Nanocrystalline CeO2-ZrO2 Solid Solution: One-step Alcohothermal Synthesis and Arsenic Removal Performance

doi:10.15541/jim20250011

Abstract

Abstract:

CeO₂-ZrO₂ solid solution is generally synthesized through chemical precipitation, followed by high-temperature calcination. However, their grains under high-temperature calcination are prone to aggregate and grow, resulting in lower specific surface area, weaker adsorption and poorer catalytic performance. In this study, nanocrystalline CeO₂-ZrO₂ solid solutions were prepared by a simple one-step alcohothermal method, avoiding effects of high-temperature calcination on grain growth and specific surface area reduction. Crystal structure, morphologies and thermal stability of the synthesized CeO₂-ZrO₂ solid solutions were characterized, and arsenic removal performance was determined. The results show that the grains in nanocrystalline CeO₂-ZrO₂ solid solutions grow sufficiently with large specific surface areas, high particle purity and good dispersibility, leading to improved adsorption effect on As(III) in water. The arsenic adsorption results show that maximum adsorption capacity of Ce_0.8Zr_0.2O₂ sample can reach 160 mg/g at an As(III) equilibrium solubility of 95 mg/L, which is much higher than pure CeO₂ and ZrO₂ samples, as well as CeO₂-ZrO₂ solid solution prepared by traditional calcination method. In addition, the prepared Ce_0.8Zr_0.2O₂ solid solution maintains a high As(III) removal rate and good acid-alkali resistance within pH range of 3-9. The arsenic adsorption mechanisms indicate that As(III) ions in the solution form coordination bonds with metal ions on the surface of Ce_0.8Zr_0.2O₂solid solution, which belongs to the chemical adsorption process.

Key words: alcohothemal, CeO₂-ZrO₂ solid solution, arsenic removal performance, adsorption mechanism

CLC Number:

O611

LI Ronghui, QIAN Jun. Nanocrystalline CeO₂-ZrO₂ Solid Solution: One-step Alcohothermal Synthesis and Arsenic Removal Performance[J]. Journal of Inorganic Materials, 2025, 40(9): 989-996.

Figures/Tables 13

Fig. 1 XRD patterns of CeO2、ZrO2 and CeO2-ZrO2 solid solutions

Table 1 Lattice parameters and specific surface areas of CeO2, ZrO2 and CeO2-ZrO2 solid solutions

Sample	Interplanar spacing/Å				D/nm	S_BET/ (m²·g^-1)
Sample	d₍₁₁₁₎	d₍₂₀₀₎	d₍₂₂₀₎	d₍₃₁₁₎	D/nm	S_BET/ (m²·g^-1)
CeO₂	3.19	2.71	1.91	1.61	7.7	184.1
Ce_0.8Zr_0.2O₂	3.14	2.65	1.85	1.53	4.3	270.6
Ce_0.6Zr_0.4O₂	3.09	2.60	1.81	1.50	5.1	256.2
Ce_0.4Zr_0.6O₂	3.05	2.54	1.75	1.46	5.9	250.8
Ce_0.2Zr_0.8O₂	3.01	2.48	1.71	1.40	6.2	235.1
ZrO₂	2.96	2.45	1.65	1.36	8.9	198.5

Fig. 2 Relationships between interplanar spacing and Zr4+ contents

Fig. 3 Microscopic morphology of Ce0.8Zr0.2O2 solid solution (a) SEM image and EDS mappings; (b) TEM and HRTEM images

Fig. 4 TG-DSC curves of Ce0.8Zr0.2O2 solid solution

Fig. 5 As(III) adsorption kinetics curves of CeO2, ZrO2 and CeO2-ZrO2 solid solutions

Table 2 Fitting parameters of pseudo second order kinetics model

Sample	h/ (mg·g^-1·min^-1)	k₂/ (g·mg^-1·min^-1)	q_e/ (mg·g^-1)	R²
CeO₂	0.3255	0.0911	1.8641	0.9947
Ce_0.8Zr_0.2O₂	0.2974	0.0816	2.0140	0.9951
Ce_0.6Zr_0.4O₂	0.2135	0.0803	1.7547	0.9905
Ce_0.4Zr_0.6O₂	0.1842	0.0795	1.5045	0.9982
Ce_0.2Zr_0.8O₂	0.1557	0.0714	1.4511	0.9911
ZrO₂	0.1095	0.0598	1.2987	0.9961

Fig. 6 Freundlich equilibrium adsorption isotherms of As(III) onto CeO2, ZrO2, Ce0.8Zr0.2O2, and CZ450 solid solutions

Table 3 Fitting parameters of Freundlich adsorption model

Sample	q_e/(mg·g^-1)	K_F	N	R²
Ce_0.8Zr_0.2O₂	163	30.34	2.685	0.9840
CeO₂	120	23.41	2.758	0.9908
ZrO₂	69	12.07	2.613	0.9840
CZ450	54	10.53	2.613	0.9908

Fig. 7 Effect of pH on arsenic adsorption performance and ion release of Ce0.8Zr0.2O2 solid solution

Fig. 8 Desorption and regeneration performance of Ce0.8Zr0.2O2 solid solution

Fig. 9 FT-IR spectra of Zr0.2Ce0.8O2 solid solution before and after As(III) adsorption

Fig. 10 O1s XPS spectra of Ce0.8Zr0.2O2 solid solution before (a) and after (b) As(III) adsorption

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Nanocrystalline CeO₂-ZrO₂ Solid Solution: One-step Alcohothermal Synthesis and Arsenic Removal Performance

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