Hierarchical porous MgBO2(OH) microspheres: Hydrothermal synthesis, thermal decomposition, and application as adsorbents for Congo red removal

doi:10.1016/j.cjche.2018.01.013

Abstract

Abstract: A facile eco-friendly hydrothermal route (180℃, 12.0 h) has been developed for the first time to the uniform hierarchical porous MgBO₂(OH) microspheres without the aid of any organic additive, surfactant or template, by using the abundant MgCl₂·6H₂O, H₃BO₃ and NaOH as the raw materials. The as-obtained porous microspheres exhibit a specific surface area of 94.752 mg·g^-1, pore volume of 0.814 cm³·g^-1, and ca. 84.0% of which have a diameter of 2.25-3.40 μm. The thermal decomposition of the porous MgBO₂(OH) microspheres (650℃, 2.5℃·min^-1) leads to the porous Mg₂B₂O₅ microspheres with well-retained morphology. When utilized as the adsorbents for the removal of CR from mimic waste water, the present porous MgBO₂(OH) microspheres exhibit satisfactory adsorption capacity, with the maximum adsorption capacity q_m of 309.1 mg·g^-1, much higher than that derived from most of the referenced adsorbents. This opens a new window for the facile green hydrothermal synthesis of the hierarchical porous MgBO₂(OH) microspheres, and extends the potential application of the 3D hierarchical porous metal borates as high-efficiency adsorbents for organic dyes removal.

Key words: Hierarchical porous microspheres, Magnesium borate hydroxide, Adsorption, Congo red, Hydrothermal

摘要： A facile eco-friendly hydrothermal route (180℃, 12.0 h) has been developed for the first time to the uniform hierarchical porous MgBO₂(OH) microspheres without the aid of any organic additive, surfactant or template, by using the abundant MgCl₂·6H₂O, H₃BO₃ and NaOH as the raw materials. The as-obtained porous microspheres exhibit a specific surface area of 94.752 mg·g^-1, pore volume of 0.814 cm³·g^-1, and ca. 84.0% of which have a diameter of 2.25-3.40 μm. The thermal decomposition of the porous MgBO₂(OH) microspheres (650℃, 2.5℃·min^-1) leads to the porous Mg₂B₂O₅ microspheres with well-retained morphology. When utilized as the adsorbents for the removal of CR from mimic waste water, the present porous MgBO₂(OH) microspheres exhibit satisfactory adsorption capacity, with the maximum adsorption capacity q_m of 309.1 mg·g^-1, much higher than that derived from most of the referenced adsorbents. This opens a new window for the facile green hydrothermal synthesis of the hierarchical porous MgBO₂(OH) microspheres, and extends the potential application of the 3D hierarchical porous metal borates as high-efficiency adsorbents for organic dyes removal.

关键词: Hierarchical porous microspheres, Magnesium borate hydroxide, Adsorption, Congo red, Hydrothermal

Panpan Sun, Liyuan Chen, Lin Xu, Wancheng Zhu. Hierarchical porous MgBO₂(OH) microspheres: Hydrothermal synthesis, thermal decomposition, and application as adsorbents for Congo red removal[J]. Chin.J.Chem.Eng., 2018, 26(7): 1561-1569.

References

[1] X.H. Wang, J.J. Ding, S.W. Yao, X.X. Wu, Q.Q. Feng, Z.H. Wang, B.Y. Geng, High supercapacitor and adsorption behaviors of flower-like MoS₂ nanostructures, J. Mater. Chem. A 2(38) (2014) 15958-15963.

[2] P.P. Sun, L. Xu, J. Li, P.Y. Zhai, H. Zhang, Z.S. Zhang, W.C. Zhu, Hydrothermal synthesis of mesoporous Mg₃Si₂O₅(OH)₄ microspheres as high-performance adsorbents for dye removal, Chem. Eng. J. 334(2018) 377-388.

[3] Z.Q. Zhang, W.C. Zhu, R.G. Wang, L.L. Zhang, L. Zhu, Q. Zhang, Ionothermal confined self-organization for hierarchical porous magnesium borate superstructures as highly efficient adsorbents for dye removal, J. Mater. Chem. A 2(45) (2014) 19167-19179.

[4] Z.Q. Zhang, H. Zhang, L. Zhu, Q. Zhang, W.C. Zhu, Hierarchical porous Ca(BO₂)₂ microspheres:Hydrothermal-thermal conversion synthesis and their applications in heavy metal ions adsorption and solvent-free oxidation of benzyl alcohol, Chem. Eng. J. 283(2016) 1273-1284.

[5] L.L. Zhang, W.C. Zhu, H. Zhang, S.W. Bi, Q. Zhang, Hydrothermal-thermal conversion synthesis of hierarchical porous MgO microrods as efficient adsorbents for lead (Ⅱ) and chromium (VI) removal, RSC Adv. 4(58) (2014) 30542-30550.

[6] W.Q. Cai, J.G. Yu, M. Jaroniec, Template-free synthesis of hierarchical spindle-like γ-Al₂O₃ materials and their adsorption affinity towards organic and inorganic pollutants in water, J. Mater. Chem. 20(22) (2010) 4587-4594.

[7] Z.H. Wei, R.G. Xing, X. Zhang, S. Liu, H.H. Yu, P.C. Li, Facile template-free fabrication of hollow nestlike α-Fe₂O₃ nanostructures for water treatment, ACS Appl. Mater. Interfaces 5(3) (2012) 598-604.

[8] Y. Zeng, T. Zhang, L.J. Wang, R. Wang, Synthesis and ethanol sensing properties of selfassembled monocrystalline ZnO nanorod bundles by poly (ethylene glycol)-assisted hydrothermal process, J. Phys. Chem. C 113(9) (2009) 3442-3448.

[9] W.C. Zhu, Q. Zhang, L. Xiang, F. Wei, X.T. Sun, X.L. Piao, S.L. Zhu, Flux-assisted thermal conversion route to pore-free high crystallinity magnesium borate nanowhiskers at a relatively low temperature, Cryst. Growth Des. 8(8) (2008) 2938-2945.

[10] Y. Li, Z.Y. Fan, J.G. Lu, R.P.H. Chang, Synthesis of magnesium borate (Mg₂B₂O₅) nanowires by chemical vapor deposition method, Chem. Mater. 16(2004) 2512-2514.

[11] B.S. Xu, T.B. Li, Y. Zhang, Z.X. Zhang, X.G. Liu, J.F. Zhao, New synthetic route and characterization of magnesium borate nanorods, Cryst. Growth Des. 8(4) (2011) 1218-1222.

[12] J. Liu, Y. Li, X. Huang, Z. Li, G. Li, H. Zeng, Hydrothermal synthesis of single-crystal szaibelyite MgBO₂(OH) nanobelt as a new host material for red-emitting rare-earth ions, Chem. Mater. 39(15) (2008) 250-257.

[13] R.Z. Ma, Y.S. Bando, D. Golberg, T.D. Sato, Nanotubes of magnesium borate, Angew. Chem. Int. Ed. 42(2003) 1836-1838.

[14] R. Ma, Y. Bando, T. Sato, Nanowires of metal borates, Appl. Phys. Lett. 81(18) (2002) 3467-3469.

[15] W.C. Zhu, G.D. Li, Q. Zhang, L. Xiang, S.L. Zhu, Hydrothermal mass production of MgBO₂(OH) nanowhiskers and subsequent thermal conversion to Mg₂B₂O₅ nanorods for biaxially oriented polypropylene resins reinforcement, Powder Technol. 203(2) (2010) 265-271.

[16] Y. Zeng, H. Yang, W. Fu, Q. Liang, L. Chang, J. Chen, Synthesis of magnesium borate (Mg₂B₂O₅) nanowires, growth mechanism and their lubricating properties, Mater. Res. Bull. 43(8-9) (2008) 2239-2247.

[17] W.C. Zhu, Q. Zhang, L. Xiang, S.L. Zhu, Green co-precipitation byproduct-assisted thermal conversion route to submicron Mg₂B₂O₅ whiskers, CrystEngComm 13(5) (2011) 1654-1663.

[18] X.Y. Tao, X.D. Li, Catalyst-free synthesis, structural, and mechanical characterization of twinned Mg₂B₂O₅ nanowires, Nano Lett. 8(2) (2008) 505.

[19] A.M. Chen, P. Gu, Z.M. Ni, 3D flower-like magnesium borate microspheres assembled by nanosheets synthesized via PVP-assisted method, Mater. Lett. 68(1) (2012) 187-189.

[20] A.M. Chen, P. Gu, J. Hu, A new mesoporous magnesium borate microsphere synthesized using sodium dodecyl sulfate as template, Adv. Mater. Res. 486(2012) 260-264.

[21] Z.H. Liu, L. Xue, Preparation of nanoplates assembled 4CaO·5B₂O₃·7H₂O oval-like microspheres via a hydrothermal method, Mater. Lett. 62(17-18) (2008) 2692-2695.

[22] W.C. Zhu, X.L. Wang, X. Zhang, H. Zhang, Q. Zhang, Hierarchical laminar superstructures of rhombic priceite (Ca₄B₁₀O₁₉·7H₂O):facile hydrothermal synthesis, shape evolution, optical, and thermal decomposition properties, Cryst. Growth Des. 11(7) (2011).

[23] C. Reichardt, Solvents and solvent effects:An introduction, Org. Process. Res. Dev. 11(1) (2007) 105-113.

[24] W.C. Zhu, L. Xiang, T.B. He, S.L. Zhu, Hydrothermal synthesis and characterization of magnesium borate hydroxide nanowhiskers, Chem. Lett. 35(10) (2006) 1158-1159.

[25] K. Latha, W.Z. Li, K. Shrinivas, K.H. Wu, C. Wei, C. Wang, Effect of surfactants on the structure and morphology of magnesium borate hydroxide nanowhiskers synthesized by hydrothermal route, Nanoscale Res. Lett. 5(1) (2009) 149-157.

[26] R.X. Chen, J.G. Yu, W. Xiao, Hierarchically porous MnO₂ microspheres with enhanced adsorption performance, J. Mater. Chem. A 1(38) (2013) 11682-11690.

[27] Y.S. Yang, Q.Z. Wu, M. Wang, J. Long, Z. Mao, X.H. Chen, Hydrothermal synthesis of hydroxyapatite with different morphologies:Influence of supersaturation of the reaction system, Cryst. Growth Des. 14(9) (2014) 4864-4871.

[28] J.B. Zhou, S.L. Yang, J.G. Yu, Facile fabrication of mesoporous MgO microspheres and their enhanced adsorption performance for phosphate from aqueous solutions, Colloids Surf. A Physicochem. Eng. Asp. 379(2011) 102-108.

[29] K.Y. Foo, B.H. Hameed, Insights into the modeling of adsorption isotherm systems, Chem. Eng. J. 156(1) (2010) 2-10.

[30] B. Wang, H.B. Wu, L. Yu, R. Xu, T.T. Lim, X.W. Lou, Template-free formation of uniform urchin-like α-FeOOH hollow spheres with superior capability for water treatment, Adv. Mater. 24(8) (2012) 1111-1116.

[31] J.R. Gao, W. Wei, M.J. Shi, H.K. Han, J.W. Lu, J.M. Xie, A controlled solvethermal approach to synthesize nanocrystalline iron oxide for Congo red adsorptive removal from aqueous solutions, J. Mater. Sci. 51(9) (2016) 4481-4494.

[32] J.C. Hu, Z. Song, L.F. Chen, H.J. Yang, J.L. Li, R. Richards, Adsorption properties of MgO (111) nanoplates for the dye pollutants from wastewater, J. Chem. Eng. Data 55(9) (2010) 3742-3748.

[33] J. Zhang, B. Yao, H. Ping, Z.Y. Fu, Y. Li, W.M. Wang, J.Y. Zhang, F. Zhang, Template-free synthesis of hierarchical porous calcium carbonate microsphere for efficient water treatment, RSC Adv. 6(1) (2015) 472-480.

[34] N. Chaukura, B.B. Mamba, S.B. Mishra, Conversion of post consumer waste polystyrene into a high value adsorbent and its sorptive properties for Congo red removal from aqueous solution, J. Environ. Manag. 193(2017) 280-289.

[35] X.H. Lu, D.Z. Zheng, M. Xu, Y.Y. Huang, S.L. Xie, Z.Q. Liu, General electrochemical assembling to porous nanowires with high adaptability to water treatment, CrystEngComm 13(7) (2011) 2451-2456.

[36] J. Li, N. Zhang, D.H.L. Ng, Synthesis of a 3D hierarchical structure of γ-AlO(OH)/Mg-AlLDH/C and its performance in organic dyes and antibiotics adsorption, J. Mater. Chem. A 3(42) (2015) 21106-21115.

[37] J. Li, L. Xu, P.P. Sun, P.Y. Zhai, X.P. Chen, H. Zhang, Z.S. Zhang, W.C. Zhu, Novel application of red mud:Facile hydrothermal-thermal conversion synthesis of hierarchical porous AlOOH and Al₂O₃ microspheres as adsorbents for dye removal, Chem. Eng. J. 321(2017) 622-634.

Hierarchical porous MgBO₂(OH) microspheres: Hydrothermal synthesis, thermal decomposition, and application as adsorbents for Congo red removal

Hierarchical porous MgBO₂(OH) microspheres: Hydrothermal synthesis, thermal decomposition, and application as adsorbents for Congo red removal

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Yingli Li, Zhishuncheng Li, Guangfei Qu, Rui Li, Shuaiyu Liang, Junhong Zhou, Wei Ji, Huiming Tang. Mechanism, behaviour and application of iron nitrate modified carbon nanotube composites for the adsorption of arsenic in aqueous solutions [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 26-36.
[2]	Jing Huang, Honghui Cai, Qian Zhao, Yunpeng Zhou, Haibo Liu, Jing Wang. Dual-functional pyrene implemented mesoporous silicon material used for the detection and adsorption of metal ions [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 108-117.
[3]	Xia Miao, Xiaofan Pang, Shiyu Li, Haoguang Wei, Jianhao Yin, Xiangming Kong. Mechanical strength and the degradation mechanism of metakaolin based geopolymer mixed with ordinary Portland cement and cured at high temperature and high relative humidity [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 118-130.
[4]	Lingli Chen, Yueting Shi, Sijun Xu, Junle Xiong, Fang Gao, Shengtao Zhang, Hongru Li. Enhanced adsorption of target branched compounds including antibiotic norfloxacin frameworks on mild steel surface for efficient protection: An experimental and molecular modelling study [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 212-227.
[5]	Alexander Nti Kani, Evans Dovi, Aaron Albert Aryee, Runping Han, Zhaohui Li, Lingbo Qu. Mechanisms and reusability potentials of zirconium-polyaziridine-engineered tiger nut residue towards anionic pollutants [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 275-292.
[6]	Yuan Liu, Hanting Xiong, Jingwen Chen, Shixia Chen, Zhenyu Zhou, Zheling Zeng, Shuguang Deng, Jun Wang. One-step ethylene separation from ternary C₂ hydrocarbon mixture with a robust zirconium metal-organic framework [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 9-15.
[7]	Hui Jiang, Zijian Zhao, Ning Yu, Yi Qin, Zhengwei Luo, Wenhua Geng, Jianliang Zhu. Synthesis, characterization, and performance comparison of boron using adsorbents based on N-methyl-D-glucosamine [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 16-31.
[8]	Runze Chen, Yuran Chen, Xuemin Liang, Yapeng Kong, Yangyang Fan, Quan Liu, Zhenyu Yang, Feiying Tang, Johnny Muya Chabu, Maru Dessie Walle, Liqiang Wang. Oxidative exfoliation of spent cathode carbon: A two-in-one strategy for its decontamination and high-valued application [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 262-269.
[9]	Shanghong Ma, Haitao Zhang, Jianbo Qu, Xiuzhong Zhu, Qingfei Hu, Jianyong Wang, Peng Ye, Futao Sai, Shiwei Chen. Preparation of waterborne polyurethane/β-cyclodextrin composite nanosponge by ion condensation method and its application in removing of dyes from wastewater [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 124-136.
[10]	Yueting Shi, Junhai Zhao, Lingli Chen, Hongru Li, Shengtao Zhang, Fang Gao. Double open mouse-like terpyridine parts based amphiphilic ionic molecules displaying strengthened chemical adsorption for anticorrosion of copper in sulfuric acid solution [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 233-246.
[11]	Jian Wang, Yuanhui Shen, Donghui Zhang, Zhongli Tang, Wenbin Li. Integrated vacuum pressure swing adsorption and Rectisol process for CO₂ capture from underground coal gasification syngas [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 265-279.
[12]	Yujia Cui, Zhiqiang Tan, Yanan Wang, Shuxian Shi, Xiaonong Chen. One-step crosslinking preparation of tannic acid particles for the adsorption and separation of cationic dyes [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 309-318.
[13]	Shanshan Mao, Tao Shen, Qing Zhao, Tong Han, Fan Ding, Xin Jin, Manglai Gao. Selective capture of silver ions from aqueous solution by series of azole derivatives-functionalized silica nanosheets [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 319-328.
[14]	Bingxiao Feng, Lining Hao, Chaoting Deng, Jiaqiang Wang, Hongbing Song, Meng Xiao, Tingting Huang, Quanhong Zhu, Hengjun Gai. A highly hydrothermal stable copper-based catalyst for catalytic wet air oxidation of m-cresol in coal chemical wastewater [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 338-348.
[15]	Lianlian Zhao, Fufu Di, Xiaonan Wang, Sumbal Farid, Suzhen Ren. Constructing a hollow core-shell structure of RuO₂ wrapped by hierarchical porous carbon shell with Ru NPs loading for supercapacitor [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 93-100.