一步醇热法制备纳米CeO2-ZrO2固溶体及其除砷性能

doi:10.15541/jim20250011

摘要/Abstract

摘要：

CeO₂-ZrO₂固溶体的制备一般通过化学沉淀和高温焙烧两步完成, 但是在高温条件下, 纳米晶粒容易聚集长大, 导致其比表面积降低, 进而削弱了其吸附和催化性能。本研究通过简单的一步醇热法制备出高比表面积的纳米CeO₂-ZrO₂固溶体, 避免了高温焙烧对晶粒长大和比表面积降低的影响。采用不同手段对制备的CeO₂-ZrO₂固溶体的晶体结构、微观形貌以及热稳定性进行表征, 并测试其除砷(As)性能。结果表明, 本研究制备的纳米CeO₂-ZrO₂固溶体晶粒发育完整, 粒子纯度高、分散性好, 对水中As(III)具有良好的吸附效果。其中, Ce_0.8Zr_0.2O₂样品在As(III)平衡溶度为95 mg/L时的饱和吸附量可达163 mg/g, 高于纯CeO₂和ZrO₂样品, 也远高于采用传统焙烧法制备的CeO₂-ZrO₂固溶体, 并且该吸附材料在pH 3~9范围内一直保持较高的As(III)去除率以及良好的耐酸碱性能。吸附机理研究表明, 溶液中As(III)离子与Ce_0.8Zr_0.2O₂固溶体表面金属离子形成配位键, 该过程属于化学吸附。

关键词: 醇热法, CeO₂-ZrO₂固溶体, 除砷性能, 吸附机理

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

中图分类号:

O611

李荣辉, 钱骏. 一步醇热法制备纳米CeO₂-ZrO₂固溶体及其除砷性能[J]. 无机材料学报, 2025, 40(9): 989-996.

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.

图/表 13

图1 CeO2、ZrO2以及CeO2-ZrO2固溶体的XRD图谱

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

表1 CeO2、ZrO2以及CeO2-ZrO2固溶体的晶格参数与比表面积

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

图2 晶面间距与Zr4+含量的关系

Fig. 2 Relationships between interplanar spacing and Zr4+ contents

图3 Ce0.8Zr0.2O2固溶体的微观形貌

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

图4 Ce0.8Zr0.2O2固溶体的TG-DSC曲线

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

图5 CeO2、ZrO2以及CeO2-ZrO2固溶体的As(III)吸附动力学曲线

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

表2 准二级动力学模型拟合参数

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

图6 As(III)在CeO2、ZrO2、Ce0.8Zr0.2O2以及CZ450固溶体上的Freundlich等温吸附曲线

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

表3 Freundlich吸附模型拟合参数

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

图7 pH对Ce0.8Zr0.2O2固溶体的砷吸附性能和离子溶出的影响

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

图8 Ce0.8Zr0.2O2固溶体的脱附与再生性能

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

图9 As(III)吸附前后Ce0.8Zr0.2O2固溶体的FT-IR图谱

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

图10 As(III)吸附前(a)后(b) Ce0.8Zr0.2O2固溶体的O1s XPS图谱

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

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一步醇热法制备纳米CeO₂-ZrO₂固溶体及其除砷性能

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

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