Adsorption of Eu(III) on Alkalized Ti3C2Tx MXene Studied by Batch Experiment and Its Mechanism Investigation

doi:10.15541/jim20190073

Abstract

Abstract:

In order to rapidly remove Eu(III) from aqueous solution, an alkalized two-dimensional titanium carbide, Na-Ti₃C₂T_x, was successfully prepared by treating inorganic two-dimensional transition metal carbide (MXene) with NaOH. Adsorption behavior of Eu(III) on Na-Ti₃C₂T_x was systematically investigated by batch experiments. The results show that the adsorption process is greatly affected by pH and ionic strength of the solution, and reached equilibrium within 5 min. Based on Langmuir model fitting results, the maximum adsorption capacity of Eu(III) on Na-Ti₃C₂T_x was calculated to be 54.05 mg/g at pH 4.0 under 298 K. The thermodynamic results suggested that the adsorption process was a spontaneous and endothermic reaction. The adsorption mechanism was further analyzed by energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (XRD) and extended X-ray absorption fine structure spectroscopy (EXAFS). These data revealed that Na ⁺ ions inside MXene galleries were exchanged by Eu ³⁺ ions and Eu(III) existed dominately in under outer-sphere surface complexation after adsorption under acidic pH conditions, but in inner-sphere surface complexation under near-neutral pH conditions. Due to its cost-effective prepatation and excellent sorption performance, Na-Ti₃C₂T_x may be a promising candidate for the efficient removal of trivalent minor actinides and lanthanides from radioactive wastewater.

Key words: Na-Ti₃C₂T_x, Eu(III), removal, interaction mechanism

CLC Number:

TQ174

SONG Huan, WANG Lin, WANG Hong-Qing, SHI Wei-Qun. Adsorption of Eu(III) on Alkalized Ti₃C₂T_x MXene Studied by Batch Experiment and Its Mechanism Investigation[J]. Journal of Inorganic Materials, 2020, 35(1): 65-72.

Figures/Tables 11

Fig. 1 XRD patterns of the synthesized Ti3AlC2, Ti3C2Tx, Na-Ti3C2Tx and Na-Ti3C2Tx-Eu

Fig. 2 SEM images of Na-Ti3C2Tx before (a-b), and after (c-d) adsorption of Eu(III), with EDS analysis resulted of Na-Ti3C2Tx before (e) and after (f) adsorption of Eu(III)

Fig. 3 Effect of sorbent dose on Eu(III) removal by Na-Ti3C2Tx (pH=(4.0±0.1), C0=20 mg/L)

Fig. 4 Effect of solution pH and ionic strength on removal of Eu(III) by Na-Ti3C2Tx (a), Zeta potential of Na-Ti3C2Tx (b), and distribution of Eu(III) species in aqueous solution as a function of pH calculated using the MEDUSA program (c)

Fig. 5 Time-dependent adsorption of Eu(III) on Na-Ti3C2Tx (pH= (4.0±0.1), T = 293 K, m/V = 0.4 g/L) (a), and pseudo-second- order kinetic plots of Eu(III) on Na-Ti3C2Tx (b)

Table 1 Optimized parameters of pseudo-first-order and pseudo-second-order kinetic models

Sample	Pseudo-first-order model		Pseudo-second-order model
Na-Ti₃C₂T_x	k₁/min^-1	R²	k₂/(g·mg^-1·min^-1)	R²
Na-Ti₃C₂T_x	0.0212	0.4111	0.1312	0.9999

Fig. 6 (a) Isotherms of Na-Ti3C2Tx towards Eu(III) under the conditions of pH (4.0±0.1) and m/V=0.40 g/L, and (b) plot of lnKd vs 1/T

Table 2 Fitting parameters of Langmuir and Freundlich models

Models	Parameters	Temperature/K
Models	Parameters	298	306	314	322
Langmuir	q_m/(mg·g^-1)	54.05	57.14	66.67	88.50
	K_L/(L·mg^-1)	0.49	5.00	3.49	1.04
	R²	0.9931	0.9999	0.9981	0.9973
Freundlich	K_F/(mg^1-ⁿ·Lⁿ·g^-1)	33.52	40.87	50.37	60.87
	1/n	9.78	10.50	10.88	10.92
	R²	0.9436	0.9487	0.9212	0.9645

Table 3 Thermodynamic parameters for removal of Eu(III) by Na-Ti3C2Tx

Temperature/K	ΔH/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)	ΔG/(kJ·mol^-1)
298	24.539	134.81	-15.57
306			-16.65
314			-17.73
322			-18.80

Fig. 7 (A) Eu L 3 edge k3-weighted EXAFS spectra (solid lines) and the best theoretical fits (dots lines) of Eu-loaded Na-Ti3C2Tx samples under different solution pH, and (B) corresponding non-phase shift corrected Fourier transforms

Table 4 Fitting parameters extracted from least-squares fitting analysis of EXAFS spectra

Sample	Path	CN^a	R^b/nm	σ^2c/(×10^-4, nm²)	ΔE^d/eV	R-factor^e
Eu³⁺(aq)	Eu-O	(9.0±0.6)	(0.243±0.001)	0.8	(3.9±0.6)	0.006
pH=4.0	Eu-O	(9.1±1.6)	(0.243±0.002)	0.9	(2.4±1.6)	0.019
pH=5.0	Eu-O	(8.7±1.4)	(0.243±0.001)	0.9	(2.6±1.5)	0.016
pH=6.0	Eu-O	(7.8±0.9)	(0.242±0.001)	1.0	(2.2±1.1)	0.008

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Adsorption of Eu(III) on Alkalized Ti₃C₂T_x MXene Studied by Batch Experiment and Its Mechanism Investigation

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