铜/凹凸棒石复合材料高效吸附放射性碘离子性能

doi:10.15541/jim20200663

无机材料学报 ›› 2021, Vol. 36 ›› Issue (8): 856-864.DOI: 10.15541/jim20200663

所属专题：【虚拟专辑】放射性污染物去除(2020~2021)；【能源环境】水体污染物去除

铜/凹凸棒石复合材料高效吸附放射性碘离子性能

余祥坤¹(), 刘坤¹, 李志鹏¹, 赵雨露¹, 沈锦优², 茆平¹(), 孙爱武¹(), 蒋金龙¹

1.淮阴工学院化学工程学院, 矿盐资源深度利用技术国家地方联合工程研究中心, 江苏省凹土资源利用重点实验室, 淮安 223003
2.南京理工大学环境与生物工程学院, 江苏省化工污染控制与资源化高校重点实验室, 南京 210094

收稿日期:2020-11-19 修回日期:2021-01-04 出版日期:2021-08-20 网络出版日期:2021-03-01
通讯作者: 茆平, 校聘副教授. E-mail: pingmao@hyit.edu.cn; 孙爱武, 教授. E-mail: sunaiwu@hyit.edu.cn
作者简介:余祥坤(1993-), 男, 硕士研究生. E-mail: yxk0079@163.com
基金资助:
国家自然科学基金(51908240);江苏省自然科学基金(BK20181064);江苏省六大人才高峰资助项目(2018-JNHB-009);江苏省高校自然科学基金重大项目(18KJA430006);江苏省研究生科研与创新计划项目(SJCX20_1331);江苏省凹土资源利用重点实验室开放课题(HPK201905);2020年省级(202011049042Y)、校级(202011049011XJ)大学生创新创业训练计划项目

Efficient Adsorption of Radioactive Iodide by Copper/Palygorskite Composite

YU Xiangkun¹(), LIU Kun¹, LI Zhipeng¹, ZHAO Yulu¹, SHEN Jinyou², MAO Ping¹(), SUN Aiwu¹(), JIANG Jinlong¹

1. Key Laboratory for Palygorskite Science and Applied Technology of Jiangsu Province, National & Local Joint Engineering Research Center for Mineral Salt Deep Utilization, School of Chemical Engineering, Huaiyin Institute of Technology, Huaian 223003, China
2. Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

Received:2020-11-19 Revised:2021-01-04 Published:2021-08-20 Online:2021-03-01
Contact: MAO Ping, associate professor. E-mail: pingmao@hyit.edu.cn; SUN Aiwu, professor. E-mail: sunaiwu@hyit.edu.cn
About author:YU Xiangkun(1993-), male, Master candidate. E-mail: yxk0079@163.com
Supported by:
National Natural Science Foundation of China(51908240);Natural Science Foundation of Jiangsu Province(BK20181064);Six Talent Peaks Project in Jiangsu Province(2018-JNHB-009);Natural Science Key Project of the Jiangsu Higher Education Institutions(18KJA430006);Postgraduate Research & Practice Innovation Program of Jiangsu Province(SJCX20_1331);Foundation of Jiangsu Provincial Key Laboratory of Palygorskite Science and Applied Technology(HPK201905);Provincial (202011049042Y), University-level (202011049011XJ) Innovation and Entrepreneurship Training Program Project for Undergraduate

摘要/Abstract

摘要：

放射性碘是核裂变必然产物。为解决现有铜基吸附剂的吸附容量低、铜利用率低、易脱附等不足, 基于凹凸棒石的廉价易得、可交换阳离子富足和层间结构等特性, 采用浸渍-还原法将单质Cu负载于凹凸棒石结构中, 制备得到Cu/凹凸棒石复合材料, 对样品进行表征并考察样品对液相碘离子的吸附性能。研究结果表明, 实验制备的Cu/凹凸棒石复合材料约有7.5%掺杂量的纳米铜颗粒负载于凹凸棒石层间结构中。与传统铜基吸附剂相比, 该材料具有高达116.1 mg/g的碘离子吸附量以及72%铜利用率; 并且可在中性、弱酸性以及SO₄^2-、NO₃^-、Na⁺、Mg⁺等干扰离子共存的环境下使用。此外, 得益于铜负载凹凸棒石结构内, 该复合材料展现出较强的抗氧化性能, 且吸附后产物也具有较强的稳定性。

关键词: 凹凸棒石, 铜, 放射性碘离子, 脱附率, 吸附容量

Abstract:

To solve the disadvantages of low adsorption capacity, low utilization and easily desorption of traditional Cu-based adsorbents for radioactive iodide, the inevitable product of nuclear fission, Cu/Palygorskite composite (Cu@PAL) was synthesized through impregnation-reduction method, characterized and applied to remove I^- anions based on the excellent traits of PAL, such as cheap, abundant exchangeable cations and interstratified structure. Results indicate that there are about 7.5wt% copper nanoparticles loaded into PAL for the as-prepared composite. Cu@PAL has better performance in the adsorption of iodide as compared with traditional Cu-based adsorbents, with 72% utilization efficiency and excellent adsorption capacity of 116.1 mg/g. Cu@PAL is suitable for adsorption of I ^- anions under the conditions of neutral, weak acid and the coexistence of interference ions. In addition, the composite exhibit strong oxidation resistance, and the adsorbed product also has strong stability due to the copper stored in the PAL structure.

Key words: palygorskite, elemental copper, radioactive iodide, desorption efficiency, adsorption capacity

中图分类号:

TB333

余祥坤, 刘坤, 李志鹏, 赵雨露, 沈锦优, 茆平, 孙爱武, 蒋金龙. 铜/凹凸棒石复合材料高效吸附放射性碘离子性能[J]. 无机材料学报, 2021, 36(8): 856-864.

YU Xiangkun, LIU Kun, LI Zhipeng, ZHAO Yulu, SHEN Jinyou, MAO Ping, SUN Aiwu, JIANG Jinlong. Efficient Adsorption of Radioactive Iodide by Copper/Palygorskite Composite[J]. Journal of Inorganic Materials, 2021, 36(8): 856-864.

图/表 18

图1 样品(a)PAL, (b)Cu2+@PAL, (c)Cu@PAL的SEM照片及(d) Cu@PAL的EDX谱图

Fig. 1 SEM images of the samples (a) PAL, (b) Cu 2+@PAL, (c) Cu@PAL and (d) EDX pattern of Cu@PAL

表1 PAL和Cu@PAL的化学组成(XRF)/wt%

Table1 Chemical analysis (XRF) of PAL and Cu@PAL/wt%

Composition	PAL	Cu@PAL
SiO₂	60.96	59.87
MgO	9.36	8.12
Al₂O₃	12.20	11.07
Fe₂O₃	8.00	7.51
CaO	5.55	0.46
CuO	0.01	9.83
Na₂O	0.12	0.01
LOI	3.80	3.13

图2 (a)样品的XRD图谱和(b)Cu@PAL的结构示意图

Fig. 2 (a) XRD patterns of the samples and (b) structural schematic diagram of Cu@PAL

图3 Cu2+@PAL的(a) TEM照片及(b) N, (c) O, (d) Al, (e) Si, (f) Cu的元素分布图

Fig. 3 (a) TEM image of Cu2+@PAL and elemental mappings of (b) N, (c) O, (d) Al, (e) Si, and (f) Cu

图4 Cu@PAL的(a) TEM照片及(b) N, (c) O, (d) Al, (e) Si, (f) Cu的元素分布图, 更高放大倍率TEM (g)和HRTEM (h) 照片

Fig. 4 (a) TEM image of Cu@PAL and elemental mappings of (b) N, (c) O, (d) Al, (e) Si, and (f) Cu; and high magnification TEM (g) and HRTEM (h) images of Cu@PAL

图5 样品的XPS谱图

Fig. 5 XPS spectra of the samples (a) Survey scans; (b) Cu2p core level spectra; (c) I 3d core level spectrum

图6 样品的(a)热失重曲线和(b) FT-IR谱图

Fig. 6 (a) TGA curves and (b) FT-IR spectra of the samples

图7 样品的(a)N2吸附脱附等温线和(b)孔径分布

Fig. 7 (a) N2 adsorption-desorption isotherms and (b) pore diameter distributions of the samples

图8 (a)pH对Cu@PAL吸附性能的影响和(b)产物的XRD谱图

Fig. 8 (a) Adsorption capacity of I- anions on Cu@PAL and (b) XRD patterns of adsorption products in the solution with different pH

图9 (a)样品的等温吸附曲线, Cu@PAL等温吸附的(b) Langmuir模型和(c) Frenudlich模型模拟曲线

Fig. 9 (a) Adsorption isotherm of the samples, fitting curves of (b) Langmuir model and (c) Frenudlich model for adsorption isotherm of Cu@PAL

表2 铜基吸附剂碘离子吸附性能对比

Table 2 Comparison of several Cu based adsorbents for iodide adsorption

Adsorbent	pH	Q_e/ (mg∙g^-1)	Utilization efficiency/%	Ref.
Cuprite sulfide	7	6.1	—	[27]
Cu₂O/Cu-C	7	41.2	10.38	[28]
Hollow Cu/Cu₂O	7	33.0	1.85	[20]
Core-shell Cu/Cu₂O	7	22.9	1.4	[12]
Cu	7	6.35	0.32	[29]
Cu/PAL	7	116.1	71.98	This work

表3 Cu@PAL等温吸附模型的拟合参数

Table 3 Isotherm parameters for the adsorption of I- anions by Cu@PAL

Langmuir model			Frenudlich model
Q_m/(mg∙g^-1)	K_l	R²	K_f	1/n	R²
1.02915	0.86041	0.99632	0.38173	0.51042	0.81026

表4 Cu@PAL和纳米铜暴露于空气中的吸附性能

Table 4 Adsorption properties of Cu@PAL and nano Cu exposed to air

Time/h	Q_e/(mg∙g^-1)
Time/h	Cu@PAL	Nano-Cu
0	74.2	234.7
12	69.4	133.8
24	68.1	110.4
48	64.1	104.6
72	60.2	96.3
144	58.7	88.4

图10 I-Cu@PAL的SEM(a), TEM(b)和HRTEM (c) 照片

Fig. 10 SEM (a) and TEM (b) and HRTEM (c) images of I-Cu@PAL

图11 Cu@PAL的吸附动力学曲线(a)以及吸附动力学曲线的伪一级动力学模型(b)和伪二级动力学模型(c)

Fig. 11 Absorption kinetic curve (a), fitting curves of the pseudo first order kinetic model (b) and pseudo second order kinetic model (c) for adsorption kinetic of Cu@PAL

表5 Cu@PAL的吸附动力学拟合参数

Table 5 Kinetic parameters for the adsorption of I- by Cu@PAL

Pseudo-first-order			Pseudo-second-order
Q_m/ (mg∙g^-1)	k₁/(g∙(mmol∙ g^-1)^-1)	R²	Q_m/ (mg∙g^-1)	k₂/(g∙(mmol∙ g^-1)^-1)	R²
56.10	0.4469	0.9704	74.1840	0.03549	0.9976

图12 (a)阴离子和(b)阳离子对Cu@PAL吸附性能的影响

Fig. 12 Effect of (a) anion and (b) cation on the adsorption of Cu@PAL

表6 Cu@PAL和纳米Cu吸附后产物的脱附解析率

Table 6 Leaching or desorption efficiencies of Cu@PAL and nano-Cu after adsorption

Adsorbent	c_NaCl/(mol∙L^-1)	Desorption efficiency/%
Cu@PAL	0	21.3
Cu@PAL	0.1	32.1
Nano-Cu	0	87.4
Nano-Cu	0.1	94.1

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铜/凹凸棒石复合材料高效吸附放射性碘离子性能

Efficient Adsorption of Radioactive Iodide by Copper/Palygorskite Composite

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