湿化学法制备Cu2O/Cu空心球异质结光催化剂

doi:10.15541/jim20240370

摘要/Abstract

摘要：

窄带隙半导体作为可见光光催化剂, 可以有效地将太阳能转化为化学能, 在缓解能源短缺和环境污染方面具有潜在的应用前景。以氯化铜(CuCl₂·H₂O)为前驱体, 盐酸羟胺(H₃NO·HCl)和硼氢化钠(NaBH₄)为还原剂, 采用一锅无模板湿化学还原法制备Cu₂O/Cu空心球异质结光催化剂。采用不同表征手段对样品形貌、晶体结构、组成、比表面积和光学性质进行分析。加入NaBH₄使Cu₂O/Cu形貌从中空截角八面体逐渐演化为中空纳米球。通过改变NaBH₄加入量可以控制Cu₂O表面Cu层厚度。NaBH₄直接还原Cu₂O使Cu₂O和Cu界面紧密结合, 这有利于载流子分离和传输, Cu的表面等离子体共振(SPR)效应使Cu₂O/Cu对可见光的吸收能力增强, 因此Cu₂O/Cu对甲基橙(MO)和无色恩诺沙星(ENR)均表现出良好的光催化活性。连续循环使用5次, Cu₂O/Cu对MO的降解率影响不大。捕获实验表明∙O₂^-和空穴是降解MO过程中主要的活性物质。Cu₂O/Cu的良好光催化活性归因于Cu₂O和Cu的协同作用。本研究为异质结光催化剂的制备提供了一种策略。

关键词: Cu₂O/Cu异质结, 纳米空心球, 光催化, Cu层厚度

Abstract:

As visible light photocatalysts, narrow bandgap semiconductors can effectively convert solar energy to chemical energy, exhibiting potential applications in alleviating energy shortage and environmental pollution. Cu₂O/Cu hollow spherical heterojunction photocatalysts were prepared by one-pot solvothermal method without any template using CuCl₂·H₂O as precursor, H₃NO·HCl and NaBH₄ as reducing agents. Morphologies, crystal structures, composition, specific surface areas, and optical properties of the products were analyzed. Addition of NaBH₄ gradually changes the morphology of Cu₂O/Cu from hollow truncated octahedra to hollow nanospheres. Thickness of Cu layer on surface of Cu₂O can be easily controlled by tuning amount of NaBH₄. Direct reduction of Cu₂O by NaBH₄ leads to intimate contact between Cu₂O and Cu interfaces, which is favorable for carrier separation and transport. Meanwhile, surface plasmon resonance effect of Cu promotes the absorption capability of Cu₂O/Cu to visible light, thus the prepared hollow sphere Cu₂O/Cu particles exhibit a higher photodegradation capability for methyl orange (MO) and colorless enrofloxacin (ENR). Catalytic performance of Cu₂O/Cu is very stable, with no significant change in its photocatalytic efficiency for MO after five recycles. Free-radical removal experiments indicate that ∙O₂^- and holes were dominant species during the MO degradation. Higher photodegradation capability of Cu₂O/Cu for MO is attributed to synergistic effect of Cu₂O and Cu. This study provides a promising strategy for preparation of heterojunction photocatalysts.

Key words: Cu₂O/Cu heterojunction, hollow nanosphere, photocatalysis, thickness of Cu layer

中图分类号:

TQ426
O644

贾相华, 张辉霞, 刘艳凤, 左桂鸿. 湿化学法制备Cu₂O/Cu空心球异质结光催化剂[J]. 无机材料学报, 2025, 40(4): 397-404.

JIA Xianghua, ZHANG Huixia, LIU Yanfeng, ZUO Guihong. Cu₂O/Cu Hollow Spherical Heterojunction Photocatalysts Prepared by Wet Chemical Approach[J]. Journal of Inorganic Materials, 2025, 40(4): 397-404.

图/表 12

图1 纯Cu2O和Cu2O/Cu样品的XRD图谱

Fig. 1 XRD patterns of the pure Cu2O and Cu2O/Cu samples

图2 纯Cu2O和Cu2O/Cu样品的SEM照片

Fig. 2 SEM images of the pure Cu2O and Cu2O/Cu samples (a) Pure Cu2O; (b-f) Cu2O/Cu with 50 mL addition of NaBH4 at concentration of (b) 0.0067, (c) 0.0080, (d) 0.0100, (e) 0.0130, and (f) 0.0200 mol/L

图3 Cu2O/Cu-0.0080样品在(a)低倍率和(b)高倍率下的TEM照片

Fig. 3 TEM images of Cu2O/Cu-0.0080 sample at (a) low and (b) high magnifications

图4 Cu2O/Cu-0.0080样品的XPS图谱

Fig. 4 XPS spectra of Cu2O/Cu-0.0080 sample (a) Survey spectrum; (b) Cu2p; (c) Cu-LMM Auger spectrum; (d) O1s

图5 纯Cu2O和Cu2O/Cu样品的紫外-可见漫反射光谱图

Fig. 5 UV-Vis diffuse reflection spectra of the pure Cu2O and Cu2O/Cu samples Colorful figure is available on website

图6 纯Cu2O和Cu2O/Cu样品的PL谱图

Fig. 6 PL spectra of the pure Cu2O and Cu2O/Cu samples

图7 纯Cu2O和Cu2O/Cu样品的N2吸附-脱附等温线

Fig. 7 N2 adsorption-desorption isotherms of the pure Cu2O and Cu2O/Cu samples Colorful figure is available on website

表1 纯Cu2O和Cu2O/Cu样品的比表面积、平均孔径和孔容

Table 1 Specific surface area, average pore diameter and pore volume of the pure Cu2O and Cu2O/Cu samples

Sample	Specific surface area/(cm²·g^-1)	Average pore diameter/nm	Pore volume/ (cm³·g^-1)
Pure Cu₂O	34.23	85.23	0.286
Cu₂O/Cu-0.0067	37.11	55.34	0.279
Cu₂O/Cu-0.0080	39.01	34.24	0.274
Cu₂O/Cu-0.0100	41.19	32.56	0.263
Cu₂O/Cu-0.0130	64.45	30.26	0.246
Cu₂O/Cu-0.0200	88.79	26.35	0.221

图8 纯Cu2O和Cu2O/Cu样品对MO和ENR的催化性能

Fig. 8 Catalytic performance of the pure Cu2O and Cu2O/Cu catalysts for MO and ENR (a) Catalytic degradation curves of the pure Cu2O and Cu2O/Cu catalysts for MO; (b) Fitting plots of pseudo-first-order kinetics; (c) Absorption spectra of Cu2O/Cu-0.0080 catalyst for ENR

图9 Cu2O/Cu-0.0080样品对光催化MO的循环稳定性

Fig. 9 Cycle stability of Cu2O/Cu-0.0080 sample for photocatalysis of MO

图10 纯Cu2O和Cu2O/Cu样品表面温度随时间的变化

Fig. 10 Time-dependent surface temperature changes of the pure Cu2O and Cu2O/Cu samples (a) Time-dependent surface temperature under irradiation with inset showing infrared thermal image of Cu2O/Cu-0.0130 sample irradiated for 8 min; (b) Time-dependent surface temperature during photocatalysis with inset showing infrared thermal image of Cu2O/Cu-0.0130 sample photocatalytic degradation for 30 min

图11 Cu2O/Cu-0.0080样品光催化降解MO的自由基捕获实验

Fig. 11 Free radical capture experiment of Cu2O/Cu-0.0080 sample for photocatalytic degradation of MO

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湿化学法制备Cu₂O/Cu空心球异质结光催化剂

Cu₂O/Cu Hollow Spherical Heterojunction Photocatalysts Prepared by Wet Chemical Approach

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