电活性镍钴双金属氧化物高选择性去除/回收水中磷酸盐离子

doi:10.15541/jim20200340

无机材料学报 ›› 2021, Vol. 36 ›› Issue (3): 292-298.DOI: 10.15541/jim20200340 CSTR: 32189.14.10.15541/jim20200340

电活性镍钴双金属氧化物高选择性去除/回收水中磷酸盐离子

杨言言¹^,²(), 李永国³, 祝小雯¹, 杜晓², 马旭莉², 郝晓刚²()

1. 上饶师范学院化学与环境科学学院, 上饶 334001
2. 太原理工大学化学化工学院, 太原 030024
3. 中国辐射防护研究院, 太原 030006

收稿日期:2020-06-20 修回日期:2020-08-27 出版日期:2021-03-20 网络出版日期:2020-09-09
通讯作者: 郝晓刚, 教授. E-mail: xghao@tyut.edu.cn, tyutxghao@hotmail.com
作者简介:杨言言(1983-), 女, 博士, 讲师. E-mail: yangyy0927@163.com
基金资助:
国家自然科学基金(21776191);国家自然科学基金(21706181);上饶师范学院校级自选课题(202028);山西省重点研发计划(201803D421094);国家重点研发计划政府间国际科技创新合作重点专项项目(2017YFE0129200)

Potential Induced Reversible Removal/Recovery of Phosphate Anions with High Selectivity Using an Electroactive NiCo-layered Double Oxide Film

YANG Yanyan¹^,²(), LI Yongguo³, ZHU Xiaowen¹, DU Xiao², MA Xuli², HAO Xiaogang²()

1. School of Chemistry and Environmental Science, Shangrao Normal University, Shangrao 334001, China
2. Department of Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
3. China Institute for Radiation Protection, Taiyuan 030006, China

Received:2020-06-20 Revised:2020-08-27 Published:2021-03-20 Online:2020-09-09
Contact: HAO Xiaogang, professor. E-mail: xghao@tyut.edu.cn, tyutxghao@hotmail.com
About author:YANG Yanyan (1983-), female, PhD, lecturer. E-mail:yangyy0927@163.com
Supported by:
National Natural Science Foundation of China(21776191);National Natural Science Foundation of China(21706181);Project of Shangrao Normal University(202028);Key R&D project of Shanxi Province(201803D421094);National Key R&D Program of China(2017YFE0129200)

摘要/Abstract

摘要：

磷是植物体生长的重要营养素, 也是引发水体富营养化的重要因素, 因此废水中磷酸盐的去除与回收均至关重要。本研究采用单极脉冲电沉积法在炭布上制备镍钴双氢氧化物, 并于管式炉中原位焙烧制得镍钴双金属氧化物(NiCo-Layered Double Oxide, NiCo-LDO), 将其用于电控离子交换(Electrochemically Switched Ion Exchange, ESIX)过程实现PO₄ ^3-的去除与回收。实验对比了ESIX与离子交换(Ion Exchange, IX)过程中NiCo-LDO对PO₄ ^3-的去除性能, 并考察了其选择性及循环稳定性。结果表明, 在(10.00±0.05) mg/L的PO₄ ^3-溶液中, ESIX过程中膜对PO₄ ^3-的离子交换量约为IX的2倍; NiCo-LDO对PO₄ ^3-具有高选择性, 且经过5次循环后, 离子交换量仍可达到初始值的92%以上; 结合XPS分析, 发现NiCo-LDO对PO₄ ^3-的ESIX过程包括一个不可逆的“记忆效应”结构恢复过程及两个可逆的层板金属离子氧化/还原和PO₄ ^3-与O-H基团的配体交换过程。

关键词: 镍钴双金属氧化物, 磷酸盐, 电控离子交换, 配体交换

Abstract:

Phosphorus is an essential nutrient for organisms growth and a major cause of eutrophication in water bodies. Thus, it is crucial for both of the removal and recovery of phosphate from wastewater. In this work, the NiCo-layered double oxide (NiCo-LDO) was successfully fabricated on carbon cloth conductive substrate via the in-situ calcination of the NiCo-layered double hydroxide (NiCo-LDH) and served as the electrochemically switched ion exchange (ESIX) film electrode for the removal and recovery of PO₄ ^3-. The performance of NiCo-LDO for PO₄ ^3- removal by ESIX and ion exchange (IX) was compared, while the selectivity and stability of NiCo-LDO for PO₄ ^3- removal were also investigated. The results revealed that, in (10.00±0.05) mg/L PO₄ ^3- solution, the ion exchange quantity of the NiCo-LDO for PO₄ ^3- removal by ESIX process was about twice over that by IX. Moreover, compared with Cl ^-, NO₃ ^-, SO₄ ^2- and I ^-, the NiCo-LDO exhibited much higher selectivity towards PO₄ ^3-. In addition, the ion exchange quantity still retained 92% of its initial value after 5 uptake and release cycles. Coupled with XPS analysis, it was found that ESIX process of NiCo-LDO film electrode for PO₄ ^3- removal and recovery mainly consisted of 3 steps, which were an irreversible “memory effect” structure recovery process, the redox reaction of metal ion in lamellar and the ligand exchange between PO₄ ^3- and O-H groups.

Key words: NiCo-layered double oxide, phosphate, electrochemically switched ion exchange, ligand exchange

中图分类号:

TQ150

杨言言, 李永国, 祝小雯, 杜晓, 马旭莉, 郝晓刚. 电活性镍钴双金属氧化物高选择性去除/回收水中磷酸盐离子[J]. 无机材料学报, 2021, 36(3): 292-298.

YANG Yanyan, LI Yongguo, ZHU Xiaowen, DU Xiao, MA Xuli, HAO Xiaogang. Potential Induced Reversible Removal/Recovery of Phosphate Anions with High Selectivity Using an Electroactive NiCo-layered Double Oxide Film[J]. Journal of Inorganic Materials, 2021, 36(3): 292-298.

图/表 9

图1 NiCo-LDH (a, c) 和NiCo-LDO (b, d)的SEM照片及NiCo-LDO的TEM照片(e)和HRTEM照片(f)

Fig. 1 SEM images of NiCo-LDH (a, c) and NiCo-LDO (b, d), TEM (e) and HRTEM (f) images of NiCo-LDO

图2 NiCo-LDH焙烧前后的XRD图谱(a)、NiCo-LDO的XPS全谱(b)、Co2p(c)及Ni2p(d)高分辨率XPS谱

Fig. 2 XRD patterns of NiCo-LDH and NiCo-LDO (a), full XPS (b), high resolution Co2p (c), and Ni2p (d) spectra of NiCo-LDO

图3 NiCo-LDO在ESIX及IX过程中对PO43-的吸附曲线(a)、NiCo-LDO氧化后Co2p(b)及Ni2p(c)高分辨率XPS谱

Fig. 3 Kinetic adsorption curves of PO43- on NiCo-LDO under ESIX or IX process (a), high resolution Co2p (b) and Ni2p (c) spectra of NiCo-LDO after oxidation

图4 NiCo-LDO在四元混合溶液中对PO43-、SO42-、I-和Cl-的竞争吸附曲线

Fig. 4 Competitive adsorption kinetics curves of PO43-, SO42-, I-, and Cl- onto NiCo-LDO in 21.19 mg/L PO43-, 21.71 mg/L SO42-, 21.64 mg/L I-, and 22.85 mg/L Cl- mixed solution

表1 NiCo-LDH与阴离子之间结合能计算结果

Table 1 Calculated binding energy between anion-and NiCo-LDH

Anion-LDH	E_cp/(kJ•mol^-1)
Cl^--LDH	-455.88
I^--LDH	-345.20
SO₄^2--LDH	-813.90
PO₄^3--LDH	-868.36

图5 NiCo-LDO的稳定性测试结果

Fig. 5 Recyclability test of NiCo-LDO for the removal of PO43-

表2 文献报道的PO43-吸附剂对PO43-吸附量的对比

Table 2 Comparison of the ion adsorption quantity with those reported PO43- ion adsorbents

Ion adsorbent	Adsorption quantity/(mg•g^-1)	Time/h	Ref.
Aluminum oxide hydroxide	36.27	4	[6]
Fe-Mn binary oxide	33.2	24	[29]
Hydroxy-aluminum	12.7	7	[30]
MgFe-Zr-LDH@magnetic particles	30	24	[31]
Am-ZrO₂	67.29	8	[32]
Mg-Fe-Cl LDH	9.8	6	[10]
Nano-La(III) (hydr)oxides	~55	10	[33]
La(OH)₃/Fe₃O₄	83.5	5	[5]
NiCo-LDO	159.36	6	This work

图6 NiCo-LDO氧化前(曲线组a)后(曲线组b)P2p(A)及O1s(B)的高分辨率XPS图谱

Fig. 6 High resolution P2p (A) and O1s (B) spectra of NiCo-LDO before (curves a) and after (curves b) oxidation

图7 NiCo-LDO去除/回收PO43-的ESIX机理

Fig. 7 Illustration of the ESIX mechanism of NiCo-LDO for removal/recovery of PO43-

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电活性镍钴双金属氧化物高选择性去除/回收水中磷酸盐离子

Potential Induced Reversible Removal/Recovery of Phosphate Anions with High Selectivity Using an Electroactive NiCo-layered Double Oxide Film

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