水解法制备二氧化硅包裹氧化亚铜及其抗氧化性能研究

doi:10.16552/j.cnki.issn1001-1625.2025.0870

摘要/Abstract

摘要：

本研究以Cu₂O为内核原料，正硅酸乙酯（TEOS）为硅源，采用水解法成功制备出具有核壳结构的SiO₂包裹Cu₂O试样（Cu₂O@SiO₂）。利用X射线衍射（XRD）、透射电子显微镜（TEM）、能谱仪（EDS）、傅里叶变换红外光谱（FT-IR）和综合热分析（DSC-TG）系统表征了试样的显微结构和抗氧化性能。结果表明，在反应温度为45 ℃、NH₃·H₂O浓度为3.96%（质量分数）、TEOS浓度为3.84%（质量分数）的条件下制备的Cu₂O@SiO₂，经380 ℃氧化气氛热处理后，Cu₂O仍为主晶相。相较于未包裹处理的纯相Cu₂O，Cu₂O@SiO₂的氧化起始温度由230 ℃提高至385 ℃，提高了155 ℃。

关键词: Cu₂O, SiO₂, 包裹, 核壳结构, 抗氧化性能

Abstract:

This study successfully prepared the SiO₂ coated Cu₂O samples （Cu₂O@SiO₂） with a core-shell structure via a hydrolysis method， using Cu₂O as the core material and tetraethyl orthosilicate （TEOS） as the silicon source. The microstructure and oxidation resistance of the samples were systematically characterized by X-ray diffraction （XRD）， transmission electron microscopy （TEM）， energy dispersive spectroscopy （EDS）， Fourier transform infrared spectroscopy （FT-IR）， and simultaneous DSC-TG analysis. The results indicate that the Cu₂O@SiO₂ prepared under the conditions of a reaction temperature of 45 ℃， NH₃·H₂O concentration of 3.96% （mass fraction）， and TEOS concentration of 3.84% （mass fraction） retained Cu₂O as the primary crystalline phase even after heat treatment at 380 ℃ in an oxidizing atmosphere. Compared to uncoated pure Cu₂O， the initial oxidation temperature of the Cu₂O@SiO₂ increases from 230 ℃ to 385 ℃， representing an improvement of 155 ℃.

Key words: Cu₂O, SiO₂, coating, core-shell structure, oxidation resistance

中图分类号:

TB321

杨月, 苗立锋, 江新民, 廖羚辰, 包镇红. 水解法制备二氧化硅包裹氧化亚铜及其抗氧化性能研究[J]. 硅酸盐通报, 2026, 45(2): 625-633.

YANG Yue, MIAO Lifeng, JIANG Xinmin, LIAO Lingchen, BAO Zhenhong. Preparation of SiO₂-Coated Cu₂O via Hydrolysis Method and Study on Its Oxidation Resistance[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2026, 45(2): 625-633.

图/表 11

图1 Cu2O@SiO2制备工艺流程图

Fig.1 Preparation process flow diagram of Cu2O@SiO2

图2 不同NH3·H2O浓度制备的Cu2O@SiO2的TEM照片

Fig.2 TEM images of Cu2O@SiO2 fabricated with different NH3·H2O concentrations

图3 A-3试样的STEM-EDS mapping照片

Fig.3 STEM-EDS mapping images of sample A-3

图4 不同NH3·H2O浓度制备的Cu2O@SiO2的DSC-TG曲线

Fig.4 DSC-TG curves of Cu2O@SiO2 fabricated with different NH3·H2O concentrations

表1 不同NH3·H2O浓度制备的Cu2O@SiO2的关键TG数据

Table 1 Key TG data of Cu2O@SiO2 fabricated with different NH3·H2O concentrations

Sample No.	Oxidation onset temperature/℃	Oxidation offset temperature/℃	Oxidative mass gain/%
Cu₂O	230	392	10.84
A-1	327	531	7.42
A-2	334	546	4.80
A-3	352	562	5.66
A-4	343	552	5.10

图5 A-3试样的FI-IR谱

Fig.5 FT-IR spectrum of sample A-3

图6 不同TEOS浓度制备的Cu2O@SiO2的XRD谱

Fig.6 XRD patterns of Cu2O@SiO2 fabricated with different TEOS concentrations

图7 不同TEOS浓度制备的Cu2O@SiO2的DSC-TG曲线

Fig.7 DSC-TG curves of Cu2O@SiO2 fabricated with different TEOS concentrations

表2 不同TEOS浓度制备的Cu2O@SiO2的关键TG数据

Table 2 Key TG data of Cu2O@SiO2 fabricated with different TEOS concentrations

Sample No.	Oxidation onset temperature/℃	Oxidation offset temperature/℃	Oxidative mass gain/%
B-1	328	563	7.28
B-2	348	558	5.78
B-3	352	562	5.66
B-4	385	595	5.26
B-5	357	572	3.34

图8 B-4在不同温度下煅烧后的XRD谱

Fig.8 XRD patterns of sample B-4 calcined at different temperatures

图9 Cu2O在不同温度下煅烧后的XRD谱

Fig.9 XRD patterns of Cu2O calcined at different temperatures

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