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

doi:10.15541/jim20200340

Abstract

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

CLC Number:

TQ150

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.

Figures/Tables 9

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

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

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

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

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

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

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

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

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

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