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Metal−Organic Framework Films and Their Potential Applications in Environmental Pollution Control Xiaojie Ma, Yuantao Chai, Ping Li, and Bo Wang*
Acc. Chem. Res. Downloaded from pubs.acs.org by UNIV AUTONOMA DE COAHUILA on 05/11/19. For personal use only.
Key Laboratory of Cluster Science, Ministry of Education, School of Chemistry, Beijing Institute of Technology, Beijing 100081, P. R. China
CONSPECTUS: Metal−organic frameworks (MOFs), an emerging class of porous hybrid inorganic−organic crystals, exhibit very important application prospects in gas storage and separation, heterogeneous catalysis, sensing, drug release, environmental decontamination, etc., due to their competitive advantages over other traditional porous materials (e.g., activated carbon and zeolite), including high surface areas, adjustable pore size, uniformly distributed metal centers, and tunable functionalities. However, MOF particles are usually difficult to be processed into application-specific devices because of their brittleness, insolubility, difficulty in molding, and low compatibility with other materials. It is an urgent need to shape MOF nanocrystals into various useful configurations by developing effective fabrication methods. Specifically, versatile functional MOF films with robustness and operation flexibility are highly desired. Although an increasing number of MOF films and their diverse applications have been demonstrated, this field is still at an emerging stage with challenging issues. In this Account, we describe our recent research progress on controllable synthesis of MOF films, highlighting postsynthetic polymerization, in situ interweaving, and solvent-free hot-pressing methods. Basically, two main synthesis concepts are involved, including incorporation of the performed MOF particles into polymer matrix and in situ growth of MOF coatings on surface. In MOF/polymer hybrid films, MOF nanocrystals were covalently linked by flexible polymer chains via graft copolymerization, interconnected by functional polymer chains via in situ polymerization, or adhered to polymer matrix via specific interactions at interface, consequently leading to a molecular-level homogeneous membrane or functional coating layer or foam. In these examples, the existence of polymer endows MOF films with favorable features of processability and flexibility, along with new functions. Moreover, we developed an in situ solvent-free hot-pressing method as a general approach for efficient fabrication of MOF coatings on various commercial substrates (e.g., cloth and metal foils), where metal ions or ligands were chemically bonded to the surface functional groups or metal sites at the early stage of nucleation and subsequently assembled into continuous, uniform, and stable MOF layers under confined conditions. We further extended it to a scalable manufacturing method, roll-to-roll production. MOF films severing as filters (MOFilters) have significant applications in air and water purification. They show high and stable performance in PM capture along with a low pressure drop, holding promise of application in both industrial and residential environments. Moreover, MOFilters can remove SO2 and O3 from air by adsorption and catalytic decomposition, respectively. Given the functional diversity of MOFs, mixed pollutants in solution could also be efficiently trapped by multifunctional MOF hollow tubes. We believe this Account will offer new insights for design and preparation of functional MOF films and coatings and accelerate the practical applications of MOFs.
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neous catalysis, sensing, etc.2−8 Especially, the vast number of combinations of metal centers and linkers provide structural and functional diversity for MOFs, which is considered as the unique and competitive advantage of MOFs over previously known porous materials, like activated carbon and zeolite.
INTRODUCTION
Metal−organic frameworks (MOFs), constructed from metal cations or clusters and organic ligands, are an intriguing new class of crystalline hybrid materials with reticular topology.1 The fascinating characteristics of high surface areas, predesignable pore size, homogeneously dispersed active sites, and versatile functionalities make MOFs very attractive candidates for gas storage, molecule separation, drug delivery, heteroge© XXXX American Chemical Society
Received: March 3, 2019
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DOI: 10.1021/acs.accounts.9b00113 Acc. Chem. Res. XXXX, XXX, XXX−XXX
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application. Each of the above strategies has its own benefits and drawbacks that we should make a balance of according to the practical needs. The following are several effective fabrication protocols we employed, including in situ interweaving, postsynthetic polymerization (PSP), and solvent-free hotpressing (HoP) methods we proposed (Figure 1), as well as electrospinning and freeze-drying methods.
Many researchers are dedicated to functional design, controllable synthesis, and precise characterization of MOFs and their structure−property relationship investigation as well as potential application exploration, and a series of major breakthroughs have been achieved over the past decades.2−4,9−11 Along with this, there is an ever-growing demand for processing MOF nanocrystals into specific devices required in practical application scenarios.12,13 However, MOFs synthesized from traditional techniques, like a solvothermal method, are commonly fine powders or tiny particles with intrinsic brittleness, insolubility, and nonthermoplastic property. They can hardly be shaped by using typical solvent and melt processing techniques. The poor processability of MOFs significantly hinders their extensive applications. It is urgently needed to develop controllable and scalable processing approaches to shape MOFs into desired configurations (e.g., films, foams, etc.), while still preserving the individual merits of MOFs. Recently there are an increasing number of processability studies of MOFs and also impressive work on the application of MOF films, foams, or other shaped bodies.12−15 Environmental remediation has become one of the most important applications of MOFs since they proved to be efficient adsorbents or catalysts for health hazard removal from air and water.16−18 In this Account, we present our recent progress in MOF film fabrication and focus on the interesting contributions of these porous films to environmental decontamination.
Figure 1. Three strategies we proposed for MOF film fabrication.
Incorporation of the Performed MOF Particles into Polymer Matrix
Starting from the first concept, here we present in situ interweaving, PSP, electrospinning and freeze-drying methods, respectively.25−27,36−38 In Situ Interweaving Method. Flexible and conductive MOF films, serving as electrodes for high-performance solidstate supercapacitors (SSC), were prepared by developing an in situ interweaving method.36 Briefly, isolated and insulating MOF crystals resting on a flexible substrate were electrochemically interwoven by intrinsically conducting polymers. The fabrication of an MOF-based electrode was a two-step process. First, ZIF-67 selected as an electrical charge storing material, was uniformly coated on the carbon cloth (CC) in the presence of Super P and a poly(vinylidene fluoride) (PVDF) binder. By using the obtained ZIF-67-CC as a working electrode, conductive polyaniline (PANI) was then synthesized from monomer aniline via an electrochemical process to interconnect nonconductive ZIF-67 crystals (Figure 2a). The crystallinity of ZIF-67 was well maintained after these procedures. The resultant PANI-ZIF-67-CC with MOF loading as high as 3.5 mg cm−2 was porous, but its specific surface area and pore volume were much lower than that of ZIF-67-CC and pristine ZIF-76. The polymer chains not only cover the outer surface of MOF but also go deep into the internal pore. This is helpful for the efficient electron migration along or accessing the backbone of MOF crystals (Figure 2b) and, consequently, brings a remarkable areal capacitance of 2146 mF cm−2 at 10 mV s−1. Photoinduced Postsynthetic Polymerization. Since postsynthetic modification (PSM) was proposed by Cohen and others,39 it has been proven to be a very powerful strategy for the functionalization of MOFs. Inspired by PSM, we have developed PSP for controlled integration of the selected MOF particles and polymers.27 Stand-alone and homogeneous MOF films with good elasticity and flexibility can be obtained by PSP strategy. The two key steps in the PSP process are covalent modification of the organic ligand with polymeriziable functional groups and subsequent graft polymerization of organic monomers on MOFs. Compared with conventional
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STRATEGIES FOR MOF FILM FABRICATION According to Fischer and co-workers,15 MOF films can be divided into two main categories, surface-mounted MOFs (SURMOFs) and polycrystalline films. The former is a kind of ultrathin and smooth MOF film newly emerging.19 Highly ordered, preferentially oriented, and thickness-tunable SURMOFs can be elaborately designed and achieved under carefully controlled conditions by using methods like the Langmuir−Blodgett technique and liquid phase epitaxy.20 By contrast, polycrystalline films are usually thick films with individual MOF particles randomly distributed in a matrix or on a surface discretely or continuously. Here, we mainly focus on the polycrystalline MOF films, which are more commonly used in environmental pollution control. Up to now, a variety of methods have been employed to produce such a kind of MOF films, including solvothermal synthesis, microwaveassisted deposition, seeded growth, electrochemical synthesis, dip-coating, freeze-drying, etc.13−15 Generally, two main concepts are introduced, including post-treatment of the performed MOF particles and in situ growth of MOF films. The first concept usually involves the transfer of the selected MOF particles onto a surface or into a matrix with or without the help of polymers.13,21−23 The integration of MOF and polymer is a very promising way which could endow MOF films with considerable flexibility and processability as well as new functions.21,24−27 On the down side, the activity of MOFs may be partly diminished due to the blockage of pores or channels by polymer chains.28,29 Also the films may lack homogeneity due to the aggregation of MOF particles.22,30 Direct growth of MOF nanocrystals on the given surface is a straightforward and useful strategy to obtain MOF coatings.14,31−35 However, some commonly used techniques, like solvothermal synthesis, usually could not lead to a firm bond between MOF layers and substrates. Also these methods may be time or energy consuming from the view of practical B
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Figure 2. (a) Schematic showing the fabrication process of an MOF-based electrode. (b) Schematic showing the electron migration in MOF interwoven by conductive PANI. Reproduced with permission from ref 36. Copyright 2015 American Chemical Society.
Figure 3. (a) Ligand modification of UiO-66-NH2 and subsequent photoinduced copolymerization. (b) SEM images of the PSP-derived membrane (20 wt % MOF loading) and UiO-66-NH2/PBMA blend membrane (20 wt % MOF loading). (c, d) PXRD patterns and CO2 adsorption curves. Reproduced with permission from ref 27. Copyright 2015 Wiley-VCH.
Figure 4. (a−c) The free-standing ZIF-8/PAN film (a), ZIF-8/PAN layer supported on the stainless-steel wire mesh (b) and flexible nonwoven fabrics (c), respectively. (d) Photos and SEM images of MOF/PAN layer (60 wt % MOF loading) supported on nonwoven fabrics. Reproduced with permission from ref 26. Copyright 2016 American Chemical Society.
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DOI: 10.1021/acs.accounts.9b00113 Acc. Chem. Res. XXXX, XXX, XXX−XXX
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Figure 5. Various hollow tube systems with conjugated, “Janus”, “cellular”, or “coaxial” structures. Reproduced with permission from ref 25. Copyright 2017 American Chemical Society.
(Figure 4).26 The composite films can meet both high MOF loading (60 wt %) and good MOF particles dispersion. As expected, the porosity as well as the surface area of polymer film were significantly increased with the addition of MOFs. For example, the ZIF-8/PAN hybrid had about a factor of 10 improvements in BET surface area over pure PAN. Benefiting from the advantages of both MOF and polymer, MOF-based nanofibrous layers supported on flexible substrates, like nonwoven fabrics, can serve as filters for air pollution control. We will discuss this in detail in the later application section. Freeze-Drying Method. Polymers, sometimes, might decrease the porosities of MOFs and have a direct influence to the activity, especially when it acts as an inactive component.28,29 One promising way to get rid of this problem is to fabricate MOF/polymer composites into porous foams through freeze-drying.42 The freeze-drying procedure involves the direct removal of template solvents by sublimation. Its potential advantages are as follows. (1) Low-temperature processing is applicable for some MOFs with poor thermostability. (2) The MOF/polymer hybrid could be easily molded into the designed shape without being influenced by the elimination of solvent molecules. (3) The unfavorable blockage of the MOF pore by polymer chains can be weakened by creating additional macro-pores and/or meso-pores via freeze-drying. The hierarchical pore structure thus formed is beneficial for the effective mass transfer in gas or liquid applications. Because of these advantages, a freeze-drying technique has been performed on MOF composites in a few studies.42 We embarked on shaping MOF nanocrystals into robust and functional foam films by employing such a powerful approach. Specifically, HKUST@Fe3O4 foams with tunable MOF loadings were generated by freeze-drying of the fluid mixture of HKUST@Fe3O4 and carboxymethyl cellulose (CMC) in a mold with a cylinder shape.38 The thus-obtained composite
polymerization techniques, photoinduced polymerization was employed due to its unique advantages, such as mild reaction condition, less side reaction, solvent-free process, and easy molding. As schematically illustrated in Figure 3a, MOF nanoparticles bearing initiator groups (UIO-66-NH-Met) were prepared by reacting methacrylic anhydride with amino groups in UIO-66-NH2. Then, the functionalized UIO-66-NH-Met nanocrystals copolymerized with acrylate monomers under UV within several minutes. As verified by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and CO2 adsorption (Figure 3b−d), homogeneous and porous UIO66-NH2/poly(butyl methacrylate) (PBMA) hybrid films were successfully derived by the PSP method without destroying the framework of MOF. Compared with the UIO-66-NH2/PBMA blend membrane, the PSP-derived membrane shows no obvious particle aggregations and interface defects (Figure 3b), due to the enhancement of polymer−MOF compatibility by forming chemical interactions. The PSP strategy is also available to obtain the UIO-66-NH-Met/poly(methyl methacrylate) (PMMA) hybrid film. It is regarded as a general and effective approach. Dong and co-workers have prepared a flexible UIO-66-urea-based film with tunable MOF loadings for dye adsorption and separation by copolymerization of UIO-66-NH2 particles with polyurethane monomers.40 Electrospinning Method. Besides postpolymerization, an alternative way for polymer incorporation is physical blending of MOF nanocrystals with polymers followed by electrospinning, freeze-drying, etc. Electrospinning is a useful and facile fiber fabrication technology, allowing for the production of MOF-based nanofibers.26,37,41 After being mixed with polyacrylonitrile (PAN), polystyrene (PS), or polyvinylpyrrolidone (PVP), four MOFs (ZIF-8, UIO-66-NH2, MOF-199, and Mg-MOF-74), distinct from topologies and surface functionalities, were electrospun into either free-standing fiber mats or nanofibrous layers on the given substrates D
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substrate surface. Alternatively, the HoP process without the use of both solvent and polymer binder was proposed to realize in situ production of continuous and robust MOF coatings speedily and efficiently.35 We have further extended this method to a large-scale roll-to-roll production technique.46 Solvent-Free HoP Method. Stable MOF layers on either rigid or flexible substrates were generated by HoP-powdered precursor mixtures (metal salts and organic linkers) in the presence of polyethylene glycol (PEG) under 200 °C for 10 min with an electric iron.35 The following two steps are involved in the HoP process. First, under the given temperature and pressure, metal ions or ligands were chemically bonded to the substrates with abundant functional groups or metal sites on the surface (e.g., cloth, metal foils) (Figure 6). Then, nucleation and subsequent MOF crystal
foams exhibit a hierarchical micromeso porous structure, low volume density (95.4% over 12 h (Figure 9b) and could be reused several times after a simple washing and drying process without significant loss of performance. The ZIF-8@Glass cloth and ZIF-8@Metal mesh with high endurable temperatures are available for the PM filtration at 200 °C. This high-temperature performance endows the MOFilter with the possibility of being applied in industry environments. In simulated indoor conditions, the ZIF-8@Plastic mesh, with a high light transmittance and good air permeability, realized a 4-fold increase in PM removal efficiency compared with bare plastic mesh. It is noteworthy, that the excellent PM filtration performance of ZIF-8@Plastic mesh could last for over one month in real environments. Besides, the “cellular” PM filter was produced by freeze-drying of ZIF-8/SA composites, as discussed above (Figure 9c−e).25 The “cellular” filter presents remarkable PM removal efficiency (PM2.5, 92 ± 2.2%; PM10, 95 ± 2.6%) along with a low pressure drop (e.g., 12 Pa, 10 cm s−1), and it might be potentially used as a diesel particulate filter in vehicles.
Concluding Remarks and Prospects
In this Account, we summarized our recent advances in controllable synthesis of MOF films and their environmental applications. We presented two strategies for polycrystalline MOF films fabrication, post-treatment of the performed MOF particles with polymers, and in situ growth of MOF layers on the substrates. Four methods, including postsynthetic polymerization, in situ interweaving, electrospinning, and freeze-drying, were introduced to achieve hybrid films with the integrated advantages of MOFs and polymers. Particularly, postsynthetic polymerization is enabled to achieve free-standing and homogeneous films due to the enhancement of polymerMOF compatibility by forming covalent interactions. Flexible and conductive MOF coatings could be produced by in situ interweaving isolated MOF particles resting on substrates via G
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Figure 10. (a) SO2 dynamic adsorption capacity of PAN filter and MOFilters. (b) Cycle performance of UiO-66-NH2/PAN filter. (c) PXRD patterns of MIL-100(Fe), nonwoven fabrics, and MOFilter. (d) Decomposition of ozone (200 ppb) on MOFilter. Reproduced with permission from refs 26 and 47. Copyright 2016 American Chemical Society. Copyright 2018 WILEY-VCH.
Figure 11. (a) Separation performance of PSP-derived membrane for Cr(VI) ions. (b) The mixed solution of AsO43− and MO before and after filtration with adouble-layer (ZIF-8 + NH2-MIL-101)@SA hollow tubes. (c) Comparison of the filtration efficiency of four different samples. Reproduced with permission from refs 27 and 25. Copyright 2015 WILEY-VCH. Copyright 2017 American Chemical Society.
MOF coatings or films, along with the interfacial interactions between MOF layers and the substrate surface. Third, it is preferred to derive hierarchical and multifunctional MOF films for the application in a complex environment by utilization of the designability of MOFs. Moreover, it is very promising to realize the precise control of the arrangement and orientation of MOF particles and the thickness of MOF films. Last but not the least, future work should give much attention to the integration of MOF films with other components in the device for practical application.
electropolymer. In situ hot-pressing and its related roll-to-roll production methods were also proposed to achieve stable MOF coatings on commercially available substrates (e.g., cloth and metal foils), where metal ions or ligands chemically bonded to the surface functional groups or metal sites at the early stage of nucleation are responsible for the robustness of MOF layers. Furthermore, we demonstrated the potential applications of these MOF films in air and water decontamination. Although significant progresses have been achieved, MOF thin film fabrication is still an emerging field full of energy and challenges. First, low-cost fabrication methods with generic applicability are largely desired, especially the solidstate synthesis techniques. Second, further detailed study is needed to access the formation process and mechanism of
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AUTHOR INFORMATION
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[email protected]. H
DOI: 10.1021/acs.accounts.9b00113 Acc. Chem. Res. XXXX, XXX, XXX−XXX
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Bo Wang: 0000-0001-9092-3252 Notes
The authors declare no competing financial interest. Biographies Xiaojie Ma received her B.S. in chemistry and chemical engineering in 2009 and M.S. in polymer chemistry and physics in 2012 from Lanzhou University. She obtained her Ph.D. in physical chemistry in 2016 from the Institute of Chemistry, Chinese Academy of Sciences. Now, she is an assistant professor at Beijing Institute of Technology. Her research interests focus on the photocatalytic activity of porous materials. Yuantao Chai received her B.S. degree in chemical processing engineering of forestry products at the Northeast Forestry University in 2016. Then, she joined Prof. Bo Wang’s group as a master student at Beijing Institute of Technology. Her current research interest focuses on metal−organic frameworks design and synthesis. Ping Li obtained her M.S. degree in analytical chemistry in 2016 from Henan University. Then, she joined Prof. Bo Wang’s group as a Ph.D. student at Beijing Institute of Technology. Her current research interest focuses on photocatalytic activity of metal−organic frameworks. Bo Wang obtained his B.S., M.S., and Ph.D. 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.
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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (Grant 2165102, 21471018, 21490570, 21674012, and 21801017), Beijing Municipal Science and Technology Project (Z181100004418001), Beijing Natural Science Foundation (2184121), and Beijing Institute of Technology Research Fund Program.
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DOI: 10.1021/acs.accounts.9b00113 Acc. Chem. Res. XXXX, XXX, XXX−XXX
