Metal–Organic Frameworks Composites as Flexible Air Filters

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Energy, Environmental, and Catalysis Applications

Textiles/Metal-Organic Frameworks (MOFs) Composites as Flexible Air Filters for Efficient Particulate Matter (PM) Removal Kun Zhang, Qian Huo, Ying-Ying Zhou, Hong-Hong Wang, Gao-Peng Li, Yao-Wu Wang, and Yao-Yu Wang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b01734 • Publication Date (Web): 05 Apr 2019 Downloaded from http://pubs.acs.org on April 8, 2019

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Textiles/Metal-Organic Frameworks (MOFs) Composites as Flexible Air Filters for Efficient Particulate Matter (PM) Removal Kun Zhang,*,†,‖ Qian Huo, § Ying-Ying Zhou,‡ Hong-Hong Wang,‡ Gao-Peng Li,*,‖ YaoWu Wang*,‡ and Yao-Yu Wang*,‖

†School

of Textile Science and Engineering, Xi’an Polytechnic University, Xi’an,

710048, P. R. China.

‡Cooperative

Innovational Center for Technical Textiles, §Transformation Center for

Scientific and Technological Achievements, Xi’an Polytechnic University, Xi’an, 710048, P. R. China.

‖Key

Laboratory of Synthetic and Natural Functional Molecule Chemistry of the

Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Materials Science, Northwest University, Xi'an, 710127, P. R. China.

KEYWORDS: metal-organic frameworks, textiles, hot pressing, coatings, air filters

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ABSTRACT:

The health-threatening air pollution especially particulate matter (PM) triggers increased demands for developing low-cost and long-service-life air cleaning technologies. In present contribution, a range of high-efficiency textiles/Metal-Organic Framework (MOFs) composites (MOFs@textiles) air filters with excellent washable reusability is presented. By processing MOFs onto textile substrates via eco-friendly solvent-free method to enable the microporous and also strong PM adhesion, we develop flexible, highly effective air filters with >95.00% PM removal efficiency (e.g., MiL-53(Al)@Aramid, PM2.5: 95.3%, PM10: 96.1%) under harmful air quality conditions (average PM2.5 mass concentration >280 μg m-3, PM10 > 360 μg m-3) in high air flow speed (the pressure drop less than 30 Pa). Therefore, these MOFs@textiles are promising composites for producing efficient and recyclable out/in-door air purifiers.

1. INTRODUCTION

The massive accumulation of particulate matter (PM), resulting from anthropogenic activities such as traffic, power plants, and many other industrial sectors, has become one of the great focal problems among various kinds of air pollutants, which has strong effects on air quality, global climate and ecosystems.1-3 The enormous amount of human epidemiologic

researches

have evidenced

that

exposure to highly polluted PM (PM2.5 and PM10) environment can cause deleterious health issues like respiratory and cardiovascular disease, even cancer.4-8 To address this

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issue, the Chinese Government has recently established the regulation to control the average particulate matter concentration (PM2.5 < 35 μg m−3, PM10 < 70 μg m−3).9 However, owing to the complicated composing and tiny size, removing and regulating PM2.5 and PM10 remain a great challenge.10-11

Air filtration can be an effective method of removing PM pollutant and lowing the PM level but still a complicated task in filter design.11-13 Although many technologies and materials have been developed and applied for PM filtration, such as porous membrane, electrospun polymers, they are often suffering from poor flexibility, limited PM removal efficiency, and high airflow resistance.14-17 Therefore, this calls for new PM filters with high efficiency.

With the advantages of high porosity, large specific surface area as well as surface charge, metal-organic frameworks (MOFs)18 represent a class of promising filter materials that exhibiting great potential in polarizing the PM surface and thus improving the electrostatic interactions between MOFs and PM.19 Therefore, it is intriguing to develop MOFs based PM filtration materials. However, for practical applications, crystalline MOFs are brittle and can be easily destroyed into powders20, which is better to fabricate MOFs into suitable substrates to improve their flexibility and mechanical strength for real application.21-22

As low-cost, widely available fibrous materials, textiles, have attracted research interest for their flexibility, robust and low airflow resistance.23-24 Besides, rich

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potential binding sites in textiles make them as promising substrates to incorporate MOFs.24 Therefore, it is of great significance to develop MOFs modified textiles for the PM removal. In this work, we selected four classical MOFs (containing MiL-53(Al), ZiF-8, UiO-66 and MFM-300(In)) as the coated materials to modified textiles. The MiL-53(Al) and UiO-66 were constructed by connecting metal central (Al(III)

and

Zr(IV)) with terephthalic acid.25-26 The ZiF-8 is well-known zeolite-like frameworks that have been extensively studied for pollutants removal.19,

27-28

While, the MFM-

300(In) is formed by linking biphenyl-3,3',5,5'-tetracarboxylic acid with In(III), which possess highly-efficiency in gas adsorption and separation.29 Importantly, all the four MOFs are porous frameworks possessing high specific surface area, thermal and chemical stability (Scheme 1, Figure S1 in the Supporting Information).30-33 By employing solvent-free hot-pressing synthesis method, we accomplished a series of flexible textiles/MOFs composites (MOFs@textiles) for high-efficiency PM filtration with low flow resistance and excellent washable reusability, in which hot pressing at appropriate temperature in 10 minutes can transform the organic ligands and metal sources into highly stable and uniform MOFs coatings on various textile substrates, including commercially available cotton, polyester and aramid. In addition, during the preparing process, precursor materials of MOFs, metal ions, or organic ligands can firstly bind to the active site on the surface of the textiles substrates, and then the growth of MOFs layers began, which was supported by ATR-FTIR and Raman spectra analysis (vide infra). The obtained air filters reveal excellent PM removal efficiency

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under very harmful air-quality conditions (average PM2.5 mass concentration >280 μg m-3, PM10 > 360 μg m-3). For instance, Mil-53(Al)@Aramid gives best remove efficiency, PM2.5: 95.3 %, PM10: 96.1 %.

2. EXPERIMENTAL SECTION

2.1 Synthetic Procedure. All reagents and raw starting materials are purchased commercially and used without additional refining treatment. Zn(Ac)2·2H2O (99%), Al(NO3)3·9H2O (99%), ZrCl4·6H2O (99%), In(NO3)3·6H2O (99%), 2-methylimidazole (98%) and 1,4-dicarboxybenzene (99%) were purchased from Aladdin Industrial Corporation. Biphenyl-3,3’,5,5’-tetracarboxylic acid was purchased from Jinan Camolai Trading Company. Textiles (cotton, aramid and polyester) were bought from Textile Company. The detailed characterization methods are showed in Section 1 in the Supporting Information.

The synthesis process of MOFs@textiles is similar. Metal sources and organic ligands were manually mixed and ground. Then, the mixed raw materials were placed on the textiles (cotton, aramid and polyester), covered with aluminum foil and further heated within hot-pressing machine at appropriate temperature for ten minutes. The MOFs@textiles was washed by DMF and ethanol after being peeled off the aluminum foil. Then, the prepared samples were dried at room temperature for 1 day for characterization.

2.2 PM removal experiment. PM particles were generated by means of burning

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incense smoke. By modulating the specific time of incense burning, the particles mass concentration was achieved the value of average PM2.5>280 μg m-3 and PM10 > 360 μg m-3. A piece of MOFs@textiles air filters with a diameter of 2.5 cm was put in the plastic container, then link to the aerosol spectrometer (Promo 2000) by plastic duct. The air filter device with MOFs@textiles filters was placed in the hazardous air-quality environment for a long-time continuous testing, and regarding the average value of the PM over this time period as the test value. The size distribution and pressure drop were measured by PALAS dust monitor. The PM removal efficiency for the MOFs@textiles filters was calculated based on the equation: Efficiency = (C0 - C)/C0, where C0 (μg m-3) and C (μg m-3) are the tested PM mass concentrations without and with the filters.

3. RESULT AND DISCUSSION

Scheme 1. The schematic representation of the hot-pressing preparation method of obtaining various textiles/MOFs composites (MOFs@textiles) air filters for particulate matter (PM) removal. Inset: structures of four classical MOFs (MiL53(Al), ZiF-8, UiO-66 and MFM-300(In)).

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Figure 1. PXRD patterns of MOFs coated on different textiles and simulated patterns for pure MOFs. a) MiL-53(Al)@textiles; b) ZiF-8@textiles; c) UiO-66@textiles and d) MFM-300(In)@textiles. The synthetic procedure for textiles/MOFs composites (MOFs@textiles) filters through hot-pressing method involved two steps (Scheme 1). Firstly, textiles were covered with powdered mixture of MOFs precursors. Then, the textiles were covered with aluminum foil, and further heated within a hot-pressing instrument (Figure S2 in the Supporting Information) at appropriate temperature for certain time, followed by cleaning and drying processes (Section 1 in the Supporting Information). Taking MiL-53(Al)@Cotton as an example, cotton was first covered with MiL-53(Al) precursors (mixture of Al(NO3)3·9H2O and 1,4-dicarboxybenzene) and heated at 130 oC

for 10 min. Then, cotton was uniformly covered with Mil-53(Al) nanocrystals,

which was evidenced by powder X-ray diffraction (PXRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDS) (Figure 1, Figure 2, Figures S3-S6 in the Supporting Information). Similarly, MiL-53(Al)@Aramid and

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MiL-53(Al)@Polyester can be also obtained through the same procedure, which were also confirmed by PXRD, SEM and EDS (Figure 1, Figure 2, Figures S3-S6 in the Supporting Information). The MiL-53(Al) loading amount ranges from 89.37 to 113.74 mg g-1 depending on the different types of textiles (Supporting Information Table S1), which suggests the different binding preference between the MiL-53(Al) and surface groups of textiles (-OH for Cotton and O=C for Aramid/Polyester). Compared with aramid and polyester, cotton contains more binding sites, which may offer more reaction sites for in-situ generating MiL-53(Al) on the substrate.

Figure 2. SEM images of the different MOFs coated textiles. a1) MiL53(Al)@Cotton; b1) MiL-53(Al)@Aramid; c1) MiL-53(Al)@Polyester; a2) ZiF8@Cotton; b2) ZiF-8@Aramid; c2) ZiF-8@Polyester; a3) UiO-66@Cotton; b3) UiO-66@Aramid; c3) UiO-66@Polyester; a4) MFM-300(In)@Cotton; b4) MFM300(In)@Aramid; c4) MFM-300(In)@Polyester. To incorporate different kinds of MOFs and textiles, we selected four types MOFs (ZiF-8, MiL-53(Al), UiO-66 and MFM-300(In)) and three kinds of textiles (cotton, aramid and polyester) for fabricating twelve types of MOFs coated textiles

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(Figure 1, Figure 2, and Section 1 in the Supporting Information). The comparison of the SEM images of blank textiles and MOFs@textiles reveals that MOFs nanocrystals are uniformly distributed on the surface of textile fibers (Figure 2 and Figure S7 in the Supporting Information). The Brunauer-Emmett-Teller surface area (SBET) of the MOFs@textiles filters was obtained via the analysis of low-pressure nitrogen gas sorption isotherms at 77K (Figure S8-S11 in the Supporting Information). The type-I physical adsorption isotherms of the MOFs@textiles reveal their microporous feature.34-35 In addition, the load capacity of textiles to MOFs was evaluated based on metal ions content through dissolving the MOFs@textiles in HCl solution (Table S1 in the Supporting Information).

Figure 3. FTIR spectra characteristics of MOFs@textiles compared to blank textiles and pure MOFs. a1) MiL-53(Al)@Cotton; b1) MiL-53(Al)@Aramid; c1) MiL-

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53(Al)@Polyester; a2) ZiF-8@Cotton; b2) ZiF-8@Aramid; c2) ZiF-8@Polyester; a3) UiO-66@Cotton; b3) UiO-66@Aramid; c3) UiO-66@Polyester; a4) MFM300(In)@Cotton; b4) MFM-300(In)@Aramid; c4) MFM-300(In)@Polyester. The new bands after coating MOFs onto textiles are highlighted in light yellow bar. In order to elucidate the interactions between MOFs and textiles, these MOFs@textiles were firstly characterized by ATR-FTIR (Figure 3). The spectrum of blank cotton includes peaks at 3600-3000, 2900 and 1050 cm-1 due to the stretching vibration of OH group, the asymmetric stretching of aliphatic C-H group and stretching vibration of C-O-C groups, respectively.36 For aramid, peaks at 3400 and 1477 cm-1 can be assigned to the N-H stretching and deformation bands, respectively. Amides I, II, and III groups appear at peaks 1647, 1531, and 1240 cm-1, respectively.37 Polyester gives two strong absorption band at 1711 and 1239 cm-1, belong to the stretching vibration of C=O and C-O in carboxylate groups, respectively.38After incorporating MOFs, besides the shifts of binding sites (hydroxyl in cotton and carbonyl in aramid/polyester) in MOFs@textiles, new peaks between 450 and 850 cm-1 were also observed (Figure 3, eg. around 830 cm-1 for MiL53(Al)@textiles; around 500 cm-1 for ZiF-8(Al)@textiles; around 780 cm-1 for UiO66@textiles; around 830 cm-1 for MFM-300(In)@textiles). To get a deep insight into the interaction between MOFs and textiles, Raman spectra was also employed to characterize the MOFs@textiles air filters (Figure 4). According to the spectra, besides the observed characteristic peak of textiles and MOFs, additional new bands also can be observed, which suggesting that there might have been coordinated

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interactions between metal and textiles.39-42 That is, there are coordination bonds between MOFs and the function groups in textiles, whereby MOFs may bond with cotton via hydroxyl group and with aramid/polyester by coordinate with carbonyl in amide/carboxylate groups.24,

43-44

The interaction mechanism between MOFs and

textiles are proposed in Figure S12-S15 (Supporting Information). Accordingly, during the formation of filters, textiles can act as chelated ligands allowing the metals interacting with the blind sites (hydroxyl in cotton and carbonyl in aramid/polyester).

Figure 4. Raman spectra for MOFs@textiles compared to blank textiles and pure MOFs.

a1)

MiL-53(Al)@Cotton;

b1)

MiL-53(Al)@Aramid;

c1)

MiL-

53(Al)@Polyester; a2) ZiF-8@Cotton; b2) ZiF-8@Aramid; c2) ZiF-8@Polyester; a3) UiO-66@Cotton; b3) UiO-66@Aramid; c3) UiO-66@Polyester; a4) MFM300(In)@Cotton; b4) MFM-300(In)@Aramid; c4) MFM-300(In)@Polyester. The new bands after coating MOFs onto textiles are highlighted in light yellow bar.

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Figure 5. Photo image of PM removal test instrument.

Figure 6. PM removal efficiency for the pure textiles and MOFs@textiles composites. The PM removal efficiency for all MOFs@textiles filters at room temperature is investigated through comparing the PM concentration before and after filtration (Figure 5, Figure 6, and Section 3 in the Support Information). As shown in Figure 6, Table 1 and Figure S17-S31 in the Support Information, the MOFs@textiles filters showed a high efficiency in PM removal with a low pressure drop (< 30 Pa). The result showed MiL-53(Al)@Aramid filters with the best removal efficiency (95.30% for PM2.5 and 96.11 % for PM10), which is much high than the value of active carbon (PM2.5:23.7%)45 and can compared to the reported filters, such as triboelectric air filter (PM2.5: 96.0%)46 and electrospun nanofiber film (PM2.5>95.0%)17. SEM images

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of Figure S32 in the Support Information show the MOFs@textiles filters after PM capture, which showed that there is no significant structural change. In addition, the PM2.5 and PM10 removal efficiency of all MOFs@ textiles filters could also maintain at high levels (>85.0 %) in a long period. Compared to uncoated textiles, the removal efficiency of MOFs@textiles filters showed a great improvement, which suggest that the accessible porosity and large specific surface area of MOFs play a significant role in PM filtering process.34 Meanwhile, the interactions between PM and MOFs could also make a contribution to the PM capturing.47 In addition, to test recycling utilization, we selected Mil-53(Al)@Aramid as example. The used Mil53(Al)@Aramid filter was washed by water, followed by drying at room temperature. Figure 7 shows the cycling PM removal performance after cleaning process. The removal efficiency of the filter was retained at high levels (> 90 %), which demonstrates excellent washable reusability. Table 1. PM removal efficiency and BET surface areas of various MOFs@textiles. Materials

PM2.5 (%)

PM10 (%)

SBET (m2 g-1)

MiL-53(Al)@Cotton

91.98

93.21

83.86

MiL-53(Al)@Aramid

95.30

96.11

69.79

MiL-53(Al)@Polyester

92.67

94.20

75.11

ZiF-8@Cotton

87.71

90.37

49.85

ZiF-8@Aramid

91.88

93.53

40.76

ZiF-8@Polyester

89.59

92.28

42.13

UiO-66@Cotton

88.83

92.12

76.18

UiO-66@Aramid

92.84

94.33

70.10

UiO-66@Polyester

90.31

92.58

72.82

MFM-300(In)@Cotton

85.46

88.69

107.15

MFM-300(In)@Aramid

91.21

93.18

95.57

MFM-300(In)@Polyester

87.32

90.43

92.11

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Figure 7. The PM removal efficiency of MiL-53(Al)@Aramid air filter washed after 1-5 times.

Figure 8. Picture of the a) bended and b) twisted ZiF-8@Cotton. c) Stretching experiment was carried out by loading an autoclave (0.6 kg) downside. d) Picture of ZiF-8@Cotton during sand paper rubbing. On the other hand, we also paid attention to the durability of these MOFs@textiles air filters, as it is a critical characteristic when used for daily-life.12 Taking ZiF-8@Cotton as the case, the filter can suffer 500 times bending and twisting without obvious weight loss (Figure 8a-b). Furthermore, the filter can withstand the stretching of one autoclave (0.6 kg) (Figure 8c). Besides, the filter could maintain its weight (weight loss less than 3 wt%) even after being rubbed by a sand paper with an autoclave placed above (Figure 8d). In addition, the MOFs@textiles filters have reasonable mechanical properties with good tensile strengths (Figure S33 in the

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Supporting Information). Therefore, the obtained MOFs@textiles air filters showed good flexibility, robustness and mechanical strength, which making them highly adaptive for real applications.

3. CONCLUSION In summary, we accomplished a series of flexible air filters by incorporating MOFs and textiles by using solvent-free method for highly efficient particulate matter (PM) removal. Through this method, MOFs can be uniformly and robustly coated on the surface of textiles, with maintained large surface area and highly porosity. Moreover, this strategy can be extended to different MOF systems (Mil-53(Al), ZiF-8, UiO-66 and MFM-300(In)) on various textiles (cotton, aramid and polyester). Such obtained filters with their optimized surface chemistry show superior PM removal efficiency with excellent washable reusability. We believe that our approach to fabricating flexible air filters will open a broader prospect for designing and producing the desired filters for PM pollution control.

ASSOCIATED CONTENT Supporting Information. XRD patterns; SEM images; N2 sorption data and PM removal experiment and result. Corresponding Author *E-mail: [email protected] (K. Z.). *E-mail: [email protected] (G.-P. L.).

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*E-mail: [email protected] (Y.-W. W.). *E-mail: [email protected] (Y.-Y. W.). Notes The authors declare that they have no competing financial interests. ACKNOWLEDGMENT This work was supported by National Natural Science Foundation of China (Grants 21531007), Natural Science Basic Research Plan in Shaanxi Province of China (Program No. 2018JQ2026), Scientific Research Program Funded by Shaanxi Provincial Education Department (Program No. 18JK0355). REFERENCES (1) Andreae, M. O.; Rosenfeld, D. Aerosol-cloud-precipitation interactions. Part 1. The nature and sources of cloud-active aerosols. Earth-Sci. Rev. 2008, 89, 13-41. (2) Mahowald, N. Aerosol Indirect Effect on Biogeochemical Cycles and Climate. Science 2011, 334, 794-796. (3) Horton, D. E.; Skinner, C. B.; Singh, D.; Diffenbaugh, N. S. Occurrence and persistence of future atmospheric stagnation events. Nat. Clim. Change 2014, 4, 698703. (4) Brunekreef, B.; Holgate, S. T. Air pollution and health. The Lancet 2002, 360, 1233-1242. (5) Anenberg, S. C.; Horowitz, L. W.; Tong, D. Q.; West, J. J. An Estimate of the Global Burden of Anthropogenic Ozone and Fine Particulate Matter on Premature Human Mortality Using Atmospheric Modeling. Environ. Health Perspect. 2010, 118, 1189-1195.

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