Construction of Anti-Ultraviolet âShielding Clothesâ on PBO fibers

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Surfaces, Interfaces, and Applications

Construction of Anti-Ultraviolet “Shielding Clothes” on PBO fibers: Metal Organic Frameworks mediated absorption strategy Zhen Hu, Fei Lu, Yingying Liu, Lei Zhao, Long Yu, Xirong Xu, Weihao Yuan, Qian Zhang, and Yudong Huang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b16845 • Publication Date (Web): 31 Oct 2018 Downloaded from http://pubs.acs.org on November 2, 2018

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ACS Applied Materials & Interfaces

Construction of Anti-Ultraviolet “Shielding Clothes” on PBO fibers: Metal Organic Frameworks mediated absorption strategy Zhen Hu, Fei Lu, Yingying Liu, Lei Zhao, Long Yu, Xirong Xu, Weihao Yuan, Qian Zhang, and Yudong Huang* School of Chemistry and Chemical Engineering, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Harbin Institute of Technology, Harbin 150001, China *Corresponding authors: Yudong Huang (E-mail: [email protected]).

ABSTRACT A metal-organic framework mediated adsorption strategy is firstly developed for improving the anti-ultraviolet properties of PBO fibers. In this work, the UIO-66 was successfully anchored onto the surface of PBO fibers by one-step microwave-assisted heating method. The experimental results showed an obviously enhanced surface energy (91.1%), roughness (268.4%), interfacial shear strength (49.0%) and anti-UV properties (66.7%) compared to pristine PBO fibers. The anti-UV dye (tartrazine) was further immobilized onto the surface of PBO fibers via adsorption strategy mediated by UIO-66. Interestingly, the PBO@tartrazine fibers demonstrated a superior anti-UV performance (further up to 81.5%) compared to PBO@UIO-66 fibers. The extraordinary anti-UV properties of PBO@tartrazine fibers could be rationally ascribed to the synergistic effects of UIO-66 and tartrazine molecules. Considering the diversities and functionalities of MOFs and targeted materials, our work indicates that the MOFs-mediated adsorption strategy would promisingly endow PBO fibers with other desired performance and applications such as solar-thermal transition and self-healing abilities.

KEYWORDS: PBO fibers, metal-organic-frameworks, adsorption strategy, anti-UV property,

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synergistic effects.

1. INTRODUCTION Poly (p-phenylene benzobisoxazole) (PBO) fibers, owning a high tensile modulus (280 GPa) and strength (5.8 GPa), have drawn comprehensive concerns and interests in various momentous fields such as aerospace, military, general industry1-2 and advanced composites.3-5 However, the PBO fibers are very sensitive to solar light especially the ultraviolet (UV) irradiation. Subsequently, the safety and reliability of PBO fibers and relevant advanced composites will be decreased seriously. The effective strategies to significantly improve the anti-UV properties for PBO fibers are in urgent need. Generally speaking, the current strategies to endow PBO fibers with excellent anti-UV properties can be primarily classified into two categories, including the bulk blending/co-polymerization and the surface physical/chemical modification. The bulk blending method is usually achieved by adding the light stabilizer or “black” nanomaterials such as OB-16 and exfoliated graphite.7 Meanwhile, the bulk co-polymerization is generally realized by introducing the “third” comonomers into the synthetic process

of

PBO

fibers,

such

as

2,

5-dihydroxyterephthalic

acid

(DHTA)8

and

2,

6-naphthalenedicarboxylic acid (NDCA).9 However, the bulk blending/co-polymerization often has obvious drawbacks of time and energy consumption. Alternatively, the surface physical/chemical modification is another feasible strategy to fabricate UV stable PBO fibers. The surface physical modification is generally accomplished by coating or sizing various materials with light stable properties on the surface of PBO fibers, such as ZnO,10 TiO2,11 graphene oxide (GO)12 and UV-P.13 Unfortunately, the surface physical modification has the great drawbacks including the worse dispersity of the introduced materials and weak binding force with the surface of PBO fibers. However, the anchored materials through in situ chemical surface modification can be well dispersed and bound onto


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the surface of PBO fibers via the chemical bonds. As a result, this method is the dominant strategy to improve the anti-UV properties of PBO fibers. Metal-organic frameworks (MOFs), combining metal ions or clusters with organic ligands as a new class of inorganic-organic hybrid crystalline porous materials, have received tremendous attention owing to the distinctive features involving large specific surface area, high porosity, tunable pore sizes and architectures.14-15 Benefiting from the inherent unique characteristics, MOFs have been explored extensively in a wide range of potential application fields such as catalysis,16-17 adsorption,18-21 drug delivery,22-23 gas storage24-25 and separation26-28 as well as sensing.29-31 Up to data, the approaches to prepare the MOFs are typically including ultrasonic chemical synthesis,32-33 solvothermal synthesis34-35 and microwave-assisted synthesis methods.36-37 Among these methods, the microwave-assisted synthesis way is gradually becoming an efficient and energy-conserving method to prepare MOFs with high speed and yields due to the uniform and intensive heating effect.38 Interestingly, correlational study has proved that introducing a well-distributed robust MOFs coating to the surface of carbon fiber is beneficial to the overall performances of fibers, including the roughness, surface energy, tensile strength of fibers and even the IFSS values of fiber/resin composites.39 More importantly, some researchers have found that nanosized MOFs also have an excellent anti-UV property towards textiles.40 In addition, dyes (such as tartrazine) with suitable wavelength ranges can well absorb the sunlight and even UV light. However, there are a few reports about using dyes to improve the UV absorbance of MOFs composites in a simple way up to now.41 As is known to all, the adsorption with high efficiency and low cost has become one of the most important application fields of MOFs due to the high BET surface area and pore volume. Moreover, a great deal of research works has focused on effectively removing colored dyes from the wastewater with the adsorption ability of MOFs. All the



above-mentioned studies potentially provide a promising strategy for enhancing the UV stabilities of PBO fibers via adsorption technique mediated by MOFs. Enlightened by the adsorption application of MOFs, the MOFs mediated adsorption strategy is firstly developed for improving the anti-UV properties of PBO fibers. In the present work, a dense and uniform UIO-66 nanolayer42 was in-situ chemically grafted onto the surface of PBO fibers (PUFs) by microwave-assisted heating method. Then, the anti-UV dye (tartrazine) was efficiently anchored onto the PBO fibers (PTFs) via the UIO-66 adsorption. Figure1 shows a schematic illustration of the fabrication of PUFs and PTFs. The surface morphologies and physicochemical properties of PBO fibers were systematically investigated and characterized. The experimental results revealed that both of the PUFs and PTFs exhibited significantly improved anti-UV properties compared to pristine PBO fibers. The present MOFs-mediated adsorption strategy would be promisingly applicable to endow PBO fibers with other fascinating properties (such as solar-thermal transition and self-healing abilities) with a variety of targeted materials.

Figure 1. Schematic demonstration of the preparation process for PUFs and PTFs.


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2. EXPERIMENTAL SECTION 2.1 Materials. The HM-PBO fibers were obtained from Toyobo Ltd., Japan with a single filament diameter of 12 μm and then subjected to Soxhlet extraction with acetone at 70 oC for 48 h in order to remove the sizing agent and contamination on the surface of PBO fibers prior to use. The terephthalic acid (TA) was obtained from our own laboratory. The zirconium (IV) chloride (ZrCl4, 98%), tartrazine (95%, HPLC) and acetic acid (99.7%), chloroacetic acid (99%) were purchased from Aladdin and Innochem (China), respectively. The N, N-dimethylformamide (DMF) and methanol were received from the XiLong Scientific Co., Ltd. (Guangdong, China). The concentrated hydrochloric acid, sulfuric acid and Sodium hydroxide were received from the Sinopharm Chemical Reagent Co., Ltd. and the deionized water was chosen to use for the subsequent reaction process. All the chemical reagents and solvents were used as received. 2.2 Preparation of PBO-COOH@UIO-66 (PUFs). The general process to prepare the PUFs was as follows. The carboxyl groups modified PBO fibers (denoted as PBO-COOH) were fabricated according to the method provided by previous work of our laboratory in the first place.5 Then the typical precursor solution of UIO-66 was prepared by adding and mixing five basic components including ZrCl4 (1.17 g)、TA (0.83 g)、DMF (40 mL)、Acetic acid (8.55 mL) and deionized water (0.54 mL) in a PTFE beaker at room temperature with proper stirring conditions until the mixed solution became transparent. Afterwards, the PBO-COOH fibers (approximately 10cm) in the form of bundles were put into the precursor solution of UIO-66 and placed in a household microwave oven to prepare the resulting PUFs under the reaction condition of 240W 、 80W for 3min and 15min, respectively. The PUFs were later purified by immersing into the fresh DMF solution for about 20 minutes and repeated for twice. Hereafter, the DMF cleaned PUFs were transferred into a



single-necked flask and further purified by fresh CH3OH solutions with the condition of condensation reflux at 70 oC overnight. Ultimately, the hybrid fibers were put into an oven at 100 oC for about 1 h to dry completely for usage. 2.3 Preparation of PBO@tartrazine (PTFs). Prior to the preparation experiment of PTFs, the above obtained PUFs were placed into an oven at 100 oC to activate the channels of UIO-66 for at least 6 h in order to better adsorb the tartrazine molecules onto the surface of PBO fibers. According to the results of zeta potential test, the adsorption experiment was conducted at pH value of 4. Then the adsorption experiment of tartrazine was conducted at room temperature through immersing the PUFs (about 20mg) into the aqueous solution of tartrazine (100 mg/L) for 24 h in order to achieve the adsorption equilibrium in a static manner. 2.4 Physicochemical Characterizations. A Nicolet iS10 FTIR Spectrometer (Thermo Scientific, America) was utilized to qualitatively analysis the surface functional groups of PBO fibers before and after modification. SEM measurements was used to characterize the morphologies of pure UIO-66 and various PBO fibers by a SUPRA 55 SAPPHIRE Instrument from Carl Zeiss compony and surface elemental composition analysis was executed by EDX. The surface morphologies of pure UIO-66 powders were further recorded by a high-resolution transmission electron microscope (TEM) purchased from JEOL. The cross-section observation is performed by another TEM machine (HITACHI, Japan) combined with an ultramicrotome (Power Tome-XL, China). The surface roughness of different PBO fibers samples were obtained by an AFM test instrument (Bruker Dimension Icon, Germany) and the arithmetic mean roughness (Ra) values of PBO samples were recorded by averaging three values from different regions with 2×2 μm. The thermal stabilities of UIO-66, PBO-COOH and PUFs and the relevant grafting mass percentage of UIO-66 on the surface of PBO fibers were


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determined by a STA F5 synchronous thermal gravimetric analyzer (NETZSCH, Germany). The UV-Vis adsorption spectrum of UIO-66 was recorded using a TU 1901 UV-Vis spectrometer (Purkinje General Instrument, Beijing) under a diffuse-reflection model in the form of solid powder. The PXRD spectrum was received by an X’ Pert PRO XRD instrument (PANalytical, Netherlands). XPS measurements acquired by a photoelectron AXIS ULTRA DLD spectrometer (KRATOS, Britain) were also employed to determine the chemical element compositions on the surfaces of UIO-66 and various PBO fibers. The N2 adsorption isotherm and pore size distribution of UIO-66 were obtained at 77K using an adsorptive instrument (ASAP 2020, Micromeritics, America). The Zeta potentials of UIO-66 were performed using a Nano Z analyzer (Malvern, Britain) with different pH values range from 2-11 adjusted by 0.1M HCl or NaOH standard solution. Dynamic contact angle tests were recorded by a dynamic contact angle meter and tensiometer (DCAT 21, Data Physics Instruments, Germany) through immersing quadruplicate PBO fibers into two different testing liquids including deionized water (γld = 21.8 mN.m-1, γlp = 51 mN.m-1) and ethylene glycol (γld = 29.0 mN.m-1, γlp= 19.0 mN.m-1), with the immersing height of 3.5mm and followed by the calculation of surface energies of various PBO samples using the collected contact angles. At least five valid values were recorded and averaged to calculate the final surface energies of PBO fibers. The surface energy was statistically calculated using the following eq (1) and (2) and the final results were shown in Figure S8:



 l 1  cos    2  lp   fp



1/ 2



 2  ld   df



1/ 2

 f   df   fp Where the superscripts d, p and γf, γl represented the dispersive, polar components and the overall surface energy of testing liquid and fiber, respectively. The θ stood for the advancing contact angles.


(1) (2)


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2.5 Mechanical and UV-accelerated Aging Tests. The single monofilament tensile test was conducted to ascertain the tensile strengths (TS) of the PBO fibers performed on a universal material testing machine (Instron 5500R, USA) according to a standard of ASTM D3379-75. Using a valid gauge length of 2 cm and a 1 cm/min loading speed, at least 50 specimens of each sample for PBO fibers were tested and the results were subsequently analyzed by Weibull statistical method. The interfacial shear strength (IFSS) was measured to estimate the interfacial compatibility and combination of PBO fibers and epoxy resin by an interfacial evaluation equipment (MODEL HM410, Japan) through pulling off the cured epoxy resin beads from the outer surface of single PBO fiber with the both ends fixed on a metal holder using the sticky glue. Before the evaluative experiment, the epoxy resin beads were prepared by dipping and dotting few E-51/H-256 mixture (w/w= 100: 32) with a steel pin and followed by programmed heating-up curing procedure at 90, 120 and 150 oC for 2 h、2 h and 3 h, respectively. The sharp blades were adjusted to block a resin marble on the PBO fibers and then fixed to pull off the resin beads when the metal holder or single PBO fiber was advancing at the slow mode during the testing process. At least 50 specimens were recorded and averaged for per PBO sample. The available values of IFSS can be calculated by the following eq 3 and the final results were shown in Figure S9:

IFSS 

Fmax dl

(3)

Where Fmax corresponded to the maximum applied load, d was the diameter of single filament, and l was the embedded length of the cured resin marble. Before the UV-accelerated aging test, the PBO fibers were fixed onto the glass slides using the adhesive in the first place. Then, the UV photo-aging test was performed in an UV-accelerated aging box, where the intensity of the UV light, experimental temperature and irradiation distance were set as


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960 W/m2, 50 oC and 50 cm respectively. The wavenumber of UV light was ranging from 300 nm~500 nm. The samples were successively taken out from the UV aging box with the irradiation time interval was setting as 48h. Finally, the anti-UV properties of various PBO fibers were evaluated by the retention of tensile strength after different UV-accelerated aging time.

3. RESULTS AND DISCUSSION. 3.1 Physicochemical Characterizations of PBO fibers. Figure 2A displays the FTIR spectra of the various PBO fibers. All the PBO fibers present the characteristic peaks of the -C=N, -C-O-C and aromatic C-H stretching vibrations, which are located centrally at 1628 cm-1, 1056 cm-1 and 3000~3100 cm-1, respectively. Besides, the identical peak located at 3400 cm-1 is related to the -OH stretching vibration. In addition, the -C=O peak located approximately at 1720 cm-1 is emerging among the chemically treated PBO fibers and becomes gradually stronger for the PUFs and PTFs. Meanwhile, two new peaks located at 660 cm-1 and 554 cm-1 are appeared on the spectra of PUFs and PTFs. Further combined with the spectrum of the pure UIO-66 (Figure S1), the two peaks can be ascribed to the Zr-μ3-O stretching and asymmetric stretching vibrations of Zr-(OC), respectively.43 The above obtained results confirm that the UIO-66 has been in-situ grown on the surface of the PBO fibers via chemical bonds. As for the PTFs, the intensities of the feature peaks are slightly descending compared to those of PUFs. This may be a useful proof to attest that the successful coverage of tartrazine on the surface of PBO fibers via adsorption strategy mediated by UIO-66. Figure 2B shows the XRD patterns of tartrazine, as-synthesized and simulated UIO-66 and various PBO fibers. First of all, the synthesized UIO-66 with well crystallinity and phase purity is obtained according to the high intensities of related peaks and the excellent agreement with the simulated UIO-66 patterns.44-45 Moreover, the signature patterns of PBO fibers are maintained well in



all samples at 16.1° (200), 25.6° (010), 27.3° (210) and 32.4° (400), respectively, which is consistent with the results reported previously.46-47 As for PUFs, two obviously new feature peaks located at 2θ = 7.3° and 8.4° are appeared and represented for the (111) and (002) crystal face diffractions of UIO-66, respectively. Therefore, the XRD pattern of PUFs also indicates that the UIO-66 crystals have been successfully in-situ grafted onto the surface of PBO fibers and shows a good agreement with the FTIR results. Compared with PUFs, the XRD pattern of PTFs equally presents the characteristic diffraction peaks of UIO-66 but with slight intensities degradation of peaks. In consistent with the FTIR result of PTFs, this also may be due to the facile adhesion of tartrazine molecules onto the surface of PBO fibers by the UIO-66-mediated adsorption strategy.48-49 However, no apparent signals concerning the diffraction peaks of tartrazine are shown in the XRD pattern of UIO-66@tartrazine (Figure S2A) and PTFs. And this result could be ascribed to two possible aspects. On the one hand, the adsorption amount of tartrazine on the PUFs is comparatively less than the self-weight of UIO-66 and PUFs, which can be well supported by the subsequent adsorption results of tartrazine on the PUFs. On the other hand, the intensities of featured peaks of tartrazine are relatively lower than or covered by those of pure UIO-66 and PBO fibers seen from Figure 2. As a result, the XRD results of PUFs and PTFs state clearly together that the successful synthesis of UIO-66 crystals and introduction of tartrazine molecules on the surface of PBO fibers, which is achieved by the in-situ growth and UIO-66-mediated adsorption strategy, respectively.


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Figure 2. (A) FTIR spectra of all the samples of PBO fibers. (B) XRD patterns of tartrazine, simulated and as synthesized UIO-66, various PBO samples. The X-ray photoelectron spectroscopy (XPS) is performed to analysis the surface elements and chemical composition of PBO fibers, and the results are shown in Figure 3. As displayed in Figure 3A~3D, the C1s curve fittings of all samples present four identical peaks assigned at 284.8, 285.8, 286.8 and 288.1 eV, which are corresponding to C-C, C-N, C-O and N=C-O functional groups, respectively. In addition, the O-C=O functional group at 289.2 eV appears in the samples after the chemical treatment of pristine PBO fibers.46 Meanwhile, the contents of the O-C=O functional group increase gradually from PBO-Acided fibers to PUFs (Table S1). As shown in Figure 3E, the PUFs show three extra feature peaks related to Zr element including Zr3d, Zr3p1 and Zr3p2, respectively. The devolution results of Zr3d peak for PUFs and PTFs (Figure 3F, 3G) all involve two peaks at 182.4 and 184.8 eV, which are also the characteristic peaks of Zr3d for pure UIO-66 powder (Figure S3).50 However, a new typical peak ascribed to S2p presents at Figure 3E for PTFs and the relevant devolution analysis (Figure 3H) appears two new peaks at 168.6 and 169.8 eV, respectively assigned to the -SO3H of the tartrazine (Figure S4).51 Therefore, the detailed XPS results also confirm that the successful in-situ growth of UIO-66 and introduction of tartrazine onto PBO fibers, which are further consistent with the results of FTIR and XRD tests.



Figure 3. XPS analysis. (A)~(D): C1s spectra for PBO-Desized, PBO-Acided, PBO-COOH, PUFs,


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respectively. (E): Wide-scan XPS spectra of all the PBO samples. (F) ~ (H): XPS curve fittings for Zr3d peak of PUFs, Zr3d and S2p peaks of PTFs. Further investigation regarding the growth and distribution status of UIO-66 onto the surface of PBO fibers is gained by EDX spectrum and elemental mappings (Figure 4). The results also reveal that the dense and uniform growth of UIO-66 crystals on PBO fibers by the rapid microwave-assisted heating method.

Figure 4. (A) EDX spectrum and (B) elemental mappings of selected area on the surface of PUFs. The surface morphologies and status of PBO fibers are recorded by scanning electron microscopy (Figure5). As shown in Figure 5B, C, some narrow axial grooves appear on the surfaces of PBO fibers and become gradually visible due to the etching effect of acid reagent compared to the smooth surface of PBO fibers (Figure 5A). As for PUFs, an evidently rough surface morphology with a densely inner UIO-66 layer and numerous nanocrystals (200~300 nm) attached onto the outer surface of PBO fibers is shown in Figure 5D. These attached UIO-66 nanocrystals are caused by the special physicochemical interactions between them and the high BET surface area (Figure S5). Besides, the geometric topologies of these naked UIO-66 nanocrystals are in agreement with those of pure UIO-66 nanocrystals (Figure S6, S7), showing a typically octahedral morphology. The surface morphologies and amounts of surface-bound nanocrystals of PTFs are almost similar and unreduced during adsorption process compared with PUFs (Figure 5E). Herein, it should be important to point out that



the adsorption of tartrazine onto the surface of PBO fibers mainly due to the numerous naked UIO-66 nanocrystals rather than the inner layer. This can be rationally explained by the larger molecular dimension of tartrazine (molecular formula: C16H9N4Na3O9S2) and the smaller micropore size (0.6nm and 1.3nm) of UIO-66. Figure 5F shows the breakage morphology of inner growth UIO-66 layer on the surface of PBO fibers and the thickness of nanolayer is approximately 300 nm, all proving to be a dense and uniform monolayer growth.

Figure 5. SEM analysis. (A)~(E): SEM images for PBO-Desized, PBO-Acided, PBO-COOH, PUFs and PTFs, respectively. (F) Breakage morphology of UIO-66 layer on PUFs. The surface morphologies and roughness of PBO fibers are further intuitively observed by the 2D and 3D AFM images (Figure 6). Compared to the rather smooth surface of pristine PBO fibers with a Ra value of 19 nm, the roughness gently increases from 25 nm to 37 nm for PBO-Acided and PBO-COOH fibers, respectively. The enhanced Ra values can be ascribed to the existence of a few narrow grooves and bulges. Moreover, a sharp increasement of Ra value (70 nm) is realized for PUFs due to the dense and uniform growth of octahedral UIO-66 nanocrystals. All the above discussed AFM results are consistent well with previous SEM results. The significantly enhanced surface roughness (268%) of PUFs compared to pristine PBO fibers is also an affirmative proof to the great improvement


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of surface energy (91.1%) and the interfacial shear strength (49%).

Figure 6. AFM images of all the PBO samples. (A)~(D): PBO-Desized, PBO-Acided, PBO-COOH and PUFs, respectively. To better investigate the grafting thickness and surface status of UIO-66 nanolayer on the PBO fibers, cross-sectional TEM images of pristine PBO fibers and PUFs with resin are shown in Figure 7. As shown in Figure 7A, there is only a narrow boundary on the interface between pristine fibers and resin. However, obvious interface layer with thickness varying from 200 nm to 500 nm is observed for PUFs shown in Figure 7B~7D. Herein, the thickness of interlayer is considered to add the particle size of outer naked UIO-66 nanocrystals. Besides, the inner thickness of UIO-66 nanolayer is lower than that of SEM results. The possible reasons could be ascribed to the destruction of UIO-66 nanolayer during the process of section and the limited or competitive growth of inner UIO-66 nanocrystals. However, the actual thickness of UIO-66 paint-coat on the surface of PBO fibers can also be basically estimated by the sizes of outer naked nanocrystals according to the SEM results. Therefore, the actual thickness is approximately 200~300 nm and further agrees well with the result of Figure 5F.



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Figure 7. Cross-sectional TEM images of (A) PBO-Desized fibers and (B) ~ (D) PUFs in radial direction. 3.2. Adsorption Amount of tartrazine at equilibrium and Adsorption Mechanism. The tartrazine, also known as Acid Yellow 23, is chose as an experimental anti-UV azo dye. The most significant features of the UV-Vis curve for tartrazine are the wide adsorption wavelength range (300~500 nm) and the λmax at 430 nm, which indicate that tartrazine has an outstanding UV light adsorption performance. Generally speaking, the adsorption amount of dyes at equilibrium is calculated by the following equation52-53:

Qe 

(Co  Ce )V m

(4)

Where Qe is amount of dye adsorbed at equilibrium (mg/g), C0 and Ce are initial and equilibrium dye concentration (mg/L), V is volume of dye solution used (L), m is the mass of adsorbent used (g). The supernatant concentrations of tartrazine aqueous solutions are obtained by a UV 9100 B spectrophotometer at wavelength of 430 nm. To study the effect of pH value on the adsorption results,


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the pH values of dye solution is adjusted from 2~11 by adding a few drops of HCl and NaOH (0.1 mol/L). The zeta potential test is utilized to ascertain the optimal pH value used for adsorption experiment and the results are shown in Figure 8B. Meanwhile, the tartrazine has three characteristic functional groups including -SO3H (pKa=2.0), -COO- (pKa=5.0) and -N=N- (pKa=10.86), respectively. As a result, the tartrazine molecules will exist in an anionic form only in the condition that the pH value of aqueous solution is larger than 2. Otherwise, the tartrazine molecules will exist in a neutral form.54 As shown in Figure 8B, the point of zero charge (pHpzc) for UIO-66 is achieved at pH value of 6.13. According to the zeta potential test, the UIO-66 nanocrystals will take on a positive charge state when the pH values of its aqueous solutions are lower than pHpzc. Besides, the UIO-66 nanocrystals will have a good stability and adsorption ability at pH=4 with a highest positive zeta potential (43.8). Therefore, the adsorption experiment of tartrazine (C0=100 mg/L) on the PUFs is conducted at pH value of 4 for 24 h in a static approach under overall consideration. The change of absorbance for tartrazine before and after adsorption is shown in Figure 8A. Herein, the measured absorbance of tartrazine is the result of tenfold dilution for original aqueous solutions. Eventually, the final Qe value of tartrazine on the surface of PBO fibers reaches to 17.55 mg/g by calculation. This is not a small value by considering the grafting percentage of UIO-66 on the PBO fibers shown in TGA measurement results (Figure S10).



Figure 8. (A) UV-Vis adsorption curve of tartrazine. (B) Zeta potential of UIO-66 in aqueous solution at various pH values. To shed light on the adsorption mechanism and molecular interaction between tartrazine and PUFs, FTIR spectrum (Figure S1) of pure UIO-66 powder and XPS results (Figure 9) of PUFs and PTFs are collected in detail. For pure UIO-66 powder, there is a typical triplet peaks assigned at 749, 712 and 662 cm-1, respectively, which are normally corresponding to the Zr-O2 bonds as longitudinal and transverse modes.55 Moreover, the characteristic peaks located at 1394 and 1025 cm-1 are belonging to the stretching and bending vibrations of Zr-OH, respectively.56 As reported previously, the -OH functional groups on the adsorbent surface are usually and mainly responsible to for the adsorption of targeted adsorbates.57 For UIO-66, there are two likely adsorption sites to combine with the targeted dyes. On the one hand, the μ3-O, namely the protonated oxygen connected to Zr elements, is the firstly primary adsorption site that provides four Zr-OH groups to attract the dyes in a basic unit Zr6 cluster. Therefore, the glacial acetic acid is used as the modulator in the synthesis process of UIO-66 in our work, which is not only to enhance the zeta potential of UIO-66 but also to form linker deficiencies of per Zr6 formula unit and yield free Zr-OH bonds.58-59 On the other hand, the Zr-O-C connection generally can be replaced by the interaction between UIO-66 and dyes, which is also a possible adsorption site for removing the dyes. However, the potential condition for the occurrence of linker exchange during the adsorption process is that the dye molecules have the small hydrogen-halogen groups (such as -NH2 groups) or the atoms of halogen are directly connected with -OH groups.49, 56 Taking these aspects into account seriously, the process of linker exchange between tartrazine and BDC is almost impossible to occur. Therefore, the Zr-O-S coordination modes are only or mainly formed from the free Zr-OH groups and -SO3H groups of tartrazine, which can be well confirmed by


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the FTIR result of UIO-66@tartrazine shown in Figure S16. Figure 9 shows the XPS spectra of PUFs and PTFs. For the Zr3d curve fitting results, there is a visible shift of binding energy for PTFs from 182.40 eV to 182.70 eV shown in Figure 9A, which was further confirmed the successful occurrence of Zr-O-S connection modes in UIO-66@tartrazine. The enhancement of binding energy of Zr3d5/2 for PTFs can be ascribed to the more electronegative property of S-O bonds that lead to the change of the chemical environment and the loss of electron density of zirconium compared with C-O bonds.49, 60 Moreover, significant changes are also found in O1s peak fitting results as shown in Figure 9B. It contains four characteristic peaks including O-C=O (533.6 eV), Zr-O-Zr (530.6 eV), Zr-O-S and S=O (532.1 eV).48, 55 The results further indicate that the tartrazine molecules have been successfully attached onto the surface of PBO fibers by strong adsorption interactions mediated by UIO-66 nanocrystals with above mentioned likely adsorption sites.

Figure 9. XPS analysis. (A) Zr3d fitting of PUFs and PTFs. (B) O1s fitting of PTFs. On the basis of aforementioned results, the possible adsorption mechanisms of tartrazine and PUFs are illustrated at Figure 10. The octahedral topological structure, two kinds of cage types and the secondary building units (SBUs) of UIO-66 are shown in the Figure 10A and B. First of all, the mainly adsorptive interactions include the van der Waals force or other weak intermolecular forces, such as π-π stacking interactions between the organic ligands of UIO-66 and the benzene rings of tartrazine



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molecules (Figure 10E). Besides, the electrostatic attraction is also existed among the negative SO3- and COO- groups with surface positive charges of UIO-66 (Figure 10C).19,

49

Simultaneously, the

chemisorption is equally involved in the adsorption process due to the formation of Zr-O-S bonds (Figure 10D). Moreover, the tartrazine molecules can be adsorbed onto the external surface and a bit micropore via physisorption and chemisorption interactions in light of the FTIR spectrum (Figure S16) and N2 adsorption and desorption isotherm results (Figure S17). Therefore, the tartrazine molecules can be facilely attached onto the surface of PBO fibers by physisorption and chemisorption interactions mediated and realized via UIO-66. Furthermore, the above-mentioned adsorption mechanism between tartrazine and UIO-66 is commendably reflected in the forenamed characterization results of PTFs.

Figure 10. Schematic illustration of adsorption mechanism between PUFs and tartrazine. (A) Brief adsorption process. (B) Cage types of UIO-66. (C) Electrostatic attraction interaction. (D) Formation of Zr-O-S bonds. (E) π-π stacking interactions. 3.3 Mechanical and anti-UV properties of various PBO fibers. The tensile strength (TS) is an


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importantly inherent mechanical performance for fibers and usually affects the corresponding in-plane properties of fiber-reinforced composites.4-5, 39 Herein, the TS values of all PBO fibers are calculated before and after UV aging tests using the Weibull distribution function in consideration of the universal dispersity for all fibers. In addition, the Weibull distribution parameters (m) and correlation coefficients (R values) are also obtained from the calculation results. Theoretically speaking, the lower of m values, the more defects of fibers have. As shown in Figure 11A, the TS values of PBO-Acided (3.89GPa) and PBO-COOH (3.44GPa) fibers show gradual decrease compared with pristine PBO fibers (4.91GPa). This is due to the etching effect of H2SO4 and chloroacetic acid, which cause obvious striations on the surface of PBO fibers illustrated in Figure 5B, C. Moreover, the TS value of PUFs also shows a further decline compared to PBO-COOH fibers. The possible reasons could be ascribed to the high energy and penetration force of microwave as well as the longer irradiation time for completely nucleating and growing process of UIO-66. In other words, the inner well-oriented molecular chains of PBO fibers may have been partially cracked during the microwave reaction process. However, the m values of PUFs and PTFs show a visible increase compared to PBO-COOH fibers, which may be ascribed to a possible “repair” and “fill” mechanisms (Table S3).61-62 Meanwhile, the m values of each set of PBO fibers irradiated by UV light show a visible reduction in contrast with pristine fibers and vary in modest dynamic, indicating the gradual destruction of PBO fibers during the UV aging process. Besides, the R values for all PBO fibers are all beyond 0.9 before and after UV aging test, ensuring the validity and comparability of the results gained by mechanical test (Table S4~S8). In the present work, the retention of TS values is chosen as one of the significant indexes to evaluate the anti-UV properties of PBO fibers.11. The UV aging time is ranging from 0~288h with the interval of 48h and the corresponding results are shown in Figure 11B. Firstly, the TS descendant rates



of PUFs and PTFs are obvious lower than the other PBO fibers at all scope of irradiation time. Besides, the TS retentions of all PBO fibers show a gradual decrease with the aging time going on. Herein, the TS retention at 288h is selected to ultimately evaluate and compare the anti-UV properties of various PBO fibers. After connected with UIO-66 and tartrazine, the PUFs and PTFs all present excellent anti-UV properties with TS retention of 45% and 49% at 288h, respectively, which are obvious higher than that of pristine PBO fibers (27%). By comparison, the anti-UV properties (TS retentions) of PUFs and PTFs are increased by 81.5% and 66.7%, respectively. The higher TS retention of PUFs is ascribed to the UV adsorption ability of UIO-66 nanocrystals (Figure S11). Moreover, the anti-UV properties of PTFs are superior to the PUFs due to the additional UV adsorption effect of tartrazine. Meanwhile, at aging time of 96h, the enhancement of anti-UV property of PTFs is more obvious compared to PUFs with the TS retention of 90% and 60%, respectively. Notably, the TS retention values of PUFs and PTFs during the UV-accelerated aging process are in the high level of values among reported literatures.6, 10-11, 13, 63-64

Figure 11. (A) Tensile strength of all the PBO fibers before and after UV irradiation ranging from 0~288h. (B) Retention of TS values for various PBO fibers with corresponding UV aging time. The surface changes of various PBO fibers during the UV accelerated aging process are further monitored by SEM test. Herein, the SEM images of pristine PBO fibers, PUFs and PTFs at


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representative UV irradiation time of 96h, 192h and 288h, respectively are presented in Figure 12. As can be seen clearly, the surface status of pristine PBO fibers is obviously changed after UV aging test. Some cortical defects and slender stripes begin to appear on the surface of fibers at 96h irradiation time (Figure 12A). Besides, the defects and damages become more visible and serious at UV irradiation time of 192h and 288h including some leaf-liked defects (Figure 12B) and deep grooves (Figure 12C) as well as pernicious fiber cracking (Figure 12D). However, the PUFs and PTFs present a discrepant evolution of surface status compared with pristine PBO fibers during the UV aging process. As for PUFs, only few open holes and slim cracks are appeared on the UIO-66 nanolayer at 96h. With the passage of time, the numbers of open holes increase by degrees. Moreover, the outer naked UIO-66 nanocrystals gradually fall off and eventually disappear from the surface of PBO fibers. As a result, the inner UIO-66 nanolayer becomes exposed as shown in Figure 12F. Then, some serious cracks on inner UIO-66 nanolayer and cortical damages of the PBO fiber surface are found at time up to 288h (Figure 12G, H). At the same time, some slender stripes are reappeared and agree with the result of Figure 5C. As for PTFs, the bare UIO-66 nanocrystals still tightly anchor onto the inner UIO-66 nanolayer and the nanolayer shows few visible cracks merely at time of 192h. With time up to 288h, there are no macroscopic defects except the big hole and shedding of inner UIO-66 protecting layer appeared. As we know, PBO fibers have a characteristic skin-core structure and the integrity of cortex with thickness about 1~2 μm is mainly responsible for the mechanical performance of PBO fibers. Therefore, the surface changes of all PBO fibers are in great consistent with the corresponding TS retention results mentioned above. Combined with the results of Figure 11B and Figure 12, it can be concluded that the successful introduction of inner UIO-66 nanolayer will do contribute to reducing the surface destruction and improving the anti-UV properties of PBO fibers to some extent. Moreover, the



adhesion of tartrazine molecules via the adsorption strategy will better protect the PBO fibers and further enhance the anti-UV properties of PBO fibers due to synergistic effects of tartrazine and UIO-66 nanocrystals. The UV-Vis solid diffuse reflectance spectra of various PBO fibers (Figure S12) further support and confirm the above conclusions obtained from the TS and SEM results, which the UV absorbance of PUFs and PTFs is obviously higher than that of pristine fibers and the Vis absorbance of PTFs is much higher than other fibers including the PUFs.

Figure 12. SEM images of various PBO samples before and after UV accelerated experiment, including PBO-Desized fibers (A) ~ (D), PUFs (E) ~ (H), PTFs (I) ~ (L), respectively. On the basis of foregoing results shown in Figure 11 and 12, the possible anti-UV mechanisms of PUFs and PTFs are proposed and shown in Figure13. First of all, the pristine PBO fibers with smooth and inert surfaces are vulnerable to UV light irradiation, leading to the breakage of benzoxazole molecular chains and the formation of DAR and TA monomers. However, combined with the foregoing discussed results, the PUFs and PTFs undoubted display well improved UV-resistant properties with gradually reduced breakage of molecular chains and cracks of bulk structure. These


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results are mainly benefited from three functions of UIO-66 and tartrazine molecule, including (1) UV reflection, (2) UV refraction, (3) UV adsorption, respectively. In other words, a piece of “shielding cloths” is likely dressed in the surface of PBO fibers to protect fibers from being destroyed. According to the UV-Vis DRS spectra of PUFs and PTFs (Figure S12), the UV-Vis absorbance of PUFs and PTFs is obviously higher than that of pristine PBO fibers. As a result, the irradiation intensity and energy of UV lights will be largely weakened by UIO-66 and tartrazine before reaching to the surface of PBO fibers. Therefore, the anti-UV performance of PUFs and PTFs is obviously improved compared to the pristine PBO fibers. Moreover, the absorbance of PTFs in the visible light region is much higher than PUFs, which also confirms the successful combination of tartrazine onto the surface of PBO fibers. This result further supports the superior Anti-UV properties of PTFs than those of PUFs. Herein, there are likely two pieces of “shielding clothes” worn on the surface of PBO fibers in PTFs due to the synergistic interaction of tartrazine molecules and UIO-66 nanocrystals. Therefore, the breakage of molecular chains and cracks of bulk structure for PBO fibers will unquestionably decrease during the UV accelerated aging process by the MOFs-mediated adsorption strategy. The above-mentioned results of TS retention and SEM images (Figure 12) further agree commendably with the proposed anti-UV mechanisms.



Figure 13. Schematic illustration of the possible UV-resistant mechanisms for PUFs and PTFs.

4. CONCLUSIONS In the present work, a UIO-66-mediated adsorption strategy was firstly and successfully developed to improve the anti-UV properties of PBO fibers. The surface energy, roughness and IFSS value of PUFs were 91.1%, 268.4% and 49.0% higher than those of pristine PBO fibers. Meanwhile, experimental results confirmed that both the PUFs and PTFs presented excellent anti-UV performance with the TS retention of 66.7% and 81.5% higher than that of pristine PBO fibers at UV aging time of 288h, respectively. The superior anti-UV performance of PTFs can be rationally ascribed to the synergistic effects of UIO-66 nanocrystals and tartrazine molecules. Our work promisingly indicates that the MOFs-mediated adsorption strategy would endow PBO fibers with other desired performance and applications (such as solar-thermal transition and self-healing abilities) based on the varieties and functionalities of MOFs and targeted materials.


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Acknowledgments We thank the National Natural Science Foundation of China (no. 51673053), the Natural Science Foundation of Heilongjiang Province (no. LC2017024), and the Fundamental Research Funds for the Central Universities (no. HIT. IBRSEM. 2013016).

* Supporting Information Figure S1: FT-IR spectra of pure UIO-66 and tartrazine powder; Figure S2: PXRD patterns of tartrazine, UIO-66 and UIO-66@tartrazine, Digital images of UIO-66 and UIO-66@tartrazine; Figure S3: XPS curve fitting of Zr3d for UIO-66; Figure S4: XPS curve fitting of S2p for tartrazine molecules and C1s for PTFs; Figure S5: N2 adsorption and desorption measurement results for UIO-66; Figure S6: SEM images of pure UIO-66 powder; Figure S7: TEM images of pure UIO-66 powder; Figure S8: dynamic contact angle test of various PBO fibers; Figure S9: single-filament pulling out process of various PBO fibers; Figure S10: TGA results of UIO-66 powder, PBO-COOH and PUFs; Figure S11: UV-Vis (DRS) spectra of UIO-66; Figure S12: UV-Vis (DRS) spectra of various PBO fibers; Figure S13: Particle size distribution results of UIO-66 powder; Figure S14: Effect of the solution pH values on the Zeta potential of UIO-66 and the Adsorption amount (Qe) towards tartrazine; Figure S15: UV-Vis adsorption curve of tartrazine before and after adsorbed by bulk UIO-66 powders; Figure S16: FTIR spectra of tartrazine, UIO-66 and UIO-66@tartrazine; Figure S17: N2 adsorption and desorption measurement results for UIO-66@tartrazine. Table S1~S2: XPS results of various PBO fibers towards the percentage content of different functional groups and elemental composition; Table S3~S8: TS values and related parameters of various PBO fibers before and after UV aging test. This material is



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available free of charge via the Internet at http://pubs.acs.org.

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