Novel sulfhydryl functionalized covalent organic frameworks for ultra-trace Hg2+ removal from aqueous solution

doi:10.1016/j.jmst.2021.04.013

J. Mater. Sci. Technol. ›› 2021, Vol. 93: 89-95.DOI: 10.1016/j.jmst.2021.04.013

• Original article • Previous Articles Next Articles

Novel sulfhydryl functionalized covalent organic frameworks for ultra-trace Hg²⁺ removal from aqueous solution

Fei Pan^a^,^b^,^c, Chunyi Tong^a, Zhaoyang Wang^a, Fenghua Xu d, Xiaofei Wang^e, Baicheng Weng^d^,^*(), Dawei Pan b, Rilong Zhu^a^,^*()

^aCollege of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha, 410082, PR China
^bCAS Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Shandong Key Laboratory of Coastal Environmental Processes, Research Center for Coastal Environment Engineering Technology of Shandong Province, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, PR China
^cUniversity of Chinese Academy of Sciences, Beijing, 100049, PR China
^dCollege of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, PR China
^eSchool of Environmental Science and Engineering, Hubei Polytechnic University, Huangshi, 435003, PR China

Accepted:2021-02-05 Published:2021-12-10 Online:2021-12-10
Contact: Baicheng Weng,Rilong Zhu
About author:zrlden@hnu.edu.cn (R. Zhu).
dwpan@yic.ac.cn (D. Pan),
*E-mail addresses: baichengweng@hotmail.com (B. Weng),

Abstract

Abstract:

Two kinds of novel sulfhydryl functionalized covalent organic frameworks were fabricated as adsorbents for the removal of ultra-trace concentrations of Hg²⁺from water. The two kinds of sulfhydryl functionalized covalent organic frameworks were obtained via a thiol-ene click reaction between the thiol groups of trithiocyanuric acid (TTC) or bismuththiol (BMT) and vinyl groups on the surface of covalent organic frameworks. The material structure was characterized by XRD, SEM, EDS, FT-IR, BET, and TG analysis. Due to their rich sulfur content, both adsorbents (COF-SH-1 and COF-SH-2) exhibited a high level of selective Hg²⁺ removal from aqueous solution with maximum adsorption capacities of 763.4 mg g^-1 and 526.3 mg g^-1, respectively. Furthermore, in the presence of ultra-low concentrations of Hg²⁺ both materials exhibited excellent performance, achieving rapid Hg²⁺ removal at concentrations from 10 μg L^-1 to less than 0.02 ng L^-1. Analysis of the adsorption mechanism indicates that the sulfur containing chelating groups exhibit a strong binding capacity for Hg²⁺. Results show that the structure determines the performance, with the amount of adsorption sites being related to the adsorption capacity. Therefore, as sulfhydryl functionalized covalent organic frameworks contain an abundance of adsorption sites, these materials can effectively achieve the removal of ultra-low trace Hg²⁺ concentrations and have promising future application potential for the environmental detection of heavy metals.

Key words: Sulfhydryl-functionalized, Covalent organic framework, Ultra-trace adsorption, Mercury adsorption

Fei Pan, Chunyi Tong, Zhaoyang Wang, Fenghua Xu d, Xiaofei Wang, Baicheng Weng, Dawei Pan b, Rilong Zhu. Novel sulfhydryl functionalized covalent organic frameworks for ultra-trace Hg²⁺ removal from aqueous solution[J]. J. Mater. Sci. Technol., 2021, 93: 89-95.

Figures/Tables 10

Fig. 1. Synthesis routes for the preparation of COF-SH-1 and COF-SH-2.

Fig. 2. SEM images of COF-V (a), COF-SH-1 (b) and COF-SH-2 (c); EDS spectra of COF-V, COF-SH-1 and COF-SH-2 (d).

Fig. 3. XRD spectra patterns for COF-V, COF-SH-1, COF-SH-2, and simulation.

Fig. 4. (a) Adsorption isotherm curves for Hg2+ on COF-SH-1 and COF-SH-2, (b) Freundlich model fitting for COF-SH-1 and COF-SH-2 and (c) Langmuir model fitting for COF-SH-1 and COF-SH-2.

Table 1. Comparison of the selective adsorption of Hg2+ by COF-SH-1 and COF-SH-2 with other previously reported adsorbents.

Adsorbents	Adsorption capacities
COF-LZU8	236 mg g^-1	[35]
MPTs-modified TO NFC	718.5 mg/g	[27]
COF-S-SH	1350 mg g^-1	[36]
ZSM-5	173 mg g^-1	[37]
SH-MiL-68(In)	450 mg g^-1	[38]
M-DAPS₅₀ COF-SH	383 mg g^-1	[39]
COF-SH-1	763.4 mg g^-1	This work
COF-SH-2	526.3 mg g^-1	This work

Fig. 5. (a) Adsorption kinetics curves for Hg2+ on COF-SH-1 and COF-SH-2, (b) pseudo-first-order kinetic model results and (c) pseudo-second-order kinetic model results.

Fig. 6. (a) Adsorption kinetics curves for Hg2+ at a low Hg2+ concentration of 10 μg L-1 for COF-SH-1 (a) and COF-SH-2 (c), respectively. Pseudo-second-order kinetics for COF-SH-(b) and COF-SH-2 (d), respectively.

Fig. 7. Selectivity of COF-SH-1and COF-SH-2 for Hg2+ in the presence of coexisting metal ions.

Fig. 8. EDS spectra of COF-SH-1 and COF-SH-2 after adsorption of Hg2+ from solution.

Fig. 9. XPS spectra of (a) N 1 s, (b) S 2p and (c) Hg 4f, of COF-SH-2 and Hg-loaded COF-SH-2, respectively.

References 39

[1]	D.S. Sholl, R.P. Lively, Nature, 532(2016), pp. 6-9.
[2]	H. He, X. Meng, Q. Yue, W. Yin, Y. Gao, P. Fang, L. Shen, Chem. Eng. J., 405(2021), Article 126743.
[3]	H. Han, M. Khalid, T. Zhou, R. Xu, J. Hazard. Mater., 369(2019), pp. 780-796.
[4]	R.S. Smith, J.G. Wiederhold, R. Kretzschmar, Environ. Sci. Technol., 49(2015), pp. 4325-4334.
[5]	Q. Zhang, N. Liu, Y. Cao, W. Zhang, Y. Wei, L. Feng, L. Jiang, Appl. Surf. Sci., 434(2018), pp. 57-62.
[6]	X. Zhao, J. Li, S. Mu, W. He, D. Zhang, X. Wu, C. Wang, H. Zeng, Environ. Pollut., 268(2021), Article 115705.
[7]	P. Qiu, S. Wang, C. Tian, Z. Lin, Environ. Pollut., 252(2019), pp. 1133-1141.
[8]	D. An, X. Sun, X. Cheng, L. Cui, X. Zhang, Y. Zhao, Y. Dong, J. Hazard. Mater., 384(2020), Article 121354.
[9]	S. Wu, P. Yan, W. Yu, K. Cheng, H. Wang, W. Yang, J. Zhou, J. Xi, J. Qiu, S. Zhu, L. Che, Fuel Process. Technol., 196(2019), Article 106167.
[10]	C.J. Hsu, Y.Z. Xiao, H.C. Hsi, Chemosphere, 263(2021), Article 127966.
[11]	H. Sadegh, G.A.M. Ali, A.S.H. Makhlouf, K.F. Chong, N.S. Alharbi, S. Agarwal, V.K. Gupta, J. Mol. Liq., 258(2018), pp. 345-353.
[12]	L. Li, X. Wang, H. Fu, X. Qu, J. Chen, S. Tao, D. Zhu, Environ. Sci. Technol., 54(2020), pp. 11137-11145.
[13]	A.J. Tchinda, E. Ngameni, I.T. Kenfack, A. Walcarius, Chem. Mater., 21(2009), pp. 4111-4121.
[14]	H. Shirzadi, A. Nezamzadeh-Ejhieh, J. Mol. Liq., 230(2017), pp. 221-229.
[15]	P.J. Waller, F. Gándara, O.M. Yaghi, Acc. Chem. Res., 48(2015), pp. 3053-3063.
[16]	X. Li, C. Yang, B. Sun, S. Cai, Z. Chen, Y. Lv, J. Zhang, Y. Liu, J. Mater. Chem. A., 8(2020), pp. 16045-16060.
[17]	G. Li, J. Ye, Q. Fang, F. Liu, Chem. Eng. J., 370(2019), pp. 822-830.
[18]	Z. Wang, S. Zhang, Y. Chen, Z. Zhang, S. Ma, Chem. Soc. Rev., 49(2020), pp. 708-735.
[19]	A.M. Khattak, Z.A. Ghazi, B. Liang, N.A. Khan, A. Iqbal, L. Li, Z. Tang, J. Mater. Chem. A., 4(2016), pp. 16312-16317.
[20]	A.F.M. El-Mahdy, C. Young, J. Kim, J. You, Y. Yamauchi, S.W. Kuo, ACS Appl. Mater. Interfaces., 11(2019), pp. 9343-9354.
[21]	H. Hu, Q. Yan, M. Wang, L. Yu, W. Pan, B. Wang, Y. Gao, Cuihua Xuebao/Chinese J. Catal., 39(2018), pp. 1437-1444.
[22]	Y. Zhang, W. Zhang, Q. Li, C. Chen, Z. Zhang, Sensors Actuators, B Chem, 324(2020), Article 128733.
[23]	Y. Yusran, X.Y. Guan, H. Li, Q.R. Fang, S.L. Qiu, Natl Sci Rev, 7(2020), pp. 170-190.
[24]	J.L. Wang, S.T. Zhuang, Coord Chem Rev, 400(2019), Article 213046.
[25]	Q.Y. Lu, Y.C. Ma, H. Li, X.Y. Guan, Y. Yusran, M. Xue, Q.R. Fang, Y.S. Yan, S.L. Qiu, V. Valtchev, Angew. Chem. Int. Ed., 57(2018), pp. 6042-6048.
[26]	K. Chen, Z. Zhang, K. Xia, X. Zhou, Y. Guo, T. Huang, ACS Omega, 4(2019), pp. 8568-8579.
[27]	B. Geng, H. Wang, S. Wu, J. Ru, C. Tong, Y. Chen, H. Liu, S. Wu, X. Liu, A.C.S. Sustain, Chem. Eng., 5(2017), pp. 11715-11726.
[28]	Y. Shen, N. Jiang, S. Liu, C. Zheng, X. Wang, T. Huang, Y. Guo, J. Environ. Chem. Eng., 6(2018), pp. 5420-5433.
[29]	Y. Li, T. Hu, R. Chen, R. Xiang, Q. Wang, Y. Zeng, C. He, Chem. Eng. J., 398(2020), Article 125566.
[30]	M. Heidari, K. Ghanemi, Y. Nikpour, Ecotoxicol. Environ. Saf., 203(2020), Article 110995.
[31]	N. Osaka, M. Ishitsuka, T. Hiaki, J. Mol. Struct., 921(2009), pp. 144-149.
[32]	S. Shinkai, H. Kawaguchi, O. Manabe, Journal of Polymer Science Part C Polymer Letters, 26(1988), pp. 391-396.
[33]	P. Lessi, N.L. Dias Filho, J.C. Moreira, J.T.S. Campos, Anal. Chim. Acta., 327(1996), pp. 183-190.
[34]	R. Qu, C. Wang, C. Sun, C. Ji, G. Cheng, X. Wang, G. Xu, J. Appl. Polym. Sci., 92(2004), pp. 1646-1652.
[35]	S.Y. Ding, M. Dong, Y.W. Wang, Y.T. Chen, H.Z. Wang, C.Y. Su, W. Wang, J. Am. Chem. Soc., 138(2016), pp. 3031-3037.
[36]	Q. Sun, B. Aguila, J. Perman, L.D. Earl, C.W. Abney, Y. Cheng, H. Wei, N. Nguyen, L. Wojtas, S. Ma, J. Am. Chem. Soc., 139(2017), pp. 2786-2793.
[37]	K. Abbas, H. Znad, M.R. Awual, Chem. Eng. J., 334(2018), pp. 432-443.
[38]	G.P. Li, K. Zhang, P.F. Zhang, W.N. Liu, W.Q. Tong, L. Hou, Y.Y. Wang, Inorg. Chem., 58(2019), pp. 3409-3415.
[39]	L. Huang, R. Shen, R. Liu, Q. Shuai, J. Hazard. Mater., 392(2020), Article 122320.

Novel sulfhydryl functionalized covalent organic frameworks for ultra-trace Hg²⁺ removal from aqueous solution

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