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In situ growth of MOF on BiOBr 2D material with excellent photocatalytic activity for dye degradation Shuai-Ru Zhu, Meng-Ke Wu, Wen-Na Zhao, Peng-Fei Liu, Feiyan Yi, Guo-Chang Li, Kai Tao, and Lei Han Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01811 • Publication Date (Web): 07 Apr 2017 Downloaded from http://pubs.acs.org on April 8, 2017

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In Situ Growth of MOF on BiOBr 2D Material with Excellent Photocatalytic Activity for Dye Degradation Shuai-Ru Zhu† Meng-Ke Wu,† Wen-Na Zhao,*,‡ Peng-Fei Liu,† Fei-Yan Yi,† Guo-Chang Li,† Kai Tao† and Lei Han*†,§ † State

Key Laboratory Base of Novel Functional Materials and Preparation Science, School of Materials Science & Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, China ‡

Key Laboratory for Molecular Design and Nutrition Engineering of Ningbo, Ningbo Institute of Technology, Zhejiang University, Ningbo, Zhejiang 315100, China §Key

Laboratory of Photoelectric Materials and Devices of Zhejiang Province, Ningbo University, Ningbo, Zhejiang 315211, China Supporting Information Placeholder ABSTRACT: The in situ growth of Bi-based MOF (CAU-17) on BiOBr 2D material was prepared for the first time by used a facile solvothermal transformation approach. The BiOBr was applied both as templates to support the growth of MOF and also as Bi3+ sources of MOF. The BiOBr/CAU-17-2h composite exhibited an enhanced photocatalytic activity for degradation of Rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) under visible light irradiation, suggesting a good synergy between BiOBr and CAU-17 MOF.

Metal-organic frameworks (MOFs), as a fascinating kind of porous crystalline materials, have received increasing attention due to their permanent porosity, tunable pore size and rich surface chemistry.1-4 Currently, there is increasing research interest in the preparation and applications of MOF-base composites, especially MOF/2D material composites.5-7 The smart integration of MOFs and 2D materials is anticipated to impart unique properties for various applications. Several types of 2D materials/MOFs composites, such as GO/MOF, 8 C3N4/MOF,9 BN/MOF,10 MoS2/MOF,11 LDH/MOF,12 have shown promise in achieving improved performance in energy storage, separation, photocatalysis, as well as chemical sensing. BiOBr, a novel 2D layered ternary oxide semiconductor, has been found to be potential photocatalytic ability under visible-light illuminated.13-15 Due to its low efficiency of light absorption, low adsorption capacity and high recombination rate of photo-induced electron–hole pairs, the photocatalytic activity of pure BiOBr is limited.16 Hence, there are two main methods to improve

the potential of BiOBr for photocatalytic activity, one is the effective separation of the photo-generated electron– hole pairs, the other is enlarged accessible surface area for more contact between photocatalyst and dye molecules.17,18 To overcome these problems, an effective strategy is incorporating them with other functional species to form BiOBr-based heterostructured composites.19-21 Therefore, the combination of BiOBr and MOF to form composites has been carried out to improve photocatalytic performance. Currently, three examples, such as BiOBr/Uio-66,22 BiOBr/MOF-523 and BiOBr/NH2MIL125(Ti),24 have been reported for dyes degradation. Nevertheless, all existing BiOBr/MOF composites were mostly synthesized by the physical mixing method or by the co-precipitation method of BiOBr and MOF precursors. These procedures usually generated insufficient chemical interactions between BiOBr and MOFs, which would limit the transfer of photogenerated electron– hole pairs. On the basis of our previous research in BiOBr/MOF composite materials,24 herein, we firstly report the in situ growth of Bi-based MOF (CAU-17) on BiOBr 2D material through a facile solvothermal transformation approach. The BiOBr was applied both as templates to support the growth of MOF and also as Bi 3+ sources of MOF. As a proof of concept, the fabricated BiOBr/CAU-17 heterostructured material was evaluated by photocatalytic activity and displayed an enhanced degradation of dyes than the previously reported BiOBr/MOF materials, suggesting a good synergy between BiOBr and CAU-17 MOF. The facile in situ solvothermal transformation of BiOBr was carried out under the mixture of BiOBr flake precursor and 1,3,5-benzenetricarboxylic acid (H3BTC) in

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Figure 1. SEM images of (a) BiOBr flake, (b) BiOBr/CAU-17-2h, (c) BiOBr/CAU17-3h, (d) BiOBr/CAU-17-6h, and (e) XRD patterns, and (f) FT-IR spectra.

MeOH/DMF solution at 120℃ (see ESI). By adjusting reaction time, this approach enables the growth of MOF on BiOBr flake with a uniform and controlled transformation. Obviously, more time increased, more MOF patterns generated. The optimized time span is about 2 h to form composite with high photocatalytic property. The morphology was observed by SEM and shown in Fig. 1. The pristine BiOBr exhibited flake-like with an average diameter approximately 500-800 nm (Fig. 1a). After reaction for two hours, the flake-like structure was still remained (Fig. 1b). At 3h, the rod-like morphology of MOF began to appear (Fig. 1c). After 6h, it can found that there are less nanosheets (Fig. 1d). X-ray diffraction revealed that the generated MOF is a reported Bi-based 3D MOF, [Bi(BTC)(H2O)] denoted CAU-17,25 which has an exceptionally complicated structure with helical Bi−O rods cross-linked by BTC ligands. As shown in Fig. 1e, the pristine BiOBr presented tetragonal-phase (JCPDS 73-2061) with well indexed crystal planes.26 Several strong diffraction peaks from CAU-17 are discernable in BiOBr/CAU-17-2h and BiOBr/CAU-173h, indicated by arrows, suggesting that the structure of CAU-17 exists into the BiOBr/CAU-17 system. Interestingly, the intensity of the (002) and (112) diffraction peaks in BiOBr/CAU-17 system differs from that of BiOBr. Thus, it is expected that CAU-17 may influence the exposed percentage of crystal planes of BiOBr. The two peaks between 6° and 10° can be observed clearly even in the pattern of BiOBr/CAU-17-3h, which possesses the higher CAU-17 content than BiOBr/CAU-17-2h sample. However, compared with CAU-17, the location of diffraction peak at 7.8° of the BiOBr/CAU-17-2h was shown to shift slightly, which further confirmed that BiOBr plays the role of an interaction based on lattice distortion of MOF.26 FT-IR spectra of BiOBr/CAU-17 composites are shown in Fig. 1f. It can be observed that a sharp peak at 510 cm−1 and a broad peak at 3400 cm-1 can be attributed to Bi-O stretching and the O–H vibration of H2O, respectively.27 The characteristic bands of carboxylate

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Figure 2. EDS analyses and mapping of BiOBr/CAU-17-2h composite.

Figure 3. (a) TEM and (b) HR-TEM images of BiOBr/CAU-17-2h composite.

group in CAU-17 were observed at 1380–1600 cm-1 as well composite. as the vibrations of O-Bi-O groups at 400–800 cm-1.25 In addition, the characteristic bands of CAU-17 in BiOBr/CAU-17-3h are stronger than those in BiOBr/CAU17-2h. This results further demonstrate that the growth of CAU-17 on BiOBr flake is controlled transformation by adjusting reaction time. Thermogravimetric analysis was used to determine the weight contents of CAU-17 in the composite photocatalysts. As illustrated in Fig. S1, the contents of CAU-17 in BiOBr/CAU-17-2h, -3h, -6h, were increased gradually. As for BiOBr/CAU-17-2h, it shows two apparent mass loss, corresponding to the pure CAU-17 and BiOBr. In addition, EDS analyses and mapping spectrum of BiOBr/CAU-17-2h (Fig. 2) shows peaks corresponding to the elements of Bi, Br, O, C, suggesting that the in situ growth of CAU-17 on BiOBr 2D material has been prepared successfully. To further prove the above conclusion, the EDS mapping was measured, which clearly shows the uniformly distribution of the elements. The typical TEM and HR-TEM images of BiOBr-CAU17-2h is shown in Fig. 3. BiOBr nanosheets became small pieces by erosion effect of CAU-17. Clear fringe with an interval of 0.282 nm could be indexed to (012) lattice plane of tetragonal BiOBr. Moreover, clear fringe with an interval of 1.517 nm and 0.846 nm could be attributed to lattice plane of lattice plane of CAU-17, which further demonstrated that the existence of the CAU-17 and BiOBr in composite.

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Figure 5. (a) UV-Vis diffuse reflectance spectra (insert is (αhv)1/2 versus energy (hv) to obtain the band gap energies of the catalysts). (b) Photocurrent responses of BiOBr, CAU-17 and BiOBr/CAU-17-2h.

Figure 4. XPS spectra of samples：(a) survey scan, (b) C1s, (c) O1s (d) Bi4f, and (e) Br3d.

In order to further investigate chemical composition and surface chemical state of the as-prepared materials, X-ray photoelectron spectroscopy (XPS) measurement was carried out. As shown in Fig. 4a, the survey spectrum of BiOBr/CAU-17-2h exhibited the existence of Bi, Br, O and C elements in the material. The C 1s (Fig. 4b) spectrum shows three peak at 284.8, 286.2 and 288.4 eV corresponding to C=C, C-C and C=O of H3BTC in CAU17, respectively.24 For BiOBr/CAU-17-2h, the C 1s is similar to that of CAU-17, demonstrating the the existence of CAU-17. The O 1s (Fig. 4d) peak could be attributed to three peaks at 530.0, 533.5 and 531.5 eV, which are related with the crystal lattice O atoms of BiOBr (Bi–O), the O in bismuth–oxo clusters, and other components such as H2O, respectively.38,39 By comparing XPS of CAU-17, the positive shift of 0.6 eV binding energies is observed at 533.5 eV. This can be resulted from electronegativity effect between Bi and possibly O atom in BiOBr material. Two peaks centered at 159.2 and 164.5 eV for BiOBr/CAU-17-2h (Fig. 4c) are assigned to Bi 4f7/2 and Bi 4f5/2, respectively. At the same time, the shift o.5 eV to the higher binding energies of 159.7 and 165.0 eV, respectively, is observed for CAU-17, indicating O of BTC does influence the electronic structures of Bi atoms. In the high-resolution spectrum of Br 3d (Fig. 4e), the peaks located at 68.2 and 69.3 eV are associated for Br 3d5/2 and Br 3d3/2, respectively.40,41 To further understand the interaction between BiOBr and CAU-17 in composite, UV-vis diffuse reflectance spectra (Fig. 5a) and photocurrent spectra (Fig. 5b) have also been carried out. Due to the absorption of CAU-17 at UV range, the absorption intensities of BiOBr/CAU17-2h were higher than BiOBr between 200 and 435 nm. The band gaps (Eg) of the catalysts can be evaluated from Tauc's plots using α(hv) = A(hv–Eg)n/2, where α, h, v, A and Eg are the absorption coefficient, Plank's con-

stant, light frequency, a constant and band gap energy, respectively, n is estimated by the optical transition of the semiconductor.22 The absorption edges of the BiOBr and BiOBr/CAU-17-2h locate in the range of 425–435 nm, corresponding to the estimated band gaps about 2.84, 2.86 eV, respectively. The photocurrent intensity of the BiOBr/CAU-17-2h was nearly 1.8 times as high as that of pristine BiOBr. This implied that a more effective separation of photo-generated electron-hole pairs and a faster interfacial charge transfer occurring in BiOBr/CAU17-2h.28,29 Therefore, the results show that charge separation efficiency may be the reason to improve photocatalytic performance. The photocatalytic performance of RhB over different samples under visible light irradiation was evaluated (Fig. 6a). Self-photodegradation of RhB can be negligible from blank text. Fig. S2 presents the corresponding changes of UV–vis absorption spectra of photocatalytic decomposition of RhB in the presence of BiOBr/CAU-172h. It shows excellent photocatalytic efficiency, as about 85.7 % of RhB was degraded under visible light irradiation for 50 min. Simultaneously, the maximum absorption band of RhB at λ = 553 nm was blue-shifted, which was attributed to the de-ethylation process.28 The photocatalytic degradation kinetics for RhB over BiOBr/CAU-17-2h photocatalyst were investigated according to the pseudo-first-order model (−ln(C/C0) = kt) and the k values are summed in Table S1. It was observed that BiOBr/CAU-17-2h composite disclosed higher rate constants than that of pristine BiOBr. The BiOBr/CAU17-2h composite has the maximum rate constant of 0.10013 min-1, which was nearly 8.3 times as high as that of pristine BiOBr (Fig. 6b). This suggests that there is optimized time span of synthesis over the BiOBr/CAU-17 catalysts. In addition, excess or a few reaction time will enhance or decrease the content of CAU-17 onto BiOBr material. A possible explanation is that when too little amount of CAU-17 will not benefit for the charge separation efficiency. However, excessive CAU-17 will decrease mass percent of BiOBr, which shows that there produces less photo-generated electron-hole pairs. Thus, we design the controllable experiments with physical mixtures of different quality percent of pristine CAU-17 and BiOBr to investigate above possible explanation. As shown in Fig. S3, it is indicated that there is an optimum value of quality percent for the physical hybrid photocatalyst between BiOBr and CAU-17. Due to weak chemical bonding with mechanical compounds, its photo-generated eletrons and holes are not conductive to transfer between

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RhB + hv → RhB+•+e− (1) BiOBr + hv → BiOBr (e− + h+) (2) O2 (dissolved) + e− → •O2− (3) •O −+ RhB/RhB+• →other products → CO + H O (4) 2 2 2 h+ + RhB/RhB+• → other products → CO2+ H2O (5)

Figure 6. (a) Photocatalytic degradation efficiencies of RhB with different sample sunder visible-light irradiation. (b) Comparison of the rate constant k in the presence of different samples. (c) Photocatalytic degradation of MB. (d) Photocatalytic degradation of MO.

BiOBr and CAU-17. Correspondingly, much lower photocatalytic activity than BiOBr/CAU-17-2h composites. At the same time, MO and MB were chosen as different types of dye pollutants to determine the photocatalytic performance of BiOBr/CAU-17-2h. Fig. 6c and 6d clearly demonstrated that BiOBr/CAU-17-2h for the photodegradation of MO and MB were also much higher ability than that of the pristine BiOBr. It should be noted that the BiOBr/CAU-17-2h has higher photocatalytic activity than the previous reported BiOBr/MOF composites, compared in Table S2.22-24 The significant activity of BiOBr/CAU-17-2h may let it become valuable photocatalytic material in potential applications for cleaning of environmental pollutants. In order to explore the reactive radical species involved in RhB photodegradation over BiOBr/CAU-17-2h material, TEOA was used as photo-induced holes (h+) scavenger,30 BQ was used as superoxide radicals (•O2−) scavenger31 and IPA was used as hydroxyl radicals ( •OH) scavenger.32 As shown in Fig. S4, it can be obviously showed that the photocatalytic decomposition of RhB was only slightly affected by addition of IPA. Whereas, the degradation efficiency of RhB was greatly inhibited by BQ and TEOA, confirming that •O2− and h+ were the main radical species in the photodegradation process. The ESR spectra of DMPO–•O2− adducts on BiOBr/CAU17-2h catalyst without RhB under methanol conditions was exhibited in Fig. S5. Comparing to no obvious signals detected in the dark, four characteristic peaks of DMPO–•O2− were observed under visible light irradiation. It proved that BiOBr-CAU-17-2h catalyst could be efficiently excited by visible light to create photoinduced electrons, additionally, reacting with adsorbed oxygen/H2O to produce •O2− on the photocatalyst surface.42-44 Jiang et al.26 confirmed that h+ (photo-generated hole) of BiOBr could be attributed to the reaction with dye molecules directly. The band edge of CB potential of BiOBr (0.27 eV vs. SHE) is not negative enough to reduce the O2 molecule to the •O2− ion radicals by the photo-generated electron. However, •O2− is also a the main

Scheme 1. Plausible mechanism for the photocatalytic degradation of RhB by BiOBr/CAU-17-2h under visible light.

radical species in the photodegradation process. Considering the potential of RhB (0.95 eV vs. SHE) and RhB* (1.42 eV vs. SHE), a reasonable explanation for the generation of •O2− is that the RhB molecules is excited to RhB* and injects electrons into CB of BiOBr under visible-light illumination. Then the electrons could reduce O 2 to form •O2− and further decompose the RhB molecules. 33,34 Meanwhile, the synergistic effect between CAU-17 and BiOBr on the catalyst surface plays an important role when the photocatalytic degradation is initiated by the direct hole oxidation and dye sensitization. 28-30,34-37 Based on the above assumption, thus a plausible mechanism is exhibited in Scheme 1. The stability of photocatalyst is a very important parameter for practical applications. Thus the as-prepared BiOBr/CAU-17-2h composite photocatalyst was also evaluated. As shown in Fig. S6, the RhB degradation efficiency decreased to around 31.74 % compared with first run after the fifth recycling runs. Simultaneously, the FT-IR spectroscopy was also investigated, and the results were depicted in Fig. S7. The characteristic bands of carboxylate groups at 1380–1600 cm-1 as well as the vibrations of O-Bi-O groups remained unchanged, revealing that there was no change in the chemical structure of BiOBr/CAU-17-2h samples before and after reactions. However, the photocatalytic efficiency of catalyst has a certain extent decline with increasing reuse times, which may be due to the mass loss during the transferring and sedimentation processes and the gradually decrease in adsorptive capacity of the catalyst.45 In summary, the in situ growth of Bi-based MOF (CAU-17) on BiOBr 2D material was prepared for the first time through a facile solvothermal transformation approach. The BiOBr was applied both as templates to support the growth of MOF and also as Bi 3+ sources of MOF. The BiOBr/CAU-17-2h composite exhibited enhanced photocatalytic activity for degradation of RhB, MB, and MO under visible light irradiation. Meanwhile, The rate constantof BiOBr/CAU-17-2h composite was about 8.3 times that of pristine BiOBr. The trapping experiments of the active species confirmed that the •O2− and h+ were the main radical species for photocatalytic

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degradation of RhB. In addition, the enhanced photocatalytic efficiency provided by BiOBr/CAU-17-2h could be ascribed to the faster interfacial charge transfer. Last but not least, this research is of considerable significance because it opens up extensive opportunities to the development of in situ growth of various MOF on 2D materials with the same metal element for water treatment and other potential applications in the future.

ASSOCIATED CONTENT Supporting Information Experimental details, TGA, UV-vis spectra, reusability of photodegradation, materials and physical measurements. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author * Email: [email protected] and [email protected].

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21471086, 91122012), the Social Development Foundation of Ningbo (no. 2014C50013), and the K. C. Wong Magna Fund in Ningbo University.

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For Table of Contents Use Only In Situ Growth of MOF on BiOBr 2D Material with Excellent Photocatalytic Activity for Dye Degradation Shuai-Ru Zhu† Meng-Ke Wu,† Wen-Na Zhao,*,‡ Peng-Fei Liu,† Fei-Yan Yi,† Guo-Chang Li,† Kai Tao† and Lei Han*†,§ † State

Key Laboratory Base of Novel Functional Materials and Preparation Science, School of Materials Science & Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, China ‡

Key Laboratory for Molecular Design and Nutrition Engineering of Ningbo, Ningbo Institute of Technology, Zhejiang University, Ningbo, Zhejiang 315100, China §Key

Laboratory of Photoelectric Materials and Devices of Zhejiang Province, Ningbo University, Ningbo, Zhejiang 315211, China

The BiOBr/CAU-17-2h composite was prepared by in situ growth of Bi-based MOF (CAU-17) on BiOBr 2D material and exhibited an enhanced photocatalytic activity for degradation of RhB, MB, and MO under visible light irradiation.

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