金属有机框架掺杂氧化石墨烯对水中锑的吸附研究

doi:10.19965/j.cnki.iwt.2022-1031

摘要/Abstract

摘要：

以金属有机框架（MOFs）MIL-53（Fe）为基体，成功将氧化石墨烯（GO）掺杂于其中，制备了GO@MIL-53（Fe）复合材料。采用扫描电镜、比表面积分析、红外光谱分析、X射线衍射、X射线光电子能谱等对制备的材料进行表征分析，考察了其在水溶液中对Sb（Ⅴ）的吸附性能。在通过响应面实验找到吸附最适条件的基础上，探究了共存离子对其吸附的影响。结果表明，Sb（Ⅴ）的最优吸附条件：Sb（Ⅴ）初始质量浓度为23.22 mg/L，吸附时间为2.7 h，吸附剂投加量为27.22 mg，反应温度为34.63 ℃，pH=4.13，此条件下，Sb（Ⅴ）去除率可达99.11%。实验吸附过程符合准二级吸附动力学模型（R ²=0.997）和Langmuir吸附等温线（R ²=0.991），2%GO@MIL-53（Fe）在318 K时的最大单分子吸附量为180.2 mg/g，并且吸附过程为自发进行；废水中CO₃ ^2-对Sb（Ⅴ）的吸附有抑制作用；经过4轮吸附-解吸实验，2%GO@MIL-53（Fe）仍保持70%以上的去除率，具有良好的洗脱再生和回收性能。

关键词: 吸附, 氧化石墨烯, 金属有机框架, MIL-53（Fe）, Sb（Ⅴ）

Abstract:

The nanocomposite GO@MIL-53（Fe） was successfully synthesized using by doping graphene oxide（GO） into the metal-organic framework（MOFs） MIL-53（Fe） matrix. The prepared material was characterized by SEM，FT-IR，XRD，XPS et al，and its adsorption performance to adsorb Sb（Ⅴ） from water was studied. The optimum condition for adsorption was determined by response surface methodology，and the effect of coexisting ions on the adsorption was investigated. The results showed that the optimal adsorption conditions for Sb（Ⅴ） were as follows：initial Sb（Ⅴ） concentration 23.22 mg/L，adsorption time 2.7 h，adsorbent dosage 27.22 mg，reaction temperature 34.63 ℃，pH=4.13，the removal rate could reach 99.11%. The pseudo-second order was the best model to fit（R ²=0.997），and the process fit Langmuir adsorption isotherm model（R ²=0.991）. 2%GO@MIL-53（Fe） reached its maximum single-molecule adsorption capacity of 180.2 mg/g at 318 K，and the adsorption process was spontaneous. The results also indicated that CO₃ ^2- had an inhibitory effect on the adsorption of Sb（Ⅴ）. 2%GO@MIL-53（Fe） maintained a removal rate of over 70% after 4 rounds of adsorption-desorption experiments，which showed its excellent recyclability.

Key words: adsorption, graphene oxide, metal-organic framework, MIL-53（Fe）, Sb（Ⅴ）

中图分类号:

X703.1

杨秀贞, 成双婵, 张浩麟, 周斌, 侯保林. 金属有机框架掺杂氧化石墨烯对水中锑的吸附研究[J]. 工业水处理, 2023, 43(9): 72-83.

Xiuzhen YANG, Shuangchan CHENG, Haolin ZHANG, Bin ZHOU, Baolin HOU. Adsorption of Sb in water with graphene oxide doped metal-organic framework[J]. Industrial Water Treatment, 2023, 43(9): 72-83.

https://www.iwt.cn/CN/Y2023/V43/I9/72

图/表 16

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物理性质	2%GO@MIL-53（Fe）	MIL-53（Fe）
比表面积/（m²·g^-1）	268.43	174.41
平均孔径/nm	2.52	3.74
微孔孔容/（cm³·g^-1）	0.12	0.05
孔容积/（cm³·g^-1）	0.18	0.11

物理性质	2%GO@MIL-53（Fe）	MIL-53（Fe）
比表面积/（m²·g^-1）	268.43	174.41
平均孔径/nm	2.52	3.74
微孔孔容/（cm³·g^-1）	0.12	0.05
孔容积/（cm³·g^-1）	0.18	0.11

实验组数	影响因素编码水平					Sb（Ⅴ）去除率/%		实验组数	影响因素编码水平					Sb（Ⅴ）去除率/%
实验组数	A	B	C	D	E	实验值	预测值	实验组数	A	B	C	D	E	实验值	预测值
1	-1	-1	0	0	0	88.48	89.33	24	0	1	1	0	0	95.82	95.81
2	1	-1	0	0	0	94.02	94.27	25	-1	0	0	-1	0	88.88	87.61
3	-1	1	0	0	0	96.59	96.07	26	1	0	0	-1	0	93.64	92.74
4	1	1	0	0	0	98.39	97.81	27	-1	0	0	1	0	97.19	97.43
5	0	0	-1	-1	0	92.95	92.23	28	1	0	0	1	0	98.37	98.98
6	0	0	1	-1	0	85.25	87.38	29	0	0	1	0	1	96.88	98.59
7	0	0	-1	1	0	98.41	96.91	30	0	0	1	0	1	97.39	95.75
8	0	0	1	1	0	97.42	98.77	31	0	0	1	0	1	93.22	94.19
9	0	-1	0	0	-1	96.85	94.08	32	0	0	1	0	1	96.44	94.05
10	0	1	0	0	-1	95.47	98.18	33	-1	0	0	0	1	95.11	96.79
11	0	-1	0	0	1	93.97	89.99	34	1	0	0	0	1	96.49	98.28
12	0	1	0	0	1	94.66	96.16	35	-1	0	0	0	1	91.52	91.90
13	-1	0	-1	0	0	96.02	94.87	36	1	0	0	0	1	96.59	97.08
14	1	0	-1	0	0	98.48	97.45	37	0	1	0	-1	0	79.33	82.21
15	-1	0	1	0	0	92.83	92.62	38	0	1	0	-1	0	95.67	95.31
16	1	0	1	0	0	96.81	96.72	39	0	1	0	1	0	97.60	98.21
17	0	0	0	-1	-1	98.05	95.54	40	0	1	0	1	0	98.02	95.39
18	0	0	0	1	-1	97.32	96.35	41	0	0	0	0	0	97.01	96.70
19	0	0	0	-1	1	84.52	85.26	42	0	0	0	0	0	95.30	96.70
20	0	0	0	1	1	98.25	99.53	43	0	0	0	0	0	96.80	96.70
21	0	-1	-1	0	0	90.88	92.17	44	0	0	0	0	0	98.20	96.70
22	0	1	-1	0	0	96.91	97.33	45	0	0	0	0	0	97.30	96.70
23	0	-1	1	0	0	89.84	90.70	46	0	0	0	0	0	95.60	96.70

实验组数	影响因素编码水平					Sb（Ⅴ）去除率/%		实验组数	影响因素编码水平					Sb（Ⅴ）去除率/%
实验组数	A	B	C	D	E	实验值	预测值	实验组数	A	B	C	D	E	实验值	预测值
1	-1	-1	0	0	0	88.48	89.33	24	0	1	1	0	0	95.82	95.81
2	1	-1	0	0	0	94.02	94.27	25	-1	0	0	-1	0	88.88	87.61
3	-1	1	0	0	0	96.59	96.07	26	1	0	0	-1	0	93.64	92.74
4	1	1	0	0	0	98.39	97.81	27	-1	0	0	1	0	97.19	97.43
5	0	0	-1	-1	0	92.95	92.23	28	1	0	0	1	0	98.37	98.98
6	0	0	1	-1	0	85.25	87.38	29	0	0	1	0	1	96.88	98.59
7	0	0	-1	1	0	98.41	96.91	30	0	0	1	0	1	97.39	95.75
8	0	0	1	1	0	97.42	98.77	31	0	0	1	0	1	93.22	94.19
9	0	-1	0	0	-1	96.85	94.08	32	0	0	1	0	1	96.44	94.05
10	0	1	0	0	-1	95.47	98.18	33	-1	0	0	0	1	95.11	96.79
11	0	-1	0	0	1	93.97	89.99	34	1	0	0	0	1	96.49	98.28
12	0	1	0	0	1	94.66	96.16	35	-1	0	0	0	1	91.52	91.90
13	-1	0	-1	0	0	96.02	94.87	36	1	0	0	0	1	96.59	97.08
14	1	0	-1	0	0	98.48	97.45	37	0	1	0	-1	0	79.33	82.21
15	-1	0	1	0	0	92.83	92.62	38	0	1	0	-1	0	95.67	95.31
16	1	0	1	0	0	96.81	96.72	39	0	1	0	1	0	97.60	98.21
17	0	0	0	-1	-1	98.05	95.54	40	0	1	0	1	0	98.02	95.39
18	0	0	0	1	-1	97.32	96.35	41	0	0	0	0	0	97.01	96.70
19	0	0	0	-1	1	84.52	85.26	42	0	0	0	0	0	95.30	96.70
20	0	0	0	1	1	98.25	99.53	43	0	0	0	0	0	96.80	96.70
21	0	-1	-1	0	0	90.88	92.17	44	0	0	0	0	0	98.20	96.70
22	0	1	-1	0	0	96.91	97.33	45	0	0	0	0	0	97.30	96.70
23	0	-1	1	0	0	89.84	90.70	46	0	0	0	0	0	95.60	96.70

来源	平方和	自由度	均方根	F值	P值	显著性
模型	651.67	20	32.58	37.70	< 0.000 1	显著
A	44.59	1	44.59	10.54	0.003 3
B	105.58	1	105.58	24.95	< 0.000 1
C	8.93	1	8.93	2.11	0.158 8
D	258.33	1	258.33	61.05	< 0.000 1
E	37.18	1	37.18	8.79	0.006 6
AB	2.56	1	2.56	0.61	0.444 0
AC	0.58	1	0.58	0.14	0.714 9
AD	3.20	1	3.20	0.76	0.392 5
AE	3.40	1	3.40	0.80	0.378 3
BC	6.25×10^-4	1	6.25×10^-4	1.48×10^-4	0.990 4
BD	63.36	1	63.36	14.97	0.000 7
BE	1.07	1	1.07	0.25	0.619 3
CD	11.26	1	11.26	2.66	0.115 4
CE	1.84	1	1.84	0.43	0.516 1
DE	52.27	1	52.27	12.35	0.001 7
A ²	1.85	1	1.85	0.44	0.514 3
B ²	30.51	1	30.51	7.21	0.012 7
C ²	5.97	1	5.97	1.41	0.245 9
D ²	36.70	1	36.70	8.67	0.006 9
E ²	0.46	1	0.46	0.11	0.745 0
残差	105.78	25	4.23
失拟误差	99.90	20	4.99	4.24	0.157 9	不显著
纯误差	5.89	5	1.18
总计	757.45	45

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