Modern progress in metal-organic frameworks and

Microporous and Mesoporous Materials 253 (2017) 251e265

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Modern progress in metal-organic frameworks and their composites for diverse applications Pawan Kumar a, Kowsalya Vellingiri b, Ki-Hyun Kim b, *, Richard J.C. Brown c, Manolis J. Manos d a

Department of Nano Science and Materials, Central University of Jammu, Jammu, J & K 180011, India Dept. of Civil & Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea Environment Division, National Physical Laboratory, Teddington, TW11 0LW, UK d Department of Chemistry, University of Ioannina, 45110 Ioannina, Greece b c

a r t i c l e i n f o

a b s t r a c t

Article history: Received 2 May 2017 Received in revised form 13 June 2017 Accepted 2 July 2017 Available online 8 July 2017

Over the last decade, metal-organic frameworks (MOFs) have received a great deal of interest in materials science due to their excellent material properties such as high surface area, porosity, high chemical and thermal stability, luminescence, high sorptive capacity, and potential use in a wide range of applications. However, several shortcomings, including laborious synthesis and analysis processes, low aqueous solubility, and poor electrical properties, are currently limiting factors for their practical application. As a means to overcome such limitations, enormous effort has been put into the development and use of MOFs composite materials (e.g., MOF-nanomaterials, MOF-carbon materials, and MOFspolymers) in a range of applications including the energy, environmental, biomedical, and sensing areas. In this review, we present the current state-of-the-art in MOF composite materials and their diverse applications. In addition, we also discuss the advantageous features of MOF composites as a promising avenue for future development. © 2017 Elsevier Inc. All rights reserved.

Keywords: MOFs MOF-Composite materials Challenges Diverse applications/utilizations

1. Introduction Over the last decade, tremendous progress has been made in the development of porous materials for gas storage, separation, catalysis, energy, sensing, and biomedical applications [1e6]. Among these classes of porous materials, porous coordination polymers (PCPs), which are popularly known as metal-organic frameworks (MOFs), have drawn a great deal of attention due to their highly functional properties (e.g., crystalline nature, high chemical and thermal stability, high surface area, and excellent optical nature) [1e11]. Moreover, the tunability and regenerability have been keys to the success of MOFs in a variety of applications. To date, around 20,000 MOFs have been produced for a range of applications with different combinations of metal nodes and organic linkers [8]. However, there are currently only a few published case studies that demonstrate the real-world commercialization of MOFs. Nevertheless, the potential advantages of MOFs have led to intensive research and publication in recent years,

* Corresponding author. E-mail address: [email protected] (K.-H. Kim). http://dx.doi.org/10.1016/j.micromeso.2017.07.003 1387-1811/© 2017 Elsevier Inc. All rights reserved.

garnering a large number of citations. According to the Web of Science Database (Thomson Reuters), the number of publication titles with ‘metal-organic framework’ in 1995, 2005, and 2015 were in the increasing order of 5, 96, and 1,465, respectively, with citations to those papers increasing from 1,1984, and 71,296, respectively. To date, many articles have reviewed the properties and the future potential of MOFs [2,7e18]. Most notably, progress on MOFs was covered extensively in the second themed issue of Chemical Society Reviews (RSC) in 2014, after earlier mentions in Chemical Reviews (ACS) in 2009 and 2012 [19]. Numerous studies and reports have reported the feasibility of using MOFs in real-world applications [8]. Nonetheless, only a few efforts have actually been made to evaluate and/or overcome the barriers that currently face the further development of MOFs. In January 2016, Coordination Chemistry Reviews (Elsevier) published a special issue entitled ‘Chemistry and applications of MOFs,’ which dealt with a broad range of MOF-related subjects. That review discussed the diversity of MOF chemistry and some of the newly emerging areas in MOFbased composites; all of these subjects are important for the continued growth of this promising field and for the realization of

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their full potential in real-world applications [20]. Nevertheless, key challenges facing MOF research must be addressed before these materials can be widely used in real-world applications. In this respect, ongoing research into MOFs must focus on their current drawbacks (e.g., laborious synthesis, complicated validation processes with some unfavorable properties, small pore size, poor solubility, low electrical conductivity, toxic nature, and nonbiodegradability) to further improve their commercial viability. These drawbacks pose big questions with respect to the future use of MOFs; for instance, when using MOFs in environmental fields, their environmental sensitivity, treatment capacity (waste management), aqueous solubility, dispersion in organic solvent systems, and chemical stability in the open environment must all be considered [13e15,17]. Many of these challenges will likely require interdisciplinary research approaches to progress further. Moreover, present research into MOFs should also consider a number of issues that have been largely ignored in the current literature. These topics include: (1) Most porous MOFs (more than 20,000) have been synthesized in non-aqueous or mixed water-non-aqueous solvents. As of now, only 62 MOFs have been prepared in aqueous media; [8] (2) Many of the current MOFs have small pore sizes relative to their analogue materials (zeolites); (3) Electrically-insulating behavior of MOFs; (4) Low chemical stability of MOFs in aqueous phases and their limited thermal stability; (5) Toxic effects of MOFs on human health; (6) High costs of MOF synthesis; (7) Disposal of MOFs after use. In this review, a comprehensive evaluation on various applications of MOF composite materials is provided together with an assessment of their limitations. In section 2, prospects of MOF research are addressed from the perspective of sensing, storage, and separation applications. In addition, we emphasized the addition of functional groups (before and after their synthesis), the activation of pendant groups (and metal ions), the design of chemical structure (e.g., bioinspired materials), and the synthesis of MOF hybrid materials (with many other approaches) [8,9,21e25]. For example, the CO2 capture and storage (CCS) capacity of MOFs under flue gas conditions has been thoroughly investigated using amine-functionalized Mg2(dobpdc) (dobpdc4
¼ 4,4’-dioxidobiphenyl-3,3’-dicarboxylate) [25]. Similarly, carboxyl group-based MOFs are also familiar due to their great affinity for dyes; for example, the MOF ZJU-24 has a removal capacity of up to 902 mg g
1 for methylene blue, with complete removal after 12 h [26]. Likewise, the bioconjugation of MOFs has been performed with drugs, enzymes, DNA, antibodies, and other biomolecules for biological and sensing purposes; this has been done with nanoparticles (NPs), quantum dots, and carbon nanotubes (CNTs) [8,9,21
25]. In addition, this review elaborates on the present and future opportunities of MOFs and their composite materials in device fabrication and associated technologies. Lastly, the performance of MOF composites (such as MOF-nanoparticles) is discussed as a means to expand their applications. Final remarks are provided to guide the direction of MOF research in order to maximize the possibility for their practical utilization in the future. 2. Prospects of MOFs and their composite The rapid increase of reports regarding new synthetic methods for MOFs and studies investigating their physicochemical properties clearly indicates their potent role as new materials for versatile

applications in various emerging fields. Presently, in the more mature fields of MOF application (e.g., gas storage, separation, and catalysis), their usage is expected to be extended to replace many commonly used materials (for applications such as drug delivery and storage). However, the present literature on MOFs also recognizes a number of shortcomings for their practical application such as: (a) high final product cost, (b) difficult synthesis methods, (c) poor hydrothermal stability, (d) lack of chemical stability toward humidity and temperature, (e) absence of a simple regeneration process, and (f) difficultly in recycling and disposal [27]. As such, some of the drawbacks of MOFs may slow their implementation. However, the scope of their chemical and structural tuning is highly advantageous and can offer improved performance for the capture and storage of gaseous pollutants relative to conventional materials (such as MEA, activated carbon, or other filtration media). In addition, the pore structures of MOFs are also suitable for developing novel approaches for post-synthetic modifications (e.g. controlled etching). Likewise, recent investigations into the toxicological properties of MOFs are encouraging for their expanded use in certain medical applications [17,27]. 2.1. Up-to-date scenarios in synthesis of MOFs and their composite As mentioned earlier, the practical use of MOFs remains challenging; as such, these materials have yet to be adopted in industry. These issues have been studied in the literature from time to time (e.g., MOFs special issue in Coordination Chemistry Review 2015-16, Chemical Society Review 2014, and Chemical Review 2012), although not in great depth. Here, we discuss these challenges in more detail. 2.1.1. Laborious synthesis and analysis processes At present, many different approaches (e.g., hydro/solvothermal, microwave, electrochemical, mechanochemical, ultrasonic, layer-by-layer, and high-throughput syntheses) using aqueous and non-aqueous media have been employed for the synthesis of MOFs. Relationships between these synthesis approaches and the important properties of MOFs have been assessed comprehensively in a number of recent research papers [28e32]. Careful consideration must be taken when choosing the synthetic method because this can affect the shape, size, phase formation, and many other properties of the resulting MOF. Note that many synthetic routes were initially developed following conventional hydrothermal, solvothermal, and slow diffusion methods using typical processing conditions (taking several hours to several days). For these conventional methods, heating was also required (e.g., electric heating, sand baths, oil baths, or heating jackets) [10,29,31,33e35]. Recently, some alternative approaches (e.g., microwave (MW)-assisted hydrothermal, ultrasound (US) irradiation synthesis, sonocrystallization, mechanosynthesis, micro precipitation, co-precipitation methods, stirring, and solventless high pressure synthesis) have been introduced, providing a number of advantages (e.g., more facile preparation, fast kinetics, high phase purity, high yield, low cost, and commercially-viable routes toward the production of MOFs) [2,10,29,31,33e35]. Presently, MW and US irradiation methods are the most attractive options due to their short crystallization time and low reaction temperature. In another series of studies, two or more phases were formed in a one-pot chemical reaction during the synthesis of MOFs; the separation of these phases remains as one of the biggest challenges for the real-world application of these MOFs. Both issues severely hamper the utilization of the synthesized MOFs because MOFs with similar structures can have enormously different properties and features. In the present literature, various approaches, including solvent-assisted separation of mixed MOFs on the basis of their density difference and metal
organic polyhedra (MOPs), have

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been investigated by leading research groups in this area [36,37]. However, their effectiveness is limited due to the density difference and toxicity induced by the separating parent solvent (CH2BrCl). More recently, a facile seed-mediated approach has been demonstrated for the effective separation of diverse MOF mixtures and the synthesis of phase-pure MOFs [38]. However, the prerequisite conditions (e.g., seeds should be introduced up until the first minute of MOF synthesis) for this approach again limit the synthesis of target MOFs for specific applications. Consequently, it is imperative to develop a general and eco-friendly approach to facilitate the separation of mixed MOFs, which are prone to form in one-pot chemical reactions. In the future, extensive, fundamental, and targeted studies on large-scale MOF synthesis for specific purposes should be undertaken to facilitate the use of MOFs in realworld applications (see Fig. 1).

2.1.2. Solubility and stability of MOFs Using materials in aqueous solvent systems is often preferable for biomedical and environmental treatments because of the nonflammable and nontoxic nature of aqueous media, biodegradability, and easy disposal for waste management. At present, aqueous synthesis approaches (e.g., solvothermal/hydrothermal, stirring, co-precipitation, and MW/US irradiation synthesis) are mainly utilized for biological applications of MOFs [10,29,31,33e35]. The structural stability of MOFs in aqueous media is largely affected by the presence of ionic oxide species (Fig. 2a) [39]. For example, MOF-5 (Zn4O(BDC)3; BDC ¼ 1,4benzenedicarboxylate) exhibits a decrease in BET surface area from 900 to 45 m2 g
1 upon exposure to water, which causes the hydrolysis of Zn4O SBUs and the formation of a new crystal

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structure. A similar situation was observed in the case of MOF-177 (Zn4O(BTB)2; BTB ¼ 1,3,5-benzenetribenzoate) [40]. More recently, other techniques were also investigated in attempts to improve the hydrostability and hydrothermal cyclic stability of these frameworks (Fig. 2b) [39]. As such, remarkable hydrolytic stability has been demonstrated in a class of MOFs that was recently developed based on octahedral Zr6 clusters and polycarboxylate ligands. In particular, MOFs based on terephthalate ligands, denoted as UiO66-type MOFs, are stable even under extremely acidic conditions [40]. The stability of these MOFs is attributed to their structures, which contain 12-connected frameworks. In addition, various members of the MIL-family, such as MIL-53 and MIL-125, are also known to be water-stable MOFs [40]. In addition to the obstacles described above, MOF research also faces many other challenges, especially in biological fields; these additional obstacles include: (a) controlling the MOF particle size to produce stable formulations amenable to specific applications; (b) a lack of understanding about the agglomeration process of MOF nanoparticles in solution and its prevention; (c) surface engineering of MOF nanoparticles in the presence of metals, counter anions, non-coordinating complexing functions, and functional groups of the linked functional (or reactive) groups on their surface; (d) testing the specific capacity for MOF nanoparticles to cross natural barriers (e.g., blood brain barriers (BBB) for targeted drug delivery applications); and (e) the development of practical and stable drug formulations to meet the requirements of real healthcare applications [36e47]. For example, Hansen solubility parameters (HSP) have been investigated for encapsulation (e.g., caffeine into certain MOFs like ZIF-8 and NH2-MIL-88B) and synthesis of their composites (poly (L-lactic acid) - HKUST-1) [48e50]. Hopefully,

Fig. 1. Diverse applications of MOFs as described in the literature to date [17].

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Fig. 2. (a) Factors controlling the structural stability of MOFs in aqueous media, and (b) methods used to improve the hydrostability and hydrothermal cyclic stability of MOFs [39].

hosteguest interactions in MOFs with organic and inorganic moieties could benefit on the basis of HSP for diverse biomedical applications. The basic principle of “like dissolves like”, i.e., the qualitative idea on the MOFs-composites is expressed in numbers for easy comparison [49,50]. Nevertheless, the lack of HSP data for MOFs is a limitation for their application. The instability of MOFs under humid conditions is generally found as the main obstructing factor of their applications. To avoid this problem, many MOF based composite materials have been investigated. For example, Li et al. (2016) reported ultrafast room temperature synthesis methods for a novel composite like Imi-CuBTC imidazole (Imi) to improve stability against moisture [48]. Interestingly, evidence indicated that the steam stability of Imi-CuBTC was improved significantly compared to simple Cu-BTC (Fig. 3) [51]. Overall, a strategy of incorporating Imi into Cu-BTC turned out to be very efficient in improving its structure stability against moisture due to the protection of Cu sites from Imi [51]. As such, the ultrafast room temperature synthesis is promising for scalable production of MOF-based materials. Overall, the lack of fundamental understanding related to the critical issues or challenges MOF application have slowed the implementation of MOFs in real-

world situations. Hence, countless efforts have been made to overcome these limitations, some of which have begun to find success. For instance, the MOF research community has fabricated more specialized families of water-stable MOFs that have great potential and affordable costs; these materials will be useful in such fields as environmental remediation, drug delivery, and biomedical imaging.

2.1.3. Electrically conductivity of MOFs Presently, the use of MOFs as components of electronic devices has been limited due to the insulating character of their organic ligands. However, progress toward the development of electrically conductive MOFs has been achieved through doping techniques that make use of their crystalline nature, high surface area, robust chemical stability, and ability to form composites with other electrically-active materials (such as graphene, CNTs, and miscellaneous nanomaterials) [30,52e56]. In addition, properties such as the high intrinsic charge mobility, guest-dependent conductivity, and different doping approaches have been considered. The present literature considers the production of state-of-the-art

Fig. 3. Graphical abstract of Imi-Cu-BTC (Imi ¼ imidazole) and Cu-BTC (HKUST-1) for enhancing the steam stability [51].

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conductive MOFs and their networks to be one of the most significant issues that must be addressed in order to achieve optimized performance for future electronic devices made from MOFs [56e58]. To date, one of the grand challenges in MOF research has been elucidating structureepropertyecomposition relationships in order to provide a clear set of a priori design principles [30,52e58]. Furthermore, issues such as a lack of appreciable band dispersion in the electronic structure and poor electron transfer in MOF structures (with poor overlap between frontier orbits and the electronic states) remain as the most important issues that must be overcome if there is to be an improvement in their charge mobility [52e58]. To counter the present lack of electrical conductivity, some new approaches have been introduced; these include adding redox or catalytic active sites into organic linkers, active guest molecules, biomolecules (e.g., enzymes or bacteria), NPs, and electrical conductors (for mixing) [56e60]. In the present literature, integrating guest molecules or mixing with electrical conductors has been carried out with conductive organic linkers and metal nodes to form long-range delocalized electrons to improve the charge mobility [56e60]. More recently, MOF films with ohmic conductivity have been produced by direct electron transfer and have been tested in electronic devices, reconfigurable electronics, and sensor [56e60]. For example, air-stable electrical conductivity has been achieved over a range of six orders of magnitude, with values as high as 7 S m
1 for Cu3(BTC)2 MOF (also identified as HKUST-1; BTC, benzene-1,3,5tricarboxylic acid) thin films upon infiltration with the molecule 7,7,8,8-tetracyanoquinododimethane (TCNQ). In this case, the TCNQ guest molecules offer improved conductivity by bridging the binuclear copper paddlewheels in the framework, leading to strong electronic coupling between the dimeric Cu subunits [60]. Two-dimensional MOFs tend to exhibit the highest conductivity due to in-plane charge delocalization and extended p-conjugation in the MOF sheets mediated by electronic communication through the metal nodes [52e62]. For example, Campbell et al. (2016) investigated the synthesis of 0.2 S cm
1 bulk conductive 2D Cu3(HITP)2 (HITP ¼ 2,3,6,7,10,11-hexaiminotriphenylene) MOFs for reversible chemiresistive sensors, which allowed detection of subppm levels of ammonia vapor [52]. In this report, the authors concluded that a careful design of MOFs allows effective tuning of functional topographies and properties [52]. 2.2. Prospects in gas storage and separation Due to the current shortage of convenient, safe, and inexpensive storage systems, clean energy resources are potential alternatives for the replacement of current energy systems based on fossil fuels. In numerous clean energy technologies, hydrogen is an appealing material [63e70]. Nevertheless, limitations of suitable media for hydrogen storage, such as compressed gas (in pressurized tanks) and liquefied hydrogen (in cryogenic tanks), present major drawbacks and challenges for the successful implementation of a “Hydrogen Economy.” Hydrogen storage requires a large amount of pressure due to its low density (89.88 g m
3) at atmospheric pressure. In addition, hydrogen storage also poses serious safety risks. While searching for an effective, safe, and affordable hydrogen storage system, diverse classes of materials have been proposed. Emphasis has been placed on solid adsorbents (e.g., activated carbon, zeolites, and metal-organic frameworks (MOFs)), conventional metal hydrides (e.g., LaNi5H6 and Mg2NiH4), complex metal hydrides (e.g., NaAlH4 and LiBH4), and chemical hydrogen storage (e.g. NH3BH3) because of their advantageous features such as molecular hydrogen binding through weak van der Waals forces (physisorption) or the more

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predominant and stronger binding of atomic hydrogen (chemisorption) [63e71]. However, using these solid materials for hydrogen storage has yet to satisfy all of the criteria required for an ideal clean energy solution, such as high volumetric and gravimetric storage capacities, fast kinetics, favorable thermodynamics, low desorption temperatures, excellent reversibility, long-term cyclic stability, and lower costs for on-board applications [63e71]. Future research on MOFs for hydrogen storage systems has been set to target 6.0 wt% of the total vehicle weight at low operating temperatures (near 77 K) and high pressures (up to 90 bar) [67] These targets for MOFs were set to overcome the 2017 storage capacity goals established by the US Department of Energy (DOE) for on-board hydrogen storage [64e71]. MOFs have great potential as hydrogen storage media to achieve the guideline targets of the DOE under ambient temperature conditions due to their advantageous properties (e.g., high isosteric heat of H2 adsorption, large surface area and pore volume, appropriate pore size, weak dispersive interactions, excellent reversibility, fast kinetics of hydrogen release, and high hydrostability and thermal stability) [64e73]. As such, the development of novel, low-cost MOFs with improved properties represents an ideal strategy to help upgrade the storage capacity by enhancing the rate of interactions between H2 and the host frameworks. Likewise, MOFs and their composite materials have been investigated intensively for air quality management through separation, capture, or catalysis of diverse pollutants. For instance, in many studies of air purification, the performance of MOFs and their composite materials has scantly been evaluated with respect to the actual environmental conditions of their removal (e.g., ambient air pressure). The practical data to accommodate the ambient environmental conditions are thus lacking for many permanent and/or toxic gases (such as CO2, O2, ammonia, sulfur dioxide, chlorine, iodine, and cyanogen chloride) [26,27]. For example, Darunte et al. used amine functionalized MIL-101(Cr) to assess direct adsorption of CO2 from highly concentrated sources (flue gas) [73]. Two types of amines such as tris (2-amino ethyl) (TREN) and low molecular weight, branched poly(ethylene imine) (PEI-800) were loaded on the MOF pores at different loading rates for the synthesis of MIL101(Cr)-TREN and MIL-101(Cr)-PEI-800. Both composites showed high adsorption capacities of CO2, although they were subjected to significant losses of amines over swing adsorption experiments at multicycle temperature (Fig. 4) [73]. Interestingly, the removal efficiency of MIL-101(Cr)-PEI-800 showed a strong dependence on the amine loading with a step change to exhibit the maximum efficiency at ~0.8 mmol poly(ethyleneime)/g [73]. Therefore, it is anticipated that in the near future MOFs and their composites will find the special demand for specialized applications. Nevertheless, the practical performance metrics of MOFs and their composites have not yet been established due to a number of constraints: (a) final product cost, (b) lack of established synthesis methods, (c) hydrothermal stability, (d) chemical stability towards humidity and temperature, (e) simple regeneration at low energy penalty, and (f) recycling and disposal of spent material [27]. 2.3. MOFs and their composite based sensing device fabrication To date, numerous studies have demonstrated the potential of fabricating sensing devices from porous materials. This interest is due to the combined effects of the structure of individual crystals and coatings with specifically designed pore sizes, arrangement, and distribution [17,74e77]. However, more research is required to obtain a better understanding of the true potential of these porous materials. Among the classes of porous materials, the importance of coordination polymers (MOFs in particular) has recently been highlighted due to their exceptionally high accessible surface area.

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Fig. 4. Graphical abstract of direct capture of CO2 using amine functionalized MIL-101(Cr) [73].

Basically, high surface area is indeed reflected as the function of the framework due to inorganic nodes and coordination bonding with organic bridging ligands [17,74e77]. MOFs are generally synthesized through self-assembly processes to allow spontaneous growth of hybrid crystals with complex supramolecular architectures of ordered crystal lattices [17,76e78]. Nevertheless, the selfassembly capacity of MOFs is a major challenge for the further development of MOF-based technologies. A number of different strategies, such as patterning, permanent and dynamic localization, and top-down MOF patterning, have been proposed to control the positions of ultra-porous crystals in MOFs [17]. The development of chemically-functionalized MOFs is a favorable strategy to attain carefully controlled growth of crystal lattices [76]. Such approaches are also favorable due to many other beneficial characteristics of these materials including their magnetism, functional porous characteristics, ability to be produced via photolithography (and imprinting), rearrangement under an external field, reactivation and recycling, and local heating capacity [17,76e78]. For example, Tran et al. (2017) reported porous Ni-MOF/MWCNTs composite based on nickel-metal organic framework (Ni-MOF) and multiwalled carbon nanotubes (MWCNTs) for non-enzymatic urea detection (Fig. 5) [79]. Ni-MOF/ MWCNT coated indium tin oxide glass electrodes showed a very high sensitivity of 685 mAmM
1cm
2, low detection limit of 3 mM and a fast response time of 10 s. Novel hybrid inorganiceorganic materials showed notable potential for designing of micro-scale. Overall, these electrochemical sensors showed remarkable stability with no loss in activity for urea sensing applications after 30 days of storage under ambient conditions [79]. Further, the stateof-the-art technique of growing surface-bound metaleorganic frameworks (SURMOFs) has been studied intensively for the deposition and patterning of MOF thin films using a liquid-phase pseudo-epitaxial process [76]. Additionally, crucial deficiencies in advanced device fabrication techniques have also been overcome to realize real-world applications [17,76e78]. In this respect, the integration of MOFs with other novel or functional materials is also a promising pursuit to stimulate device fabrication techniques.

Fig. 5. Steam stability map of MOFs. The position of the MOF structure represents its maximum structural stability (as probed by XRD analysis), while the energy of activation for ligand displacement by a water molecule (as determined by molecular modeling) is represented by the magenta numbers (in kcal mol
1) [79].

3. Progressive trends in MOFs-composite As of now, little work has been conducted to examine the interactions between MOFs and nanomaterials such as MOFnanoparticles, MOF-carbon materials, and MOF-nanocomposites [79e125]. However, this subject is currently becoming the main focal area for MOF research across a diverse range of technical areas (e.g., storage, separation, sensing, catalysis, and many other emerging areas). These applications aim not only to overcome the drawbacks of using MOFs but also to provide significant improvements to the characteristics of MOFs (such as adding conductivity to MOFs). MOFs have also been used increasingly for novel industrial applications such as gas separations/storage, sensing small molecules, and clean energy applications (including batteries, fuel cells, and capacitors). Thus, it is anticipated that this pioneering work will speed up the onset of widespread practical applications

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of MOFs. Moreover, in the coming years, the use of MOFs will increase considerably to expand into the realm of real-world applications. In this section, we summarize the literature in this area, highlight some of the extraordinary features of MOFs, and discuss how these findings have been beneficial to a wide range of applications (Table 1) [79e125]. The present literature describing potential solutions to -MOF challenges is currently scant because this emerging research field is in the early stages of development. Advancement of this subject in future will require consideration of the following aspects: 1) the potential for integrating sophisticated inorganic nano-systemMOFs with a variety of properties, including plasmonic, electro-/ thermo-chromic, and up-/down-conversion properties, into their composites; 2) the ever-increasing number of MOFs and their hybrid materials, which enable customized chemical functionalities and tailored pore size and arrangement; 3) the rapid progress in the preparation methods for MOFs and their hybrid materials, which will further facilitate their integration; and 4) the potential to engineer multicomponent systems that can incorporate multiple nanoparticles within different/novel MOFs systems. 3.1. MOF-nanoparticles composite Recently, research into NPs has been growing very rapidly through the invention of new materials with new structures, diverse compositions, and optimized functionalities. Applications of NPs are broad and variable, including use in sensors, drug delivery, imaging, electronic devices, magnetic heterogeneous catalysis, and energy storage [13,94,97,126]. In addition, for healthcare applications (in vivo or in vitro), a series of pre-requisites (e.g.,

Table 1 Superior features of MOF's composite over other materials.

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minimal toxicity, good blood compatibility, low immunogenicity, and tunable degradation properties) must be satisfied effectively by materials [94,97]. Importantly, the size of NPs is important in determining their potential use in biological applications. Size must be very carefully controlled in the biomedicine field, especially when considering the need for in vivo administration via common pathways (e.g., oral, intravenous, intranasal, cutaneous, ocular, otic, etc.) [91,94,108,110,118,121,127]. For example, NPs with a 500 nm diameter can enter cells by endocytosis, whereas those with a 200 nm diameter are more likely to be removed through the splenic filtration system. Those that are smaller than 10 nm are cleared through the renal filtering system [94]. In addition, physicochemical properties of the nano-sized materials (e.g., particle size, surface charge, rheological properties, and colloidal stability) will determine their affinity, distribution, and passage through different biological structures and matrices. The combined effects of these various factors may be directly or indirectly critical in determining the feasibility of their applications [91,94,108,110,118,121,127]. Therefore, the challenge for the use of nano-sized materials in biological or other applications resides not only in controlling the particle size, but also in the ability to suitably assess the materials with respect to design, synthesis, and formulation. Micro/nanostructured MOFs were investigated along with NPs, referred to as MOF-nanoparticles; the results accordingly demonstrated superior features for biomedical applications [101,125]. Recently, a critical review was presented to describe the synthesis methods for the incorporation of functional nanoscale metals, oxides, alloys, and semiconductors quantum dots (QDs)-MOFs [126e129]. These authors also discussed the location of the nanoparticles/QDs in the MOF structure to determine their utility in a

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wide variety of applications including drug delivery, catalysis, sensing, and light-driven reactions. For example, a pioneering work on the encapsulation of Au-NPs in ZIF-8 (for molecular sieving) with functional characteristics of the isolated NPs was demonstrated to be successful in biological applications. This approach can be utilized for a wide range of proteins and other biomolecules. Likewise, many other MOFs (e.g., MOF-5, MIL-100, and MIL-101c) have been investigated in terms of biological applications [123,125]. Recently, Han et al. (2016) investigated in-situ synthesis of SiO2MOF composites for high-efficiency removal of aniline from aqueous solution [127]. Accordingly, 7% SiO2-MIL-68(Al) composites were seen to possess high adsorption capacity (531.9 mg g
1) towards aniline. Likewise, the fabrication of core-shell Fe3O4-MIL100(Fe) magnetic microspheres was reported for the removal of Cr(VI) in aqueous solution [127]. For the synthesis of the highly porous MOFs (e.g., MIL-100(Fe)), magnetic iron oxide particles were successfully synthesized by using Fe3O4 precursor as crystal seed to grow MIL-100(Fe) shell based on in-situ step hydrothermal reaction (Fig. 6) [127]. Highly porous magnetic iron oxide particles with diameter of about 350 nm were successfully utilized in adsorptive removal of Cr(VI) via batch sorption mode under the following conditions (contact time (0e1000 min), pH (from 2 to 12), dose of adsorbent (4e25 mg), and initial Cr(VI) concentration (range from 10 to 100 ppm)) [127]. Apart from this, Mirzaie et al. (2016) reported sonochemical synthesis of magnetic responsive Fe3O4-TMU17-NH2 composite; it was then proved as sorbent for highly efficient ultrasonic-assisted denitrogenation of fossil fuel [128]. Encapsulation process of Fe3O4 nanoparticles into aminofunctionalized MOF (TMU-17-NH2) under ultrasound irradiation was performed for adsorptive removal of nitrogen-contain compounds in model liquid fuel. Adsorption capacity of IND and QUI composite using magnetic responsive Fe3O4-TMU-17-NH2 composite was investigated as 375.93 and 310.18 mg g
1 at 25  C, respectively [128]. Likewise, ordered meso- and microporosity silicaeZIF-8-coreeshell spheres have been synthesized at room temperature [130]. Hydrophobic micropore ZIF-8 shell was seen to control the access of guest molecules into the hydrophilic silica mesoporous structure. Likewise, many other examples on silicacoreeshell -ZIF-8- composite material have been reported extensively in current literature [130e132]. All in all, hydrophobic character, tunable behavior, and good interaction of silicaeZIF-8coreeshell composite material are attractive for many applications including gas separation and storage [130e132].

Interestingly, the synthesis of AuNp-MOF was reported by using nanowhisker of Al2O3 silanized with (3-aminopropyl)triethoxysilane (APTES) and gold nanoparticles (AuNp) (Fig. 7) [133]. This AuNp-MOF was employed as carbon paste (CPE) electrode to determine bisphenol A (BPA). This composite exhibited 2.3 time enhancement in electroactive surface area relative to raw CPE. It should be noted that the presence of AuNp played an important role in enhancing the signal of BPA detection by 2.5 times based on differential pulse voltammetry (DPV) [133]. To fully assess the potential of this research area, enormous efforts should be put to imbue NPs-MOFs with their unique properties (e.g., the spill-over effect, heat transfer mechanisms, and energy gap modulation). Such efforts will allow researchers to discover more advanced methods for NPs-MOFs while facilitating their ability to engineer novel multicomponent systems for real-world applications. Table 2 summarizes some of the more recent examples of MOFnanoparticles employed in a diverse range of applications [125e133]. As more studies are to be performed to expand the practical applicability of MOF-nanoparticles, researchers will have more opportunities to take full advantage of their unique properties. 3.2. MOF-carbon composite materials Carbon materials (such as fullerenes, carbon nanotubes (CNTs), and graphene) have been extensively investigated due to their advantageous characteristics such as high surface area, mesoporosity, electrical conductivity, mechanical strength, and corrosion resistance. These properties are superior to those of many other nanomaterial forms (e.g., NPs, quantum dots, or charge transport materials for polymer solar cells) [85,94e96,101,109,115]. Specifically, both CNTs and graphene have been studied intensively for diverse applications including sensing, storage, removal/separations, and many other energy/environmental applications [101,109,115]. Because of their good electron mobility and low percolation threshold, they exhibit many excellent features as electrode materials or electrode additives in the development of high-performance supercapacitors and batteries [85,94e96,101,109,115]. For example, Fleker et al. (2016) reported a novel technique to impart electrical conductivity to nonconducting MOFs through synthesis of MOFs within the conducting matrix of mesoporous activated carbon (AC) i.e., HKUST-1AC (Fig. 8) [134]. Basically, MOFs grown within the carbon matrix to

Fig. 6. Graphical abstract of highly porous MIL-100(Fe) and magnetic iron oxide particles (denoted as MMCs) utilized for Cr(VI) anions removal in aqueous solution [127].

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259

Fig. 7. Graphical abstract of AuNp-MOF composite as electrochemical material for the determination of bisphenol A and its oxidation behavior study [133].

Table 2 Summary of different MOF composite classes that have received significant attention in recent years. Sr. Materials MOF composites No. class A. MOFenanomaterial composites 1. Pd/MIL-100(Al) 2. Pd-MOF-5 3. AuNi-MIL-101 4. [Ni(C10H26N6)]2þ (NiL12þ) 5. MNP-MOF-5 (M ¼ Pd, Au, and Cu) 6. Au-ZIF-8 7. GQD-ZIF-8 B. MOFeorganic polymer composites 8. Polystyrene-ZIF-8 9. 10. 11. 12. 13.

Polystyrene-MIL101(Fe) Homopolymer-modified Gd-MOF 1,4 PEG-porous Cu(II)-based coordination nanocage HKUST-1-polyHIPE CAU-1-PMMA

14. ZIF-8/PS C. MOFecarbon composites 15. CNT-MOF-5 16. MWCNT-MOF-5 17. Pt-loaded MWCNT-MOF-5 18. SWCNT-MIL-101 19. CNT-HKUST-1 20.

CNT-HKUST-1

21. ZIF-8/CNT 22. GO/MOF-5 23. GO/MIL-100(Fe) 24. GO/HKUST-1 25. GO/MOF-5 26. BFG/MOF-5 D. MOFebiomolecules composites 27. Microperoxidase-11/Cu-MOFs 28. Tb-mesoMOF 29.

MP-11-Tb-mesoMOF and MP-11-MCM-41

30.

Dye-bio-MOF-1

31. 32.

MP-MOF Encapsulated Fe3þ- and Mn3þ-tetrakis(4sulphonatophenyl)porphyrin-HKUST-1 BSA-ZIF-8 MOR-1-HA

33. 34.

Improved features/applications

Reference

High metal content of 10 wt% without degradation of the porous host Controlled loading of the metal ions High chemical and thermal stability Increase in the redox reaction activity High sensitivity with increased pore-opening (7.8 Å) of the cavities for sensitive water tracing Surface modification and successive adsorption of PVP-modified NPs/biomedical applications Chemical inertness, low cytotoxicity, and excellent biocompatibility/biomedical applications

[112] [80] [111] [111] [94]

Hosteguest cross polymerization and active sites on pore surfaces are capable of acting as both nanomolds and catalysts for polymer synthesis Hosteguest cross polymerization and active sites on pore surfaces are capable of acting as both nanomolds and catalysts for polymer synthesis Positive contrast agent in magnetic resonance imaging/biomedical applications Surface functionalization with hydrophilic polymers can tune the nanocages into colloids to enhance their water stability/drug delivery Thermogravimetric analysis/biomedical applications Increased column efficiency and loading capacity/capillary electrochromatography applications Enhanced water stability/surface pore-forming agent applications

[105]

Enhanced structural stability/H2 storage capacity High structural stability/H2 storage enhancement High mesoporosity/H2 storage capacity Decrease in mesopores as well as an increase in ultra-micropores/H2 storage capacity Enhancement of gas adsorption capacity through the strong affinity of Liþ ions for gas molecules Considerably enhanced selectivity/separation and purification of CO2 from a CO2eCH4 mixture High selectivity of N2 over CO2 (7) for a 50:50 N2eCO2 mixture High loading and greater affinity of metallic centers More irregular texture and a larger amount of the amorphous phase in the composite Synergy effect to enhance the ammonia adsorption capacity and retention at ambient temperatures High-density and strong coordination bonds with enhanced connectivity

[157] [158] [159] [160] [161]

Proteolytic degradation of cytochrome c for enzymatic catalytic applications Excellent platform for investigating the interactions between enzyme molecules and MOF pores for enzymatic catalytic applications Immobilization and high initial reaction rate for monitoring the oxidation reaction of 3,5dit-butyl-catechol (DTBC) to the corresponding o-quinone Large absorption cross-section and encapsulation-enhanced luminescence efficiency for biomimetic catalysis Catalysts for the oxidation of cyclohexane Excellent catalytic performance in selective oxidation reactions for biomedical applications

[137] [145]

Bio-encapsulation for biological applications Coating of MOF particles for column ion-exchange applications

[136] [109]

[151] [152] [153] [154] [155] [156]

[162] [163] [164] [91] [133] [107]

[143] [142] [136] [140] [22] [146]

260

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Fig. 8. Graphical presentation of high conductivity HKUST-1- AC for pseudocapacitors application [134].

maintain their crystalline characteristics and their surface area. Surprisingly, HKUST-1- AC 2D layer orientation, high degree of bond conjugation, and high degree of conjugation greatly enhanced MOF conductivity [134]. In general, composite materials analysed through electron paramagnetic resonance (EPR) spectroscopy revealed high conductivity as a high-performance electrode for use as pseudo-capacitors [134]. Likewise, graphene-MOF composites reported have been reported as a potential photosensitizer material in dye-sensitized solar cells (DSSCs) [135]. In this case, the graphene-MOF hybrid composite thin film electrochemically assembled on a TiO2/FTO substrate and demonstrated the potency of an alternative solid-state DSSC configuration. The prepared thin film of graphene-MOF composite has shown 2.2% power conversion efficiency for photoanode applications [135]. A comparison of key properties between MOFs and other materials is listed in Table 1. In the recent literature, carbon materials (especially graphene) have been developed as nanocomposite materials to enhance dispersive interactions and to expand the pore space for adsorbate storage. However, due to their high electrical conductivity, they have several drawbacks, including absence of a band gap, low surface area, and luminescence; they are also susceptible to oxidative conditions with certain level of toxicity [91e98]. To rectify these problems, the properties of graphene-based nanocomposites (e.g., MOFs/graphene, CNT/graphene, NPs/graphene, and quantum dots/graphene) have been studied. Interestingly, among these nanocomposites, the combination of MOF/graphene was observed to provide strong, non-specific adsorption forces to retain small molecules at ambient conditions [85,94e96,101,109,134e142]. More importantly, the 2- and 3dimensional structures of MOFs can also be designed because they have the maximum degree of freedom in their metal ions and organic linkers, their metal ions are spherical in shape, and there are well-defined points of contact between their organic linkers. In addition, because MOFs have many other merits, they can also exert positive synergetic effects (e.g., intermolecular interactions and metaleligand coordination) on MOF/graphene. The expression of such effects in these combined materials will help expand the range of their applications [85,94e96,101,109,134e142]. For example, Yang et al. (2016) investigated three-dimensional (3D) porous hybrid composites for high-performance microwave attenuation [138]. Rational construction/synthesis of graphene oxide with MOF-derived porous NiFe-C nanocubes consisting of NiFe nanoparticles embedded within carbon nanocubes decorated on graphene oxide (GO) sheets (NiFe-C nanocubes-GO). Thus unique 3D porous hybrid composite exhibited good magnetic and dielectric losses as well as a proper impedance match with minimum reflection loss for microwave attenuation ability (RL) ofe51 dB at 7.7 GHz at a thickness of 2.8 mm [138]. Likewise, Ma et al. (2016)

reported simple strategy to fabricate porous CuO/carbon composites through nitrate impregnation into a ZIF-67 template [139]. Basically, hollow CuO/carbon composite polyhedra exhibited excellent impedance matching, light weight and strong absorption with optimal reflection loss (RL) of
57.5 dB at 14.9 GHz with a matching thickness of 1.55 mm and RL values less than
10 dB can be gained in the range of 13e17.7 GHz. CuO/carbon composites have shown been best absorbing performance originates from the high loss of the porous carbon through carbonization of ZIF-67 [139]. A variety of transition and noble metals can be used to form MOF structures with active sites for reactive adsorption or heterogeneous catalysis. Continued research efforts in this developing field should result in great advancements in photovoltaics. For example, the MOF-5/GO composite, synthesized using a solvothermal synthesis route, was studied for its ammonia adsorption capacity [111,136,140]. Interestingly, the MOF-5/GO composite, which preserves the chemical structure of MOF-5 and GO, exhibited synergistic enhancement of the adsorption capacity relative to the sum of the adsorption capacities of each component [136,140]. This was ascribed to the creation of new pores between the two phases (MOF units and GO). Likewise, MOFs containing Zn and Cu (MOF-5 and HKUST-1), when synthesized with graphite oxide hybrid materials, exhibited enhanced features analogous to their parent MOFs (in terms of their crystalline structure, high porosity, and surface area). Moreover, the novel composite material GrO-MIL-101, synthesized using a solvothermal synthesis method, exhibited a small crystal size, high surface area, and an increased pore volume relative to MIL-101 (Fig. 9) [120]. Finally, these authors measured the adsorption capacity of acetone by GrO-MIL-101 to be 20.10 mmol g
1 (288 K and 161.8 mbar), which was far higher (44.4%) than that of neat MIL-101 (Fig. 9) [120]. Note that the insulating nature of MOFs has often been a barrier for their widespread use, although such properties have not been extensively studied. The synthesis of MOF-based composites with carbon-based materials (for the fabrication of electronic devices) has been investigated intensively as a solution to expand their applicability. For example, MOF-5/graphene composite materials, decorated with intercalated graphene with carboxylic groups at the basal plane, exhibited new electrical properties (Fig. 10) [105]. The intercalation of graphene also led to a considerable enhancement in the non-specific adsorption kinetics. In addition, the high conductivity and specific surface area of graphene helped improve the dielectric and conducting properties of the MOF material [84,95,99]. Likewise, the conductive properties of a copper-based MOF (a (HKUST-1)/graphene-like composite) were measured through a stepwise oxidation/reduction wet treatment (Fig. 11) [80]. Interestingly, HKUST-1/graphene composites were seen to preserve the main features of the parent MOF but also possessed a tunable electrical conductivity [60]. As such, the properties of many types of carbon materials/MOFs composites have been improved (Table 2). 3.3. MOF-polymers composites materials Recently, MOF-polymers based composite materials including MOF-based mixed-matrix membranes (MMMs) and polymer supported MOF membranes have been studied extensively [141e149]. As summarized by Calvez et al. [141], emulsion templating synthesis of MOF-polymer composites can be achieved via three different routes: (1) growing MOF crystals on a pre-synthesized polymer support; (2) carrying polymerization around the preformed MOF crystals; or (3) copolymerizing monomers with MOF initially modified with polymerizable functional groups. Recently, Abbasi et al. [118] investigated a simple fabrication approach for

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261

Fig. 9. Morphological investigation using SEM images of (a) GrO, (b) MIL-101, and (c) GrO-MIL-101; TEM images of (d) GrO, (e) MIL-101, and (f) GrO-MIL-101; XRD patterns of (G) MIL-101, GrO-MIL-101, GrO þ MIL-101, and GrO; and (H) adsorption isotherms of acetone on the samples (288e318 K) [120].

Fig. 10. Graphical representation of the structure-directing role of graphene in the synthesis of metal
organic framework nanowires [105].

ZIF-8/polymer composite beads through phase inversion method for applications toward efficient oil sorption. The analysis showed that ZIF-8 particles were well coated and dispersed into the polymer bead composites surface at higher loadings to maximize oil sorption [118]. ZIF-8/PES beads were thus demonstrated to be efficient for recycling with easy handling relative to pristine ZIF-8 powder or common natural sorbents (like activated carbon). All

in all, the phase inversion method using MOF-polymer composite or functional composite was demonstrated to have great expressions as bead materials for specific adsorption or gas storage applications [118]. Recently, one-step synthesis approaches based on emulsion templating approach and polymerization of the internal phase of the emulsion have been introduced for the production of

262

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Fig. 11. Graphical presentation of the synthesis and characterization of conductive copper-based MOF/graphene-like composites [80].

chance to develop novel material properties [23,27,92,95,105,111,117]. Over the past decades, polymers have received a great deal of attention and have experienced a dramatic transition from being simple chemical curiosities to revolutionary materials. Research into PCPs/MOFs has increased in such a way that recent reviews have been directed toward particular polymer classes or their specific applications [114,140e173]. Table 2 presents information related to different classes of polymers and their derivatives (e.g., p-doped polymers, polypyrrole (PPy), polyaniline (PAni), and polythiophene (PT)). In light of their unique properties (e.g., semiconductivity, electroactivity, and potential applications as plastic conductors or light-emitting diodes (LEDs)), most of the earlier studies focused on their applications in the field of energy storage [30,92,95,111,117]. The design of hybrid materials or nanocomposites offers the ability to produce optimum properties in novel materials, as has been achieved in the design of coordination polymers and MOFs [8,9,13,21,23e25]. 4. Concluding remarks

MOFepolymer composites [141]. Such emulsion templating approach has simultaneously led to crystallization and polymerization in the internal phase of the emulsion for the production of porous MOFepolyHIPE composites. A noticeable improvement in mechanical stability acquired through one-step synthesis of MOFepolyHIPE composites materials could help widen their potential applications in various fields [141]. In another series, De et al. (2016) investigated water-based dispersions of MIL-101(Cr) to facilitate the formation of robust polymereMOF hybrid coatings [142]. Basically, aqueous solution of poly(styrene sulfonate) has been utilized on the nano MIL-101(Cr) dispersion, yielding linear film growth and coatings with a MOF content as high as 77 wt%. The formation of MOF- polymer coatings approach is surface-agnostic so that the coating can be applied successfully to silicon, glass, flexible plastic, and even cotton fabric, conformally coated individual fibers. These authors thus confirmed that the complex and unusual surfaces of MOFs-polymer composites are feasible for a wide variety of applications including textiles, storage, and sensors [142]. Interestingly, Zhang et al. (2016) presented a literature survey on the challenges and recent advances in MOF-polymer composite membranes for gas separation [149]. In addition, they also proposed the possible solutions and strategies to fabricate MOF-polymer composite membranes with ideal morphology and performance for real world gas storage, separation and catalysis applications. All these trends on MOF-polymer composites are relatively new fields of research that can open the possibility for various polymer functionalities and merits (e.g., light weight, facile processability, and chemical stability). In the future, these composites could potentially be integrated into various devices for a variety of applications including biomedical device, sensors, separation, and energy storage [149]. 3.4. Miscellaneous composite materials of MOFs Many types of MOF composites have been developed to make use of the main aspects of MOF chemistry and to realize the full potential for their future utility. A recent example includes UiO-66NH2-alginic acid (HA) composites. In contrast to the as-prepared MOF material, a thin layer of water-insoluble HA coats the MOF NPs, resulting in a composite that cannot form a water suspension. Thus, the composite is suitable for use as a stationary phase in an ion-exchange column (because it remains fixed in the column), whereas MOFs that form as fine water suspensions flow out of the column. The increased number of materials that can be bound to each other (MOFs, hybrid materials, and nanocomposites) offers a

This review article highlights MOF research, which is one of the hottest topics in materials science, coordination, inorganic, and supra-molecular chemistry. The applicability of MOFs has been successfully demonstrated in a diverse range of applications such as catalysis, energy storage, drug delivery, nonlinear optics, and gas storage. There is no doubt that the sorptive capacity of MOFs is their most intensely studied property; this field of study is now a fairly mature area and is widely used for separation and storage applications of various gaseous components (e.g., hydrogen, CO2, CH4, O2, etc.). In addition, the use of MOFs for very sensitive and specific sensing devices (for small molecules, solvents, pollutants, and explosives) has been made possible with the aid of luminescent and conductive CP/MOFs. Increased growth in MOF research is still expected in the coming years due to the specific advantages of MOFs compared to other materials; these advantages include their high surface area, porosity, high chemical and thermal stability, luminescence, highly-sorptive nature, molecular sensing, inclusion of receptor molecules, and the possibility of regeneration. At present, several barriers of MOF technology (e.g., laborious nature of synthesis (and characterization processing), aqueous insolubility, insulating nature, and the high cost of the final product) remain to restrict their widespread use. These challenges are currently the main focal area of MOF research so that a variety of approaches are investigated to resolve those barriers; these methods include incorporating MOFs with various options (e.g., biomolecules, graphene, CNTs, metal nodes, integrating guest molecules, and redox (or catalytic active) sites). These approaches not only aim to overcome the drawbacks of MOF use, but should also provide significant improvements to the characteristics of MOFs (such as adding conductivity to MOFs). The MOFs and their composites have been increasingly investigated for novel industrial applications including separation/storage of gas, sensing small molecules, and clean energy generation (as batteries, fuel cells, and capacitors). It is thus believed that, in the coming years, the use of MOFs and their composites will increase significantly in line with the significant advances achieved to improve their structural stability, tunable composition, and final product cost. This should results in a deepening and widening of their practical application. Acknowledgements This study was supported by a National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (No. 2016R1E1A1A01940995). PK thanks the Vice

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Chancellor, Central University of Jammu, Jammu for infrastructural facilities and UGC, New Delhi for a start-up Research Grant.

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