Photodegradation of Some Organic Dyes over Two MetalâOrganic

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Photodegradation of Some Organic Dyes over Two MetalOrganic Frameworks Especially High Efficiency for Safranine T Ling Qin, Hong-Zhe Chen, Jiang Lei, Yan-Qing Wang, Tongqi Ye, and He-Gen Zheng Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01690 • Publication Date (Web): 08 Feb 2017 Downloaded from http://pubs.acs.org on February 9, 2017

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Crystal Growth & Design

Photodegradation of Some Organic Dyes over Two Metal-Organic Frameworks Especially High Efficiency for Safranine T Ling Qin†,‡, Hong-Zhe Chen†, Jiang Lei†, Yan-Qing Wang†, Tong-Qi Ye†, and He-Gen Zheng‡,*

†

Department of chemical engineering and food processing, Xuancheng Campus, Hefei

University of Technology, Xuancheng, 242000, Anhui, PR. China. ‡

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical

Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, P. R. China

Abstract:

Two

new

networks,

namely

{[Cd(bpba)(H2bptc)1/2.H2O]}n

(1),

{[Co(bpba)(bdc)1/2]}n (2), where Hbpba = 3,5-bis(pyridin-4-ylmethoxy)benzoic acid, H4bptc = 3,3',5,5'-biphenyltetracarboxylate, H2bdc = 1,4-benzenedicarboxylate, have been

synthesized

hydrothermally

and

characterized.

Compound

1

is

a

three-dimensional (3D) net with a rare jea topology. The flexible pyridyl arms may afford a dimension extension in the crystal structure. While, for compound 2, the flexible pyridyl arms are not involved in coordination, the Co (II) paddle-wheel secondary building units are bridged by the mixed ligands, bpba- and bdc2-, to furnish a 2D layer. In addition, their heterogeneous catalytic oxidation activities toward Methyl orange (MO), Methyl blue (MB), Neutral red (NR), Methylene blue (MEB), and Safranine T (ST) in the presence of H2O2 are investigated in aqueous solution. The results suggested that the photocatalytic efficiency of ST is found to be 100% for MOF-2.

Introduction Organic dyes have been widely used in solar cells, biological imagings, textiles, medicines, and some other industries.1-3 However, its dumping into the water is

ACS Paragon Plus Environment


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harmful to human, which is attributed to their toxicity and carcinogenicity. Over the past years, various technologies and methods have been used to eliminate organic dyes from wastewater.4-9 Among these attempts, photodegradation has been deemed to one of effective means of eliminating dyes.10-13 Since Honda and Fujishima discovered that TiO2 electrodes can be used to photocatalytic splitting of water,14 many traditional semiconductors as photocatalyses have been extensively used to degrade organic dyes.15-20 While, it has some impedimences such as loss of reactivity, separation, and so on. Therefore, new catalytic materials with high efficiency for environmental protection should be solved urgently. In recent years, more and more researches about metal-organic frameworks (MOFs) self-assembling from metal ions and organic ligands are transfering from a centre on structure characteristics to their application aspects, such as magnetism, luminescence, catalysis, light harvesting, ferroelectricity, ion exchange, gas storage, and biomedical imaging.21-27 Recently, MOFs have been researched as photocatalysts for dye degradation and waste watertreatment.28-32 As we know, many factors can determine the self-assembly process of MOFs.33-38 While, the structure characteristics of organic ligands have an important effect. As the previous reported literatures, the flexible pyridyl-carboxylate bifunctional ligands have more advantages because of their abundant coordination sites and their flexibilities and conformational freedoms in favour of meeting the coordination environment of metal ions.39-41 To continue the study on pyridyl-carboxylate based MOFs, we selected and used the flexible 3,5-bis(4-pyridylmethoxy)benzoic acid (Hbpba)42-43 as a primary ligand. Hbpba contains a rigid phenylcarboxyl molecular block and two flexible pyridyl parts. The pyridyl groups can rotate through methoxy groups to satisfy the coordination configuration of metal ions, and the use of Hbpba ligand may generate novel structures. On the other hand, the Hbpba is a bifunctional ligand with one carboxylate group, we chose another two polycarboxylates44-47 as the second ligand to supply the more negative charge. The using of the mixed ligands is beneficial to construct various structures. Herein, two new networks, namely {[Cd(bpba)(H2bptc)1/2

.

H2O]}n (1), {[Co(bpba)(bdc)1/2]}n (2), where Hbpba =


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3,5-bis(pyridin-4-ylmethoxy)benzoic acid, H4bptc = 3,3',5,5'-biphenyltetracarboxylate, H2bdc = 1,4-benzenedicarboxylate, have been synthesized hydrothermally and characterized. In addition, their heterogeneous catalytic oxidation activities toward some dyes, such as: Methyl orange (MO), Methyl blue (MB), Neutral red (NR), Methylene blue (MEB), and Safranine T (ST), were also investigated in the presence of H2O2 in aqueous solution.

RESULTS AND DISCUSSION Structure of {[Cd(bpba)(H2bptc)1/2 . H2O]}n (1) In the asymmetric unit, there are one Cd2+ cation, one bpba-, 1/2 partially deprotonated H2bptc2- ligand and one coordinated water molecule, which crystallizes in the monoclinic C2/c space group. Each Cd(II) ion is defined by two N atoms and two carboxylate O atoms of bpba- ligands, two carboxylate oxygen atoms of one H2bptc2- ligand, together with one water molecule to construct a pentagonal bipyramid (Figure 1a). The bpbaligand connects three Cd2+ ions to form a 2D layer (Figure 1b). Each H2bptc2- ligand connecting with two Cd2+ ions link the 2D layers to generate a 3D net (Figure 1c). As shown in Figure 1d, each bpbaligand connects three Cd2+ cations and acts as a 3-connected node, each H2bptc2- ligand links two Cd2+ cations as a linker, while each Cd2+ cation is surrounded by three bpba- ligands and one H2bptc2ligand to afford a 4-connected node. Therefore, the topology result48 of 1 shows the structure is a (3,4)-connected 3D network and attributes to jea type net49-50 with the {63}{65.8} topology symbol. Besides, the larger flexible ligands are easier to form the various entanglements. As shown in Figure 1e, two sets of identical 3D nets are penetrated to each other, resulting in a 2-fold interpenetrated 3D framework.



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Figure 1 (a) Coordination environment of Cd2+ cation in compound 1 with 30% ellipsoid probability (Symmetry code: #1 = 1.5 - x, - 0.5 + y, 0.5 - z; #2 = 1.5 - x, - 0.5 + y, 1.5 - z). (b) Schematic views of the 2D layer formed by Cd2+ cation and bpbaligand. (c) Schematic views of the 3D nets formed by Cd2+ cation, bpba- and H2bptc2ligands. (d) Schematic views of the (3,4)-c net 1 with jea topology. (e) Schematic representations of the two-fold interpenetrating nets.

Structure of {[Co(bpba)(bdc)1/2]}n (2)


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The X-ray crystallographic analysis reveals that compound 2 crystallizes in the triclinic space group P-1. The asymmetric unit of 2 consists of one Co (II) cation, one bpbaligand, and 1/2 bdc2- ligand. As shown in Figure 2a, each Co1 cation is five-coordinated with a square-pyramidal geometry, which is formed by four oxygen atoms from two bdc2- and two bpba-, respectively, together with one N atom from one bpbaligand at the apical position. Each pair of Co (II) ions is bridged by four carboxylate groups to generate a paddle-wheel secondary building unit (SBU). As shown in Figure 2b, the SBUs are connected by mixed ligands to furnish a 2D structure. The 2D layers are stacked in a parallel manner, and only one flexible pyridyl part in the bpbaligand takes part in coordination (Figure 2c).

Figure 2 (a) Coordination environment of Co2+ cation in compound 2 with 30% ellipsoid probability, all hydrogen atoms were omitted for clarity (Symmetry code: #1 = 1 - x, 2 - y, - z; #2 = 1 - x, 2 - y, 1 - z). (b) Views of the 2D layers formed by Co2+ cation, bpba- and bdc2- ligands. (c) The representations of parallel stacking of the compound 2.



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Dye Adsorption and Photocatalytic Activity. The dye adsorption and photocatalytic performance of the as-synthesized MOFs 1 and 2 were measured by dye of Methyl orange (MO), Methyl blue (MB), Neutral red (NR), Methylene blue (MEB), and Safranine T (ST) solution at room temperature. The two sets of experiments were run: (a) with MOFs-1 or 2 under dark condition to verify the adsorption; and (b) with MOFs-1 or 2 or H2O2 under UV irradiation to testify the degration. The adsorption experiments were run as follows: 5 mg of MOF-1 or MOF-2 was added to 6 mL 40 ppm dye aqueous solutions under dark condition. At different time intervals, the clear solution after centrifugating was transferred to a quartz cell to measure UV-vis spectra from 300-800 nm. The degration experiments were run as follows: 5 mg of MOFs-1 or 2 was added to 6 mL 40 ppm dye aqueous solution with 30% H2O2 in a glass bottle under UV light for 180 min. During the experiment process, the mixtures were persistently stirred. A 500W Hg lamp was selected as the light source. At the different time, the mixtures were taken out from the reactor and centrifugated. As shown in Figures S3-S7, the declines for absorption peaks of all dyes under the UV light are similar with those under dark light for MOF-1. These results indicated that the main reason for declines of absorption peaks may be contributed to the adsorption for compound 1. The largest amount of NR can be taken up to nearly 100 mg g-1 for 24 hours. And we provided the adsorption kinetics and adsorption isotherms for NR dye with different low concentrations, as shown in Figures 3 and S8. To really prove whether NR molecules can enter the pores of MOF-1 material or only absorb on the surface of MOF-1, the experiment about dye release from NR@1 was investigated. The release for dye molecules in NR@1 is not obvious in saturated NaCl solution or in the deionized water for 30 min. The results shown that the NR molecules are not only absorbed on the surface of MOF-1. The adsorbed quantities of NR dye over MOF-1 is the largest in comparison to the other four dyes which may be attributed to the suitable size of NR and H-bond interaction between the uncoordinated carboxylate groups and NR molecules.


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Figure 3. The adsorption kinetics for NR dye with different low concentrations in MOF-1. As shown in Figures 4-5 and S9-S11, in the presence of 2, the declines for absorption peaks of all dyes under the UV light are more obvious than those under dark light. The photocatalytic activity of dyes increased with time increasing from 0 to 180 min which was confirmed by the decreasing intensity value of the absorption spectra. After 180 min, the photocatalytic efficiencies of MO, MB, NR, MEB, ST were found to be 56%, 95%, 41%, 84%, and 100% for MOF-2, respectively.

Figure 4. The UV-vis absorption spectra of the ST solution and after adsorption and degradation reaction with MOF-2. (Insert) The above and under photographs of ST



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solutions for MOF-2 before and after catalytic degradation, respectively. The left solutions are the same to the right under the dark light as a control experiment.

Figure 5. The UV-vis absorption spectra of the MB solution and after adsorption and degradation reaction with MOF-2. (Insert) The above and under photographs of MB solutions for MOF-2 before and after catalytic degradation, respectively. The left solutions are the same to the right under the dark light as a control experiment. In these dyes, the absorption peaks of MB and ST decreased significantly under UV light. Therefore, we chose MB and ST for compound 2 as representatives to research the process of photo-degradation (Figures S12-13). 10 mg of MOFs-1 or 2 was added to 12 mL 40 ppm dye aqueous solution with 30% H2O2 in a glass bottle under UV light for 300 min. Four groups of experiments were run: (a) with compound 2 and H2O2 under normal condition; (b) with compound 2 and H2O2 under UV light condition; (c) with compound 2 under UV light condition; (d) with H2O2 under UV light condition. The declines for absorption peaks of both dyes were not obvious under visible light, which shows that the catalytic activity is best in the UV light. Absence of compound 2 or H2O2, the declines for absorption peaks did not change significantly, which confirms that catalytic oxidation is a UV light-catalyst-H2O2-dye quaternary system and the color fading for dye molecules is exclusively due to catalytic oxidation. The degradation of ST of MOF-2 in different catalyst concentrations (5mg, 10mg,


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15mg, 20mg, in Figures S14-18) has been achieved. The following degradation experiment was tested: MOF-2 was joined to 12 mL 40 ppm ST aqueous solution with 0.5mL 30% H2O2 in a quartz bottle under a 500W Hg lamp. The clear solution was taken out after 60min, 120min, 180min, 240min and 300min. At each catalyst concentration, plots of the absorption vs time (0-300 min) are given (Figure 6). The results suggested that the different catalyst concentration did not show significant change in the catalytic oxidation. And 15mg of catalyst is slightly better.

Figure 6. Change of absorption of the solution of ST in the presence of 0.5 mL H2O2 with different MOF-2 catalyst concentrations (5mg, 10mg, 15mg, and 20mg) under exposure of UV light at room temperature. The degradation of ST by MOF-2 in different H2O2 concentrations has been conducted (Figures S19-23). The following degradation experiment of was conducted: 10mg MOF-2 was incorporated into 12 mL 40 ppm ST aqueous solution accompanied by H2O2 with different H2O2 concentrations (0.25mL, 0.50mL, 0.75mL, and 1.0mL) in a quartz bottle under a 500W Hg lamp. The clear solution was taken out after 60min, 120min, 180min, 240min and 300min. At each H2O2 concentration, plots of the Abs vs time (0-300 min) are given (Figure 7). The results suggested that the impact for H2O2 concentration in the catalytic oxidation is stronger than that for the concentration of the catalyst. And 1.0 mL of H2O2 concentration is optimal.



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Figure 7. Change of absorption of the solution of ST in the presence of 10 mg MOF-2 with different H2O2 concentrations under exposure of UV light at room temperature. The clear difference between MOF-1 (Cd-II) and MOF-2 (Co-II) is worth noting in the degration experiments. For MOF-1 (Cd-II), in presence of hydrogen peroxide, only a small number of dye molecules appear to have a photo catalytic degradation reaction, which should be due to •OH radicals generated by the hydrogen peroxide. While for MOF-2, the photo catalytic degradation reactions are obvious. By comparing the results, the possible mechanisms are given as follows. The photocatalytic reactions were originated when photocatalyst absorbs photons with energies larger than that of its band gap energy (2.63 eV, Figure S26). Under the irradiation of light, UV light can induce the photocatalyst to generate LMCT, which can be deactivated by oxygenating H2O2 into •OH radicals. Then one electron can be captured from H2O2, which generates •OH radicals. The •OH radicals have a high activity oxidizing and decompose the organic dyes to complete the photodegration process. The mass spectrometry (MS) spectra were run after four hours to certify the products of dye degradation, as shown in Figures S24 and S25. No ST can be found in MS spectra as there is no sign in 350.1. The MB was not completely degraded, which can be found in MS spectra as there was a sign in 798. The complete degraded product may be CO2 and H2O. The reusability of compound 2 was evaluated by 40.0 ppm MB and ST degradation in the presence of H2O2. After each experiment, the MOF-2 was filtered


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and recycled. As shown in Figures S27-28, the catalytic activity of MOF-2 did not show obvious damage and the degradation efficiency was higher than 78% and 99% after three cycles for MB and ST, respectively. To corroborate that the dyes degradation over the catalysts is actually a catalytic process and to prove the MOF-2 is stable, we characterized the PXRD of the fresh catalysts and the ones used for 3 cycles in the dyes degradation experiment. We found the PXRD pattern of 2 remains unchanged, as shown in Figure S29. The results demonstrated that 2 may be recycled for the catalytic degration of dye molecules and treatment with waste water.

CONCLUSIONS In summary, two new MOFs based flexible pyridyl-carboxylate ligands have been synthesized solvothermally, characterized and used to treat wastewater. The flexible pyridyl parts may provide an extension of the structure. Compound 1 is a three dimesional net with a rare jea topology. For compound 2, one flexible pyridyl arm is not involved in coordination, each Co (II) paddle-wheel unit is connected by mixed ligands to furnish a 2D layer. The results about heterogeneous catalytic oxidation activities toward MO, MB, NR, MEB, and ST in the presence of H2O2 show that the absorption is dominant in compound 1. However, in compound 2, the photodegradation is dominant and degradation efficiency is one hundred percent for ST within 3 hours.

ASSOCIATED CONTENT Supplementary information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/ Crystallographic data for 1 in CIF format (CIF) Crystallographic data for 2 in CIF format (CIF) AUTHOR INFORMATION Corresponding Author: [email protected] ACKNOWLEDGMENTS



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We would like to kindly acknowledge the National Natural Science Foundation of China (No. 21601045, 21371092), and National Basic Research Program of China (2010CB923303),

and

China

Postdoctoral

Fund

(2016M601768),

and the

Fundamental Research Funds for the Central Universities (JZ2016HGTA0679).

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(47) Qin, L.; Hu, J. S.; Zhang, M. D.; Li, Y. Z.; Zheng, H. G. CrystEngComm 2012, 14, 8274-8279. (48) Blatov, V. A.; Shevchenko, A. P.; Serezhkin, V. N. J. Appl. Crystallogr. 2000, 33, 1193. (49) See the Web Page in RCSR: http://rcsr.net/nets/jea. (50) Qin, J. S.; Du, D. Y.; Li, M.; Lian, X. Z.; Dong, L. Z.; Bosch, M.; Su, Z. M.; Zhang, Q.; Li, S. L.; Lan, Y. Q.; Yuan, S.; Zhou, H. C. J. Am. Chem. Soc. 2016, 138, 5299-5307.



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Photodegradation of Some Organic Dyes over Two Metal-Organic Frameworks Especially High Efficiency for Safranine T Ling Qin†,‡, Hong-Zhe Chen†, Jiang Lei†, Yan-Qing Wang†, Tong-Qi Ye†, and He-Gen Zheng‡,*

Two new networks have been synthesized hydrothermally and characterized. Compound 1 is a 3D net with a rare jea topology. The flexible pyridyl arms are not involved in coordination, which generated the 2D layer 2. In addition, their heterogeneous catalytic oxidation activities toward Methyl orange (MO), Methyl blue (MB), Neutral red (NR), Methylene blue (MEB), and Safranine T (ST) in the presence of H2O2 were investigated in aqueous solution. The results suggested that the photocatalytic efficiencies of ST were found to be 100% for MOF-2.


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Photodegradation of Some Organic Dyes over Two MetalâOrganic

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Photodegradation of Some Organic Dyes over Two MetalâOrganic