow range of pH

naproxen

MIL‒101(Cr)85

naproxen

UiO‒66(Zr)86

ibuprofen

UiO‒66(Zr)86

good capacity of ~120 mg g-1,

narrow range of pH,

short equilibrium time of 2 h

unknown reusability

high capacity of 460 mg g-1,

long equilibrium time

reusable

of ~25 h



reusable

of ~60 h long equilibrium time

ibuprofen

MIL‒80886

good capacity of ~206 mg g-1

of 10 h, unknown reusability

sulfonamide antibiotic SCP

high capacity of

417 mg g-1,

Chloroform activated

short equilibrium time of 30

long‒term stability is

UiO‒6687

min, wide pH range 3.5‒7.5,

unknown

reusable high capacity of 1.89 mmol g-1,

PFOA

MIL‒101(Cr)‒QDMEN88

short equilibrium time of 90

narrow pH range

min, reusable high capacity of 156.8 mg g-1, BPA

short equilibrium time of 1 h,

MIL-101(Cr)89

unknown reusability

wide pH range 3.0‒9.0 methylene blue (MB) methylene blue (MB)

MOF‒23590

Fe3O4/ CU3(BTC)291

methyl orange

MOF‒23590

(MO) malachite green (MG)

high capacity of 477 mg g‒1,

narrow pH range,

short equilibrium time of 30 min

unknown reusability

high capacity of 241 mg g-1


wide pH range 2‒11, reusable

of 20 h


narrow pH range,

short equilibrium time of 30 min

unknown reusability

high capacity of 140 mg g-1, MIL‒100(Fe)92

short equilibrium time of 1 h, wide pH range 3.0‒7.0, reusable


In the year 2000, an initial list of 33 priority substances was identified under the EU Water Framework Directive (WFD) 2000/60/EC to be used as a control measure 12 ACS Paragon Plus Environment

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for the next 20 years. In 2007, PPCPs such as diclofenac, carbamazepine were identified as future emerging priority candidates. Ibuprofen, clofibric acid, triclosan, phthalates and bisphenol A were proposed additions to this list.93 There has been increasing awareness of the unintentional presence of emerging contaminants in various aquatic environment.6 Although these chemicals exist in the trace concentration in the environment, they have become a major concern because these chemicals are extensively and increasingly used in human and veterinary medicine, resulting in the continuous release to the environment. A limited efficiency of their removal by commonly employed technologies prompts a search for more efficient and more cost‒effective methods. Recently, Seo and co-authors84 studied the adsorption of typical PPCPs such as naproxen, ibuprofen and oxybenzone from aqueous solutions using the functionalized MIL-101. Their results demonstrated that MIL-101s functionalized with H-donor functional groups (‒OH, ‒(OH)2, ‒NH2) could effectively adsorb naproxen. The MIL-101-OH could be recycled several times by simple washing with ethanol, suggesting potential application in the adsorptive removal of PPCPs from water. Hasan et al.85 found the naproxen could be effectively removed through adsorption with MOFs by electrostatic interaction. They studied the adsorption capacities of MIL-101(Cr) and MIL-100(Fe) and compared them with activated carbon. The results showed MIL-101(Cr) has the best adsorption rate and adsorption capacity of tested organic compound following by MIL-100(Fe) and active carbon. Following this work, Hasan et al.94 found that ethylenediamine (ED) functionalized MIL-101 have the highest removal efficiency and adsorption capacity. On the contrary, the performance of the acidic AMSA-MIL-101 was very poor. The common −NH2 functional group was coordinated on open metal sites or coordinatively unsaturated sites (CUSs) of the MIL-101. The adsorption mechanism may be explained with an acid–base interaction between the PPCPs and the adsorbents. Moreover, the functionalized basic MOF (with −NH2) can be regenerated by simple washing with ethanol which is important for commercial applications. 13 ACS Paragon Plus Environment


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Another work studied the adsorptive removal of a toxic sulfonamide antibiotic sulfachloropyradazine

(SCP)

from

aqueous

solution

using

UiO-66

(Zr–

benzenedicarboxylate, Zr–BDC).87 UiO-66 was shown to have an adsorption capacity of 417 mg g-1. The main adsorption mechanisms were found to be π-π interaction and electrostatic interaction. Fluorinated organic compounds perfluorooctanoic acid (PFOA) is contaminating water system worldwide.95-97 It comes from manufacture releases when employed in specialized industrial processes, such as the semiconductor, medical devices etc. PFOA is nonflammable and resistant towards acids, bases, the majority of oxidants and reductants. The carbon‒fluorine bonds are the strongest bonds in organic chemistry because of a high electronegativity and a small size of the F atom.98,99 The present tertiary water treatment technologies are not satisfied for the effective removal of these contaninants.100 Thus more advanced technologies should be developed.101 Liu et al.88 examined the adsorptive removal of perfluorooctanoic acid (PFOA) with anionic-exchange MIL-101(Cr). The adsorption capacity of PFOA ranged from 1.19 to 1.89 mmol g-1 depending on different synthetic methods of MOFs. They revealed the mechanisms of PFOA adsorption include anion-exchange, Lewis acid/base complexation between PFOA and Cr (III) and the electrostatic interaction between PFOA and the protonated carboxyl groups of the terephthalic acid linker. MIL-101(Cr) was also used to remove bisphenol A (BPA) from contaminated water via adsorption.89 Qin et al.89 found the average pore size and specific surface area of MIL-101(Cr) are the most important parameters determining the adsorption kinetics and capacity of BPA, respectively. They revealed the adsorption mechanisms of BPA over MIL-101(Cr) include π-π interaction and hydrogen bonding. Haque et al.90 reported that MOF-235 could efficiently remove harmful dyes (cationic dye methylene blue (MB) and anionic dye methyl orange (MO)) via adsorption. The adsorption capacities of MO and MB over MOF-235 reached as high as 477 and 187 mg g−1, respectively, while the corresponding values with activated carbon were only 11 and 26 mg g−1. The adsorption rates using 14 ACS Paragon Plus Environment

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MOF-235 were also found to be much faster than that using the activated carbon. The authors also noticed that the pH of the solution greatly influence the adsorption capacities of MO and MB dyes. In the solution with a high value of pH, the adsorbent has less positive charges and more negative charges, thus leading to an increased MB adsorption and decreased MO adsorption, respectively. Huo et al.92 reported the malachite green (MG) could be removed by MIL-100(Fe). They found the Lewis acid/base interaction between N(CH3)2 groups in MG and the open metal sites of MIL-100(Fe) was the reason for the adsorption. MOFs-based Advanced Oxidation Process (AOPs) Adsorption only focus on removing pollutants from water, however, these technologies do not completely “destroy” the pollutants into less toxic organic pollutants. Therefore, the advanced oxidation processes (AOPs), such as the Fenton and Fenton-like reaction, photocatalysis, sonolysis, ozonation, and various combination technologies are commonly applied to degrade contaminants by in situ generating highly reactive and nonselective chemical oxidants (i.e. H2O2, •OH, •O2‒, O3). The Fenton process has attracted considerable attention in the field of environmental remediation.12,102 In the classical Fenton reaction, the ferrous ions (Fe2+) catalyze the decomposition of H2O2, resulting in the generation of •OH radicals. The formed ferric ions can be reduced to ferrous ions again, which is known as Fenton‒like reaction. •OH radicals are the second most reactive chemical species which can initiate the decomposition of organic pollutants by hydrogen abstraction effectively. The Fenton reaction and its derivative technologies, including electron‒Fenton and photo‒Fenton have been extensively studied for environmental remediation following the pioneering practical in the 1930s. Although the technology is promising, the traditional Fenton-like process still suffers from some drawbacks such as the strict pH regulation (pH= 2.8~3.5) and sludge generation. MOF-derived catalysts have been reported in recent years103-107. The growing number of studies on



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this topic suggests that MOF-based Fenton-like catalysis will play a significant role in the elimination of organic pollutants. MOF-based Photo-Fenton Process. During the Fenton-like process, introducing photo energies (UV-light/visible light) can enhance the degradation efficiency significantly. MOFs-derived Fenton-like catalysts have been found that they can overcome several drawbacks in traditional Fenton-like process. Table 3 lists the degradation performance of various environmental pollutants by MOFs-based heterogeneous Fenton-like catalysis process, such as methylene blue (MB), rhodamine B, phenols and emerging contaminants. Table 3. Degradation performance of MOFs-based heterogeneous Fenton-like catalysis for organic contaminants Pollutants

MOFs

Performance

Mechanism

Methylene blue

FeII@MIL-100(Fe) ;

FeII@MIL-100(Fe)>

electrostatic

MIL-100(Fe)>Fe2O3

interaction;

Wide pH range 3‒8

synergistic

(MB)108

effect FeII Methylene blue

NH2-MIL-88B(Fe)

Good recyclability

(MB)109

Methylene blue

Wide pH range 3‒11; Fe- BTC; MIL-100(Fe)

(MB)110

hydroxyl radicals from H2O2

low dosage H2O2 Neutral

hydroxyl

pH conditions

radicals from H2O2

Methyl orange

Fe3O4@MIL-100(Fe)-OSO3H/MW

(MO)111

Fast removal 99.9% removal in 6 min Optimal pH condition 3.0

hydroxyl radicals from H2O2 (Microwaves promote)

Rhodamine B

MIL-53(Fe) magnetic nanospheres

(RhB)112

decoration

98.7% removal in 70 min

•OH from H2O2 react with electrons

Phenol113

Fe-bpydc

90% removal in 120 min near neutral conditions


hydroxyl radicals from

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H2O2 Phenol114

Fe-MIL-88B

Fe-MIL-88B> (Fe2O3,

hydroxyl

α-FeOOH, Fe3O4,

radicals from

MIL-53(Fe),

H2O2

MIL-101(Fe)) Tetracycline115

Fe-MIL-101; Fe-MIL-100; Fe-MIL-53;

180 min: 96%, 54% and

•O ‒, 2

40% removal by

h+

•OH and

Fe-MIL-101, Fe-MIL-100

the degradation

contribute to

and Fe-MIL-53 Clofibric acid

MIL-53(Fe)

(CA)116 Carbamazepine (CBZ)116

98% removal in 270 min;

Electrostatic

Max adsorption capacity

interaction

0.8 mmol/g MIL-53(Fe)

90% removal in 270 min;

π–π interactions

Max adsorption capacity 0.57 mmol/g

Recent studies have shown that in the presence of hydrogen peroxide, MOFs-based Fenton-like process can be very effective in removing organic pollutants, including methylene blue, rhodamine B, phenol and pharmaceuticals.111 108,112,115,116 Most reactions can be performed under a wide pH range.108-110,113 In the presence of visible light and H2O2, the catalytic performance of MIL-53(Fe) can be improved significantly.117 This enhancement can be evaluated by using the synergetic index: SI= kMVH/(kMH + kMV). The kMVH, kMV, and kMH were the apparent rate constants in the catalytic systems of MIL-53(Fe)/visible light/H2O2, MIL-53(Fe)/visible light and MIL-53(Fe)/H2O2 respectively. The SI (SI= 2.22) implies the synergistic effect played an important role in the catalytic activity of MIL-53(Fe). H2O2 functioned in two ways during this photo‒Fenton process: H2O2 was decomposed to produce •OH radicals catalyzed by MIL-53(Fe); H2O2 captured the electrons generated from excitation of MIL-53(Fe) to form •OH radicals under visible light irradiation.117 Another advantage of using MOFs-based Fenton-like catalyst is that small size of Fe3-µ3-oxo cluster in MOFs can reduce recombination,118 leading to a high photocatalytic activity. Studies have shown nanoscale α-FeOOH and α-Fe2O3 catalysts appeared to be more active than the 17 ACS Paragon Plus Environment


micro-meter-sized ones.118 It is well known that the high electron–hole recombination rate limits the yield of highly oxidizing species during the photocatalysis process. Reducing the catalysts particle dimensions might overcome this limitation.

Figure 3. Photocatalytic degradation mechanism of MB over the MIL-100(Fe) under light irradiation.119 Reprinted with permission from Ref.[118].Copyright 2013, The Royal Society of Chemistry. MOFs-based catalysts have difficulties in recycling them from the aqueous solution since they are highly dispersive. To overcome this issue, a novel core-shell structure was developed in which Fe3O4 was used as core and MOFs were used as the shell. A novel magnetic core-shell structure MOFs: Fe3O4@MIL-100 (Fe) catalyst has been developed recently to degrade MB.119,120 Besides it exhibited high adsorption capacity for MB, it could be easily recycled from liquid media by an external magnetic field. H2O2 addition into this system could significantly enhance the photodegradation efficiency of MB. As can be seen from Figure 3, MIL-100(Fe) with transition metals ions can be recognized as the semiconductor since a conduction band could be formed by mixing the empty d metal orbitals with the LUMOs of the organic linkers. MB can be degraded through two mechanisms. The photo generated hole (h+) in the valence band can oxidize MB directly because of the strong oxidation capacity; On the other hand, the electron is excited from the valence band to the conduction band. The photo induced electrons transfer to H2O2/H2O by producing more hydroxyl radicals, which resists the recombination of electron-hole pairs efficiently.119 Further research found 18 ACS Paragon Plus Environment

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that the Fenton-like reaction efficiency is highly dependent on the thickness of MOFs shell.120 Recently, incorporating or doping MOFs with more than one metal ion have aroused increasingly attention. This technique enhances the particular activities.121,122 PB (PB, Fe3[Fe(CN)6]4·14H2O) analogues (PBAs) has been found to have excellent catalytic

capacity

to

remove

organic

pollutants

RhB.123

The

Fe(II)-Co

PBA/H2O2/visible system has a degradation capacity comparable to that of the homogeneous photo-Fenton process (Fe3+/H2O2) under similar conditions at a wide range of pH values from 3 to 8.5. Fe (II)‒peroxide complexes which could generate •OH radicals to degrade RhB were produced as a result of the replacement of the H2O molecules bonded to metal sites by H2O2 molecules. To enhance catalytic activities of MOFs, highly dispersed noble-metal nanoparticles (e.g. Au, Pd, Pt) were immobilized on MIL-100(Fe). A Pd@MIL-100 (Fe) was fabricated using a facile alcohol reduction method.124 Pd atoms could improve the degradation efficiency by reducing the recombination of photogenerated electron-hole pairs. When small amount of H2O2 was added, the photocatalytic activity efficiency of PPCPs rapidly increased. During this process, the H2O2 and H2O were captured by the photogenerated electrons and holes, respectively, to generate •OH radicals (Eq (1‒5)). Also, Fe(III)–O clusters on the surface of Pd@MIL100(Fe) can catalyze the decomposition of H2O2 to produce •OH radicals by Fenton-like process.124 Pd@MIL-100(Fe) → Pd@MIL-100(Fe) (h+ + e−) h+ + H2O → •OH + H+

(2)

e− + H2O2→ •OH + OH−

(3)

(1)

Fe(III) species + H2O2 → Fe(II) species + •HOO + H+

(4)

Fe(II) species + H2O2→ Fe(III) species + •OH + OH−

(5)

In order to improve the photocatalytic oxidation performance, Fe-C oxide nanoparticles were assembled on the open metal sites of MIL-101 through a simple 19 ACS Paragon Plus Environment


organic-acid-directed approach. The results revealed that Fe3+-CA/MIL-101(Cr) system exhibited 10 times more activity than Fe3+-CA/MIL-53(Cr) system, which suggested that the structures of the MOFs greatly influenced the catalysis of decomposing H2O2. MOF-based Electron-Fenton Process. The Electro-Fenton processes have unique advantages that it could in situ produce H2O2 continuously and regenerate Fe2+ by cathodic reduction. Recently a novel cathode made of mixed carbon aerogel (CA) and MOF (2Fe/Co) was developed for degradation of rhodamine B and dimethyl phthalate using solar photo-electron-Fenton (SPEF) process. As shown in Figure 4, the photo-electron-Fenton process with MOF (2Fe/Co)/CA as cathode and solar irradiation has the best degradation performance both for rhodamine B and dimethyl phthalate compared to other configurations of solar photocalysis (SP), electron-Fenton (EF) and photo-electron-Fenton processes. During SPEF process, the H2O2 was produced by reducing the adsorbed O2 through two–electron reduction with MOF (2Fe/Mo)/CA as catalyst (Eq 6‒8). Then the generated H2O2 could either react with the electrons to produce •OH radicals which is the major pathway or directly decompose induced by photo energy which is the minor pathway (Eq (9‒10)). MOF (2Fe/Co) + hν → hνb + ecb−

(6)

O2 + ecb− (+ H+) → O2•−+ (HO2•)

(7)

2HO2• → O2 + H2O2

(8)

ecb− + H2O2 → •OH +OH‒ (strong)

(9)

H2O2 + hν → 2•OH (weak)

(10)


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Figure 4. The degradation efficiency of rhodamine B (left) and dimethyl phthalate (right) with different configurations.125 Reprinted from Ref.[124] Copyright 2016, Elsevier. Currently, few investigations on MOF-based electron-Fenton process have been reported since most of MOFs are not electrically conductive. However, with the continuous discoveries of conductive MOFs,126-129 the MOF-based electron-Fenton process could be a promising technique for degrading organic compounds in wastewater. MOFs-based Membrane for Filtration In addition to remove pollutions through adsorption and catalytic degradation, porous MOFs could also be fabricated into membranes for water filtration. Membrane separations are driven by a positive pressure while the filtration membranes are designed to allow small (non-harmful) species to permeate and reject large (harmful) species. Membrane separation technique has been used for water treatment such as wastewater purification and desalination, offering low energy consumption and good efficiency of removal. Although the powders or crystals of MOFs can be useful as adsorbents in packed-bed systems, they are not suitable for membrane based techniques. Therefore, shaping MOF into membranes is required for membrane based applications. MOFs membranes have several unique advantages for water filtration. 21 ACS Paragon Plus Environment


First, MOF-based membranes could avoid the complicated system for cycling water between adsorptive and desorptive states as required for packed beds. Second, the structural and chemical diversity of MOFs allow for water filtration with high fidelity and high flux. The combination of selective pore structures and high permeability allows MOF-based membrane have both high selectivity and high flux making it competitive for industrial wastewater filtration. Moreover, the introduction of MOFs into membrane-based water filtration also enables the water treatment processes by multifunctional effects, such as adsorption and catalytic degradation. In order to fully take the advantage of the potential of MOFs, it requires the MOFs membranes have good dispersibility, good mechanical robustness, good chemical stability, less defects, low cost and viability of large scale production. To fulfill these requirements, a number of fabrication methods of MOFs membrane have been developed which could be categorized into two main fabrication strategies. They are continuously growth leading to pure‒MOFs membranes and composite systems wherein the MOFs are combined with other materials. Continuous Growth. MOFs membranes fabricated through continuous growth method result in pure MOFs. Therefore the chemical properties solely depend on the MOFs itself unchanged by other components in composite materials. Approaches to in situ continuous MOFs films include solvothermal growth, layer‒by‒layer growth, interfacial diffusion method and roll‒to‒roll hot pressing. During solvothermal/hydrothermal fabrication of MOFs membranes, the mixed precursor solutions of organic ligand and metal salt are heated until the MOFs forms with a substrate added in the precursor solution to support the growth of continuously intergrown polycrystalline structures. A major limitation of the solvothermal method is that the imperfect intergrowth of the polycrystalline could cause large amount of film defects, mainly cracks or voids. A research found a polycrystalline UiO‒66 membrane prepared by in situ solvothermal growth on alumina hollow fibers successfully blocked more than 80 percent of large sized hydrated ions in the solution 22 ACS Paragon Plus Environment

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however still failed to 100 percent.130 Although no evident defects (pinhole or crack) were observed in the UiO-66 membrane under SEM, the reason for the pass of large sized ion might be the missed linkers within the MOFs. Another limitation is that the film quality highly dependent on the chosen substrate. For example, Zacher et al.131 reported HKUST‒1 films could grow on the alumina substrate rather than silica substrate. A technique to possibly overcome this limitation is treating the substrate with self‒assembled monolayers (SAMs) for better MOFs adhesion. During Layer‒by‒layer method or liquid phase epitaxy method, the substrate is exposed to one MOF component (either metal‒only or ligand‒only solutions) at a time and repeatedly cycled with intermediate washing steps, to add MOFs layers in a highly controlled manner. Similar to solvothermal growth, layer‒by‒layer methods may require pretreatment of the substrate with SAMs for stronger MOFs adhesion. Although the layer‒by‒layer method could generate application‒ready films, it is more appropriate for preparation of research‒scale MOFs membranes with highly controllable thickness and low number of defects,132 because the growth process is time‒consuming, synthetically non‒trivial, and difficult to scale up. For interfacial diffusion method, opposite faces of a substrate are covered by metal-only solution and ligand‒only solution respectively. The two components met at the interface by diffusion and formed a MOFs membrane. A unique advantage of the diffusion method is that the defects could be self‒repaired because the species diffuse faster at voids than in those areas already covered with MOFs automatically forming a continuous film with minimized defects. So far, this method has only been reported with several MOFs.133-136 Extending this approach to other MOFs would greatly promote it for MOFs membrane fabrication. Recently, we developed a facile and scalable roll‒to‒roll hot‒pressing method for mass production of continuous MOFs coating on substrates.61 The substrates covered with MOFs precursors rolled between the two rollers for hot pressing and MOFs 23 ACS Paragon Plus Environment


nanocrystals were generated and coated on the substrate after several rolling cycles. The authors fabricated a series of MOF membranes combining different MOFs (i.e., ZIF-8, ZIF-67, and Ni-ZIF-8) and substrates (i.e., plastic mesh, glass cloth, metal mesh, nonwoven fabric, and melamine foam). With an adoption of industrial roll‒to‒roll hot‒pressing facilities, the roll‒to‒roll hot-pressing method can be easily scaled up for large area MOFs membranes. MOFs loading could be easily tuned through increasing or decreasing the number of hot‒pressing cycle. With the increased cycling number, the MOF loadings increased and the distribution of MOFs on substrates transformed from sparse to dense. The average particle size will also gradually increases with increasing hot‒pressing cycles. Because of the strong interactions between MOFs and substrates, the prepared MOFs membranes are very robust. The authors showed the ZIF-8 nanocrystals on plastic mesh substrate could sustain rubbing with a sand paper with no change in crystallinity and morphology. In addition, ZIF‒8 on melamine foam substrate shows negligible weight loss after being bended and twisted each for 100 times. Composite Systems. Since the syntheses results of most MOFs are microcrystalline powders, MOFs have been incorporated into polymeric binders to fabricate MOF‒based Mixed Matrix Membranes (MMMs). The MOFs powder is added to a polymeric solution to form a polymer dope, followed by casting into membranes. In sharp contrast with the continuous MOFs membranes described above which needs substrates, MMMs are free‒standing membranes. Because MMMs use preformed MOFs particles, a wide range of MOFs could be used regardless of their original synthetic conditions. With a low MOFs loading, MOFs in MMMs mainly functioned in a supporting role that enhances the properties of polymer membranes such as providing enhanced flux. If the amount of MOFs in MMMs increased, the MOFs rather than the polymer could dominate the properties of MMMs where the polymer only worked as a binder.137,138 MOFs MMMs have been demonstrated as effective filters for nano-filtration. For example, MOFs MMMs have demonstrated 24 ACS Paragon Plus Environment

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effective adsorptive removal of dyes138-141 and heavy metal ions142 from water. So far MOFs MMMs still have challenges and limitations. For example, the MOFs and polymeric matrix have a tendency to phase segregate leading to aggregation of MOFs particles, which is the main reason for film void defects.143 Electrospinning is commonly used for facile fabrication of fibers.144-147 Recently electrospinning was applied with MOFs as the filler to prepare MOFs loaded electrospun fibers.148-151 We systematically studied shaping MOFs with different structures and surface properties into nanofibers by electrospinning.59 They embedded four MOFs including MOF-119, UiO-66, MOF-74 and ZIF-8 into three polymers including polyacrylonitrile (PAN), polystyrene (PS) and polyvinylpyrrolidone (PVP) to fabricate nanofibrous filters. They observed no obvious aggregations even at a high MOFs loading of 60 wt%. The electrospinning method could fabricate both free-standing fibrous membrane and the fibrous layers on substrates. The diameter of the fibers can be tuned by adjusting the polymer concentration and MOFs loading. The incorporation of MOFs largely improves the porosity and specific surface area of the original polymer filter. Efome et al. applied the nanofibrous MOF-808 membrane fabricated by electrospinning to remove Pb(II) from aqueous solution.152 The membrane has a high flux of 348 L m-2 h-1 and could treat 395 mL of 100 ppb Pb (II) solution to less than 10 ppb (drink water standard).



Figure 5. Preparation of a PSP‒derived membrane by photoinduced postsynthetic polymerization.142 Reprinted with permission from Ref.[141].Copyright 2015, John Wiley and Sons Postsynthetic polymerization (PSP) is a method to integrate MOFs powders into membranes by polymerizing MOFs crystals with a comonomer.142 We demonstrated PSP method by postsynthetically functionalizing UiO-66-NH2 with methacrylamide groups then polymerizing the MOFs crystals with butyl methacrylate.142 A flexible and defect-free membrane could be achieved (Figure 5). The polymerization was conducted by ultraviolet exposure which is rapid and scalable. Yao et al. fabricated a UiO-66-NH2/polyurethane PSP membrane with 70 wt% MOFs which could effectively remove organic dyes from aqueous solution.153 PSP method bridges the gap between the easy and facile operation of MMMs and the optimal performance of continuous MOFs membranes. In-situ self-assembly method is a novel strategy for the preparation of MOF hybrid membranes,140,154 during which the MOF particles and the polymer assembly together through coordination bonds between the metal ions of MOFs and the functional groups in polymer chains.95,154 Use ZIF-8/poly(sodium 4‒styrenesulfonate) (PSS) 26 ACS Paragon Plus Environment

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hybrid membrane as an example. To fabricate such a hybrid membrane, the metal ions of MOF (Zn2+) were first fixed on a substrate (PAN or ceramic). Then the substrate with metal ions on top was dipped into the mixed solution of organic ligands (Hmim) and polymer (PSS). The Zn2+ formed coordination bonds with both organic ligands and polymer simultaneously to generate a layer of MOF hybrid membrane via in situ self‒assembly. This process could be repeated for fabricating multiple layers. The prepared ZIF-8/PSS hybrid membrane demonstrated good stability owning to the strong binding between MOFs particles and polymer via the coordination bond. The advantages of the in situ self‒assembly method are the good compatibility and that the MOFs particles could be uniformly dispersed without any agglomeration. Conclusion and Future Outlook The safety of water resource is becoming one of the top challenging sustainability issues throughout the world. A variety of hazardous materials exist in water environment including emerging contaminants (e.g. pharmaceutical and personal care products, fluorinated compound, endocrine disrupter compounds) as well as the many well‒defined groups (e.g. polyaromatic compounds, persistent organic pollutants, toxic heavy metal ions).4-6,8,9,100 The sewage generated from chemicals and agricultural wastewater were around two million tons according to the 2003 World Water Assessment Program (WWAP) report. They are estimated to be liberated into water system. Recently Environmental Protection Agency in the U.S. has delivered messages to public water utility experts about the water quality issues should be highlighted to face current water challenges including the scarcity and emerging contaminants. The U.S. federal agencies are announcing the program to improve the efficiency of water purification and water reuse with nanotechnologies.155 In addition, the WWAP meeting emphasized how the quality of water supports sustainable economic development (UNSECO, Oct 2016).156,157 Also, WWTPs (wastewater treatment plants) has become one of the major means of water protection against pollution originating from various anthropogenic and natural processes. 158-160 27 ACS Paragon Plus Environment


In this current review, the recent progress of applying MOFs for hazardous materials removal during wastewater treatment process is summarized. It has been shown a large number of target heavy metal ions and organic contaminates could be effectively removed by MOFs through adsorption, heterogeneous Fenton-like AOPs and separation. MOFs which have highly ordered structural and porous crystal could be recognized as a potential alternative to overcome several drawbacks of traditional porous material for wastewater treatment process, such as (i) MOF structures can be rationally designed through facile control on the architecture and functionalization of the pores. For example, emerging contaminants are structurally diverse, multi-functional sites can be introduced through the introduction of multiple functional species. As a result, pollutants could be selectively removed. The proposed mechanism might contain hydrogen bonding, π interaction and electrostatic interaction simultaneously. For example, the thiol functional group has been introduced to Cu‒BTC in order to capture Hg (II) based on strong Hg‒S bond; Acidic (‒SO3H) and basic (‒NH2) group will increase the adsorption capacity between PPCPs and adsorbents by acid‒base interaction. (ii) The adsorption capacity of MOFs for various environment pollutions was usually the highest. In addition, MOFs are easy in operation and simple in design and are reusable. (iii) MOF‒based heterogeneous Fenton-like reaction can overcome the limitations of narrow pH range (2.8~3.3) in traditional Fenton-like reaction. (iv) Easy doping of heteroatoms, from MOFs precursors or guest species, offering more opportunities for catalysis reaction. In terms of performance MOF/MOF‒based materials are competitive with conventional materials used in industries for adsorption or degradation. However, to the best of our knowledge, so far no MOFs have been industrially realized for pollution control even though more than a thousand patents related to new MOFs compounds, new fabrication methods and new applications or improvements have been filed to date.40 In this context, the concern in this community has shifted to the promotion of industrial applications of MOFs. The durability of MOFs is a 28 ACS Paragon Plus Environment

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questionable challenge. Whether the MOFs could fully maintain their functions and critical structure after multi ‒ cycle applications requires further investigation. In previous researches, researchers have mainly focused on studying the hydrothermal stability of MOFs, while their stability after being put into practical wastewater environment still needs further assessment. Similar to pristine MOFs, challenges about the long term stability in realistic condition still remained for the industrial application of MOFs membranes. More detailed investigations on the long‒term stability of MOFs membranes in acidic/basic environments, in complicated organic solvent systems, and at high temperatures are required. In addition, the successful application of a new material in industry usually requires their multifunctionality. Given the great designability of MOFs, preparing MOFs with multifunctionality could greatly accelerate the industry adoption of MOFs. Future efforts should be put on the development of MOFs or MOFs membranes that not only have a long‒term stability, but also have multifunctional applications such as adsorption and photocatalytic process. Another issue blocking the large‒scale practical application is the cost of MOFs. The proper selection of readily obtained organic ligands instead of expensive organic ligands could greatly lower the cost of large‒scale synthesis of MOFs. Only very recently, the interest has arisen in the community to develop low‒cost, economically viable strategies that do not rely on expensive or rare raw metal and organic ligands. Therefore, more cost‒effective design strategies should be invented to promote the industrial application of MOFs. Companies like BASF have been developing the ton scale synthesized method of MOFs which aimed to fulfill the need the low cost MOFs in industry application. With the continuous effort put by the academics and industrial companies, it can be expected that MOFs products will generate real impact on the market.



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Acknowledge This work was financially supported by the National Natural Science Foundation of China (Grant No. 21625102, 21471018), Beijing Municipal Science and Technology Project (Z181100004418001), and Beijing Institute of Technology Research Fund Program. Reference (1) Sharma, P.; Bihari, V.; Agarwal, S. K.; Verma, V.; Kesavachandran, C. N.; Pangtey, B. S.; Mathur, N.; Singh, K. P.; Srivastava, M.; Goel, S. K. Groundwater Contaminated with Hexavalent Chromium [Cr(VI)]: A Health Survey and Clinical Examination of Community Inhabitants (Kanpur, India). PLOS ONE 2012, 7(10), e47877, DOI: 10.1371/journal.pone.0047877. (2) Nakano, Y.; Takeshita, K.; Tsutsumi, T. Adsorption mechanism of hexavalent chromium by redox within condensed-tannin gel. Water Res. 2001, 35(2), 496-500, DOI: 10.1016/S0043-1354(00)00279-7. (3) Kikuchi, M.; Syudo, A.; Hukumori, M.; Naito, C.; Sawai, J. Changes in aquatic toxicity of potassium dichromate as a function of water quality parameters. Chemosphere 2017, 170, 113-117, DOI: 10.1016/j.chemosphere.2016.11.158. (4) Mandal, B. K.; Suzuki, K. T. Arsenic round the world: a review. Talanta 2002, 58(1), 201-235, DOI: 10.1016/S0039-9140(02)00268-0. (5) Järup, L. Hazards of heavy metal contamination. British Medical Bulletin 2003, 68, 167-182, DOI: 10.1093/bmb/ldg032. (6) Richmond, E. K.; Rosi, E. J.; Walters, D. M.; Fick, J.; Hamilton, S. K.; Brodin, T.; Sundelin, A.; Grace, M. R. A diverse suite of pharmaceuticals contaminates stream and

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DOI:

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For Table of Contents Use Only

Figure description: Metal organic frameworks have been proved to be a promising alternative for future water treatment.

Explanation of the sustainability of this article One of the most challenging sustainability issues faced by the society is the safety of the water resource. Water pollution caused by hazardous contaminants is a serious issue because of acute toxicities and carcinogenic nature of the pollutants. This perspective article reports recent progress in the applications of MOFs in the field of environmental pollutants elimination, including the adsorption, advanced oxidation processes (AOPs) heterogeneous Fenton-like reactions and MOF-based membranes for pollutants filtration.

Biographies of all the listed authors

Xiang Li is currently an assistant professor at Beijing Institute of Technology. She received her Ph.D. in Environmental Chemistry from Tsinghua University in Beijing, China, in 2016. She worked as postdoctoral fellowship at Temple University from 2016 to 2018. Then she joined Beijing Institute of Technology in 2018 where she works on the emerging contaminants treatment based on advanced technologies.


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Bo Wang obtained his BS, MS and PhD from Peking University in 2004, University of Michigan in 2006 and University of California Los Angeles in 2008, respectively. He has been a professor at the School of Chemistry and Chemical Engineering, Beijing Institute of Technology since 2011. His research interests focus on metal–organic frameworks, membranes/films and other functional porous composites for gas separation, purification and toxicant capture and sensing.

Yuhua Cao obtained her B.S. degree from Hainan Normal University in 2018. She is currently studying at Professor Wang's research group at the Key Laboratory of Cluster Science, Beijing Institute of Technology. Her research interests focus on emerging contaminants degradation by metal organic frameworks.

Shuang Zhao obtained M.S. degrees from Beijing University of Technology in China in 2018. Then, He joined Prof. Bo Wang’s group at the key Laboratory of Cluster Science, Beijing Institute of Technology, as a doctoral student. His scientific interests focus on metal organic framework materials for gas separation and water treatment.



Hang Wang obtained B.S. and M.S. degrees from Northeast Normal University in China in 2014 and 2016, respectively. Then, he joined the research group of Prof. Bo Wang as a doctoral student at the Key Laboratory of Cluster Science, Beijing Institute of Technology. His current research interest focuses on metal organic framework materials for the treatment of toxic and hazardous substances

Xiao Feng received his B.S. degree in materials chemistry in 2004 and his Ph.D. degree in materials science in 2008 from Beijing Institute of Technology. He carried out a joint Ph.D. research program at the Institute for Molecular Science, Japan (2009–2012). He is now an associate professor at Beijing Institute of Technology and his current research interests focus on functional porous materials, including metal–organic frameworks and covalent organic frameworks.


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Junwen Zhou is an assistant professor at Beijing Institute of Technology. He received his PhD in inorganic chemistry in 2015 from Peking University. His current research interests focus on functional porous materials, composites, and membranes/films for emerging electrochemical energy storage technologies.

Xiaojie Ma is an assistant professor at Beijing Institute of Technology. She received her BS in Chemistry and Chemical Engineering in 2012 and Ph.D. in chemistry in 2016. Her research interests focus on the photocatalytic activity of porous materials.


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