Adsorption of Arsenate in Water by Zirconia-halloysite Nanotube Material

doi:10.15541/jim20220576

Abstract

Abstract:

Drinking water contaminated with arsenic for a long time will inevitably lead to serious human health problems. Suitable adsorbent for arsenic removal from water is an urgent but a challenging task. In this study, halloysite nanotubes-supported ZrO₂ (ZrO₂/HNT), a novel and efficient arsenate adsorbent, was prepared using a straightforward hydrothermal method. Its morphology and structure were characterized. ZrO₂ nanoparticles with monoclinic phase were well dispersed on the outer walls of halloysite nanotubes. And the ZrO₂/HNT could effectively remove As(V), achieving adsorption equilibrium within 30 min. The saturation As(V) adsorption capacity was 27.46 mg/g at 25 ℃. Its adsorption capacity decreased with the increase of the solution’s pH. Coexistent ions (except phosphate) showed little effect on adsorption performance of As(V). The As(V) adsorption kinetics fitted well with pseudo-second-order modeland the As(V) removal processes were endothermic which was verified as chemisorption reactions based on calculation of Gibbs free energy and Dubinin-Radushkevich (D-R) isotherm model. Fourier transform infrared (FT-IR) and X-ray photoelectron spectrometer (XPS) study indicated that the As(V) adsorption processes mainly proceeded through ligand exchange between As(V) and hydroxyl groups on the surface of ZrO₂ in the ZrO₂/HNT and formation of inner-sphere surface complexes. This study suggest that the as-synthesized ZrO₂/ HNT is a potential candidate for practical applications of As(V) removal from water.

Key words: halloysite, zirconia, adsorption, arsenate

CLC Number:

GUO Chunxia, CHEN Weidong, YAN Shufang, ZHAO Xueping, YANG Ao, MA Wen. Adsorption of Arsenate in Water by Zirconia-halloysite Nanotube Material[J]. Journal of Inorganic Materials, 2023, 38(5): 529-536.

Figures/Tables 15

Fig. 1 SEM images of (a) HNT and (b) ZrO2/HNT composite

Fig. 2 Morphologies and element distribution of HNT and ZrO2/HNT (a, b) TEM images of HNT (a) and ZrO2/HNT (b); (c) HRTEM image of ZrO2/HNT; (d-i) TEM-EDS mapping images of ZrO2/HNT-As(V) (d), Al (e), Si (f), O (g), Zr (h), and As (i)

Fig. 3 XRD patterns of (a) ZrO2/HNT and (b) HNT

Fig. 4 FT-IR spectra of HNT, ZrO2/HNT, and ZrO2/HNT-As(V)

Fig. 5 Adsorption kinetics for As(V) adsorption on HNT and ZrO2/HNT

Table 1 Adsorption kinetics parameters for As(V) adsorption on ZrO2/HNT

Model	Parameter
Psedo-first-order	Q_e/(mg•g^-1)	K₁/min^-1	R²
Psedo-first-order	20.49	0.6985	0.924
Psedo-second-order	Q_e/(mg•g^-1)	K₂/(g•mg^-1•min^-1)	R²
Psedo-second-order	21.16	0.0548	0.984

Fig. 6 Adsorption isotherms of As(V) on ZrO2/HNT under different temperatures

Table 2 Fitting results of isotherms for As(V) adsorption onto ZrO2/HNT

Isotherm model	Parameter	Temperature/℃
Isotherm model	Parameter	25	35	45
Langmuir model	Q_m/(mg•g^-1)	27.45819	30.03619	31.59709
	k_L/(L•mg^-1)	1.75844	2.36858	3.45464
	R²	0.9972	0.9994	0.9999
Freundlich model	n	9.30552	9.26368	9.98317
	k_F/(mg^1-(1/ⁿ⁾•L^1/ⁿ•g^-1)	17.15745	18.92668	20.52261
	R²	0.7370	0.76954	0.74909
D-R model	q_m/(mol•g^-1)	8.09×10^-4
	β/(mol²•kJ^-2)	4.42×10^-9
	E/(kJ•mol^-1)	10.64
	R²	0.94213

Table 3 Comparison of ZrO2/HNT with other reported similar adsorbents for As(V) adsorption

Adsorbent	pH	Adsorption capacity/ (mg•g^-1)	Ref.
ZrO₂/multiwall carbon nanotube	6	5	[12]
Ferric oxyhydroxides/ activated carbon	7	5	[26]
Cerium-loaded cation exchange resin	5-6	1.03	[27]
Hydrous zirconium oxide/D401	3.16	11.84	[28]
Magnetic iron oxide/ carbon encapsulates	7	17.9	[29]
Fe₃O₄-MnO₂/graphite	2-12	12.2	[30]
ZrO₂/sawdust	3-11	12	[31]
Iron oxide/carbon nanotubes	5.5	9.74	[32]
γ-Fe₂O₃ cores coated with ZrO₂	9	18.3	[33]
ZrO₂/HNT	3	27.46	This study

Table 4 Temperature-dependent thermodynamic characteristics of As(V) adsorption on ZrO2/HNT

	Thermodynamic parameter
Temperature/℃	ΔG°/ (kJ•mol^-1)	ΔH°/ (kJ•mol^-1)	ΔS°/ (kJ•mol^-1•K^-1)
25	-20.41	37.75	0.19
35	-21.96
45	-24.33

Fig. 7 Effect of pH on Zeta potential and adsorption capacity of ZrO2/HNT for As(V)

Fig. 8 Effects of co-existing ions on adsorption of As(V) by ZrO2/HNT

Fig. 9 (a) Survey, (b) As3d, and (c) Zr3d XPS spectra of (1) ZrO2/HNT and (2) ZrO2/HNT-As(V)

Fig. S1 D-R isotherm plots obtained for the adsorption of As(V) on ZrO2/HNT

Fig. S2 Plot of lnKd versus 1/T obtained for the adsorption of As(V) on ZrO2/HNT

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