基于可变价NiFe-LDH/rGO对磷酸根离子的特异性电控分离

doi:10.11949/0438-1157.20220329

化工学报 ›› 2022, Vol. 73 ›› Issue (7): 3057-3067.DOI: 10.11949/0438-1157.20220329

基于可变价NiFe-LDH/rGO对磷酸根离子的特异性电控分离

朱江伟¹(),马鹏飞¹(),杜晓¹,杨言言²,郝晓刚¹(),罗善霞³

^1.太原理工大学化学化工学院，山西太原 030024
^2.上饶师范学院化学与环境科学学院，江西上饶 334001
^3.河北省区域地质调查院，河北廊坊 065000

收稿日期:2022-03-03 修回日期:2022-05-19 出版日期:2022-07-05 发布日期:2022-08-01
通讯作者: 马鹏飞,郝晓刚
作者简介:朱江伟（1997—），男，硕士研究生，zhujiangwei9712@163.com
基金资助:
中国博士后科学基金项目(2020M680916);国家自然科学基金区域创新发展联合基金项目(U21A20303);上饶市高校研发投入后补助资金科技计划项目

Specific electronically controlled separation of phosphate anions based on variable valence NiFe-LDH/rGO

Jiangwei ZHU¹(),Pengfei MA¹(),Xiao DU¹,Yanyan YANG²,Xiaogang HAO¹(),Shanxia LUO³

^1.Department of Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.School of Chemistry and Environmental Science, Shangrao Normal University, Shangrao 334001, Jiangxi, China
^3.Hebei Institute of Regional Geological Survey, Langfang 065000, Hebei, China

Received:2022-03-03 Revised:2022-05-19 Online:2022-07-05 Published:2022-08-01
Contact: Pengfei MA,Xiaogang HAO

摘要/Abstract

摘要：

磷是一种不可再生资源。为解决现有磷污染以及磷资源流失等问题，通过油浴与热化学还原相结合的方法，成功制备出一种NiFe-LDH/rGO电活性杂化膜材料。使用电化学方法，在氧化还原电位的控制下，Ni、Fe(Ⅱ/Ⅲ)双金属发生核外电子的跃迁，高价态的Ni、Fe(Ⅲ)与 $P O 4 3 -$ 发生内球络合作用，实现 $P O 4 3 -$ 的选择性置入-置出。实验获得270 mg·g^-1的高 $P O 4 3 -$ 吸附容量及85%以上的再生效率。此外，该杂化膜材料在共存离子存在的复杂水体中，对 $P O 4 3 -$ 具有优异的选择性，为磷石膏渗滤液以及各种含磷废水污染等问题的解决提供有效的理论技术支撑，具有广阔的应用前景。

关键词: NiFe-LDH/rGO, PO₄^3-, 电化学, 选择性, 吸附容量, 稳定性

Abstract:

Phosphorus is a non-renewable resource. In order to solve the problems of existing phosphorus pollution and phosphorus resource loss, a NiFe-LDH/rGO electroactive hybrid film material was successfully prepared in this study by a combination of oil bath and thermochemical reduction. An ESIX process allows the NiFe-LDH/rGO hybrid film achieving a controllably selective uptake and release of the phosphate anions. This route involves tuning potential steps to regulate the redox states of the composite film and the variable metal (e.g., Ni, Fe (Ⅱ)/(Ⅲ)) in coordination centers, as the inner-sphere complexation of the metals to phosphate anions is combined with the assistance of the outer electric field. A high absorption capacity (270 mg·g^-1) and regeneration rate (>85%) were achieved, together with good cycle stability. This route provides an efficient, theoretical and technical support to solve the problems phosphogypsum leachate and various phosphorus wastewater pollution, which presents a broad application prospect.

Key words: NiFe-LDH/rGO, phosphate anions, electrochemistry, selectivity, adsorption capacity, stability

中图分类号:

O 646

朱江伟, 马鹏飞, 杜晓, 杨言言, 郝晓刚, 罗善霞. 基于可变价NiFe-LDH/rGO对磷酸根离子的特异性电控分离[J]. 化工学报, 2022, 73(7): 3057-3067.

Jiangwei ZHU, Pengfei MA, Xiao DU, Yanyan YANG, Xiaogang HAO, Shanxia LUO. Specific electronically controlled separation of phosphate anions based on variable valence NiFe-LDH/rGO[J]. CIESC Journal, 2022, 73(7): 3057-3067.

图/表 12

图1 (a)~(c) 不同放大倍数下LDH的SEM图; (d) LDH/GO杂化材料的SEM图; (e)、(f)不同放大倍数下LDH/rGO杂化材料的SEM图

Fig.1 (a)—(c) SEM images of LDH at different magnification; (d) SEM image of LDH/GO hybrid matrials;(e), (f) SEM images of LDH/rGO hybrid matrials at different magnification

图2 NiFe-LDH、NiFe-LDH/GO和NiFe-LDH/rGO的XRD谱图

Fig.2 XRD patterns of NiFe-LDH, NiFe-LDH/GO and NiFe-LDH/rGO hybrid matrials

图3 (a) 0.1 mol·L-1 Na3PO4溶液中NiFe-LDH/rGO杂化膜在50 mV·s-1扫速下的CV曲线; (b) 0.1 mol·L-1 Na3PO4溶液中NiFe-LDH/rGO杂化膜阳极和阴极峰值电流随扫速平方根的变化规律

Fig.3 (a) CV curves of NiFe-LDH/rGO hybrid films in 0.1 mol·L-1 Na3PO4 solution at 50 mV·s-1; (b) The variation of anode and cathode peak current of the NiFe-LDH /rGO hybrid film with the square root of scanning speed in 0.1 mol·L-1 Na3PO4 solution

表1 0.1 mol·L-1 Na3PO4溶液中不同扫速对应的阴、阳极峰值电流

Table 1 Cathodic and anodic peak currents corresponding to different scanning rates in 0.1 mol·L-1 Na3PO4 solution

$v$ /(mV·s^-1)	$v$ ^1/2/(mV·s^-1)^1/2	I/mA
$v$ /(mV·s^-1)	$v$ ^1/2/(mV·s^-1)^1/2	Ni(阳极)	Ni(阴极)	Fe(阳极)	Fe(阴极)
10	3.162	0.167	-0.232	-0.038	-0.188
20	4.472	0.291	-0.362	-0.021	-0.241
30	5.477	0.390	-0.481	0.002	-0.294
40	6.324	0.500	-0.590	0.020	-0.342
50	7.071	0.589	-0.693	0.047	-0.389

表1 0.1 mol·L-1 Na3PO4溶液中不同扫速对应的阴、阳极峰值电流

Table 1 Cathodic and anodic peak currents corresponding to different scanning rates in 0.1 mol·L-1 Na3PO4 solution

$v$ /(mV·s^-1)	$v$ ^1/2/(mV·s^-1)^1/2	I/mA
$v$ /(mV·s^-1)	$v$ ^1/2/(mV·s^-1)^1/2	Ni(阳极)	Ni(阴极)	Fe(阳极)	Fe(阴极)
10	3.162	0.167	-0.232	-0.038	-0.188
20	4.472	0.291	-0.362	-0.021	-0.241
30	5.477	0.390	-0.481	0.002	-0.294
40	6.324	0.500	-0.590	0.020	-0.342
50	7.071	0.589	-0.693	0.047	-0.389

图4 0.1 mol·L-1 Na3PO4溶液中NiFe-LDH/rGO杂化膜在初始(上)、氧化(中)与还原(下)状态时的XPS谱图

Fig.4 XPS spectra of NiFe-LDH/rGO hybrid film in 0.1 mol·L-1 Na3PO4 solution at initial (top), oxidation (middle) and reduction (bottom) states

图5 不同初始浓度下NiFe-LDH/rGO杂化膜对PO43-的吸附容量

Fig.5 The adsorption capacity of NiFe-LDH/rGO hybrid films for phosphate anionsat different initial concentrations

表2 不同浓度下NiFe-LDH/rGO杂化膜对PO43-的动力学模型参数和相关因子

Table 2 Kinetic model parameters and related factors of phosphate anions induced by NiFe-LDH/rGO hybrid film at different concentrations

C₀/(mg·L^-1)	q_e(exp)/( mg·g^-1)	Pseudo-first-order			Pseudo-second-order
C₀/(mg·L^-1)	q_e(exp)/( mg·g^-1)	k₁/min^-1	q_e(cal)/( mg·g^-1)	R²	k₂/min^-1	q_e(cal)/(mg·g^-1)	R²
101.58	76.35	0.011	60.138	0.948	1.55×10^-4	90.090	0.997
192.72	121.74	0.017	105.047	0.866	8.87×10^-5	149.477	0.986
301.93	200.18	0.018	174.493	0.971	4.38×10^-5	236.967	0.996
512.36	269.68	0.012	265.219	0.966	4.57×10^-5	282.486	0.996

图6 ESIX (rGO)、 IX (NiFe-LDH/rGO)、 ESIX (NiFe-LDH)和ESIX (NiFe-LDH/rGO)对磷酸盐阴离子的吸附容量曲线

Fig.6 Phosphate anions uptake capacity curves of ESIX (rGO), IX (NiFe-LDH/rGO), ESIX (NiFe-LDH) and ESIX (NiFe-LDH/rGO)

图7 （a）NiFe-LDH/rGO杂化膜在初始浓度均为300 mg·L-1下对PO43-、 SO42-、 NO3-和Cl-的竞争性吸附； (b) 0.30 mol·L-1 NaNO3, 0.30 mol·L-1 NaCl, 0.15 mol·L-1 Na2SO4和0.10 mol·L-1 Na3PO4电解液中NiFe-LDH/rGO复合膜的CV曲线

Fig.7 (a) Competitive adsorption of PO43-, SO42-, NO3-, and Cl- for NiFe-LDH/rGO hybrid films at an initial concentration of 300 mg·L-1; (b) CV curves of NiFe-LDH/rGO hybrid film in 0.30 mol·L-1 NaNO3, 0.30 mol·L-1 NaCl, 0.15 mol·L-1 Na2SO4, and 0.10 mol·L-1 Na3PO4 electrolytic solutions

表3 NiFe-LDH/rGO杂化膜在初始浓度均为300 mg·L-1下对PO43-、SO42-、NO3-和Cl-的分离系数和相对分离因子

Table 3 Separation coefficients and relative separation factors of PO43-， SO42-， NO3-， and Cl- of the NiFe-LDH/rGO hybrid film at the initial concentration of 300 mg·L-1

Anion	Adsorption capacity/（mg·g^-1）	Separation coefficient (K_D)	Relative separation factor (α)
$P O 4 3 -$	178.012	0.865	1
$S O 4 2 -$	70.871	0.274	3.163
$N O 3 -$	50.336	0.185	4.678
Cl^-	45.248	0.156	5.551

表3 NiFe-LDH/rGO杂化膜在初始浓度均为300 mg·L-1下对PO43-、SO42-、NO3-和Cl-的分离系数和相对分离因子

Table 3 Separation coefficients and relative separation factors of PO43-， SO42-， NO3-， and Cl- of the NiFe-LDH/rGO hybrid film at the initial concentration of 300 mg·L-1

Anion	Adsorption capacity/（mg·g^-1）	Separation coefficient (K_D)	Relative separation factor (α)
$P O 4 3 -$	178.012	0.865	1
$S O 4 2 -$	70.871	0.274	3.163
$N O 3 -$	50.336	0.185	4.678
Cl^-	45.248	0.156	5.551

图8 NiFe-LDH/rGO杂化膜在300 mg·L-1的磷酸钠 (吸附) 和硝酸钠 (脱附) 溶液中对PO43-的吸脱附容量(a)和再生效率(b)

Fig.8 The adsorption and desorption capacity (a) and regeneration rate (b) of NiFe-LDH /rGO hybrid film for phosphate ions in 300 mg·L-1 sodium phosphate and sodium nitrate solutions, respectively

图9 不同pH下NiFe-LDH/rGO杂化膜对磷酸根离子的吸附容量

Fig. 9 Adsorption capacity of NiFe-LDH/rGO hybrid film for phosphate ion at different pH

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基于可变价NiFe-LDH/rGO对磷酸根离子的特异性电控分离

Specific electronically controlled separation of phosphate anions based on variable valence NiFe-LDH/rGO

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