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

doi:10.11949/0438-1157.20220329

Abstract

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

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

CLC Number:

O 646

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.

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.

Figures/Tables 12

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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