用于水中有机污染物处理的Co3O4/TiO2/多孔炭复合材料

doi:10.16085/j.issn.1000-6613.2020-2303

摘要/Abstract

摘要：

具有高吸附、强降解、易回收特性的新型功能材料在治理水中有机污染物上具有广泛的应用前景。本研究以多孔Ti基MOF材料NH₂-MIL-125(Ti)为前体，通过后修饰方法在孔洞中引入Co²⁺，再通过高温炭化制备得到Co₃O₄/TiO₂/多孔炭复合材料，并通过多种手段对复合材料进行了表征。实验用甲基橙模拟水中有机污染物，研究了复合材料对甲基橙的吸附性能、光催化降解性能及回收再利用能力。研究结果表明复合材料对甲基橙的吸附过程符合准二级动力学方程，其吸附能力随着复合材料中Co₃O₄含量先增加后减小，C120（5.23% Co₃O₄/48.72%TiO₂/多孔炭）具有最强的平衡吸附量，达到273.22mg/g_sample。同时该样品对甲基橙也具有较强的光催化降解能力，并且由于Co₃O₄的强磁性，可以很容易地通过外磁场从水中分离。本工作为应用于有机废水处理的新型功能材料的开发提供了实验依据。

关键词: 复合材料, 吸附, 降解, 回收

Abstract:

Multifunctional materials with high adsorption ability, remarkable photocatalytic property, and easy recycle have a great potential in organic wastewater treatment. In this study, a multifunctional composite, Co₃O₄/TiO₂/porous carbon, was prepared through a three-steps process. Firstly, the porous MOF NH₂-MIL-125(Ti) was synthesized. Secondly, Co²⁺ ions were introduced into the pores of NH₂-MIL-125(Ti). And finally, the Co²⁺ embedded MOFs was pyrolyzed to transform into the composites. The composites were characterized by different methods. Methyl orange (MO) was then used as model organic pollutant to investigate the adsorption ability, photocatalytic property and recyclability of Co₃O₄/TiO₂/porous carbon. The results showed that the adsorption of MO on the composite was fitted well with a pseudo-second-order kinetic model. The equilibrium adsorption capacities of MO increased at first and then decreased with the increase of the amount of Co₃O₄ in the composites. The sample C120 exhibited the highest equilibrium adsorption capacities of MO (273.22mg/g_sample). Meanwhile, C120 exhibited strong photocatalytic ability, and can be easily separated from water by external magnetic field. This work provides a significant experimental basis for the development of new functional materials for organic wastewater treatment.

Key words: composites, adsorption, degradation, recovery

中图分类号:

TB333

张书泉, 徐敏, 王国滔. 用于水中有机污染物处理的Co₃O₄/TiO₂/多孔炭复合材料[J]. 化工进展, 2021, 40(8): 4600-4609.

ZHANG Shuquan, XU Min, WANG Guotao. Co₃O₄/TiO₂/porous carbon for organic wastewater treatment[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4600-4609.

图/表 17

参考文献 37

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样品	合成时加入的NH₂-MIL-125（Ti）质量/mg	合成时加入的Co（NO₃）₂·6H₂O质量/mg	实测样品中TiO₂的质量分数/%	实测样品中Co₃O₄的质量分数/%
C0	800	0	52.48	0
C80	800	80	49.66	3.49
C120	800	120	48.72	5.23
C160	800	160	48.87	6.91
C200	800	200	46..69	8.56
C240	800	240	45.73	9.87

样品	合成时加入的NH₂-MIL-125（Ti）质量/mg	合成时加入的Co（NO₃）₂·6H₂O质量/mg	实测样品中TiO₂的质量分数/%	实测样品中Co₃O₄的质量分数/%
C0	800	0	52.48	0
C80	800	80	49.66	3.49
C120	800	120	48.72	5.23
C160	800	160	48.87	6.91
C200	800	200	46..69	8.56
C240	800	240	45.73	9.87

样品	比表面积/m²?g^-1	孔容/cm³?g^-1
C0	298	0.217
C80	238	0.172
C120	279	0.213
C160	247	0.190
C200	230	0.154

样品	比表面积/m²?g^-1	孔容/cm³?g^-1
C0	298	0.217
C80	238	0.172
C120	279	0.213
C160	247	0.190
C200	230	0.154

样品	甲基橙的平衡吸附量q_e/mg·g^-1_sample	吸附速率常数k₂/g_sample·mg^-1·min^-1	相关系数R²/%
C80	252.53	2.91×10^-3	99.7
C120	273.22	2.55×10^-3	99.9
C160	253.81	2.91×10^-3	99.9
C200	164.47	6.50×10^-3	99.5
C240	144.09	8.16×10^-3	99.7

用于水中有机污染物处理的Co₃O₄/TiO₂/多孔炭复合材料

Co₃O₄/TiO₂/porous carbon for organic wastewater treatment

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参考文献 37

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吸附剂	甲基橙的平衡吸附量q_e/mg·g^-1_sample	吸附条件	参考文献
Ni/多孔炭/碳纳米管	271	5mg吸附剂于10mL MO水溶液（20~350mg·L^-1）；吸附时间60min；吸附温度室温	［23］
（Fe₂O₃，Fe₃C，Fe）@多孔炭	183	10mg吸附剂于20mL MO水溶液（12.5~400mg·L^-1）；吸附时间90min；吸附温度室温	［24］
ZnFe₂O₄/木质素衍生炭	113	20mg吸附剂于20mL MO水溶液（20~180mg·L^-1）；吸附时间160min；吸附温度293K；pH=5	［25］
Fe负载多孔炭	187	20mg吸附剂于50mL MO水溶液（10~100mg·L^-1）；吸附时间60min；吸附温度室温；pH=7	［26］
Fe₂O₃/Mn₃O₄	333	200mg吸附剂于200mL MO水溶液（60~1000mg·L^-1）；吸附时间45min；吸附温度室温；pH=2	［27］
SiO₂@Fe₃O₄	240	5mg吸附剂于10mL MO水溶液（0~100mg·L^-1）；吸附时间180min；吸附温度293K；pH=5.5	［28］
NiFe₂O₄/活性炭	183	300mg吸附剂于100mL MO水溶液（0~200mg·L^-1）；吸附时间30min；吸附温度303K；pH=3	［29］
Fe₃O₄/季铵壳聚糖衍生物	267	100mg吸附剂于100mL MO水溶液（50~300mg·L^-1）；吸附时间60min；吸附温度293K	［30］
Fe₃O₄/PPY	149	10mg吸附剂于10mL MO水溶液（60~320mg·L^-1）；吸附时间90min；吸附温度298K	［31］
LnBDC/活性炭	125	5mg吸附剂于10mL MO水溶液（0~200mg·L^-1）；吸附时间1440min；吸附温度303K；pH=5	［32］
Co₃O₄/TiO₂/多孔炭	273	50mg吸附剂于100mL MO水溶液（30~300mg·L^-1）；吸附时间30min；吸附温度室温	本工作

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