Page 127 - 《精细化工》2021年第5期

第 38 卷第 5 期 精 细 化 工 Vol.38, No.5
202 1 年 5 月 FINE CHEMICALS May 2021

催化与分离提纯技术
CuO-SiO 气凝胶@TiO 纳米纤维
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无牺牲剂光催化还原 CO
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文 曼 ，任贝贝 ，叶祥志 ，贺建雄 ，熊春荣
（1. 海南大学 南海海洋资源与利用国家重点实验室，海南省特种玻璃重点实验室，海南 海口 570228；
2. 海南海控特玻科技有限公司，海南 澄迈 571900）
摘要：采用溶胶-凝胶法制备 CuO-SiO 2 复合气凝胶，通过在气凝胶孔道内填充 TiCl 4 ，然后将其气相水解，得到
了在 CuO-SiO 2 气凝胶表面生长了高结晶度的 TiO 2 纳米纤维（CuO-SiO 2 @TiO 2 ），纤维直径~16 nm。通过 XPS、UPS、
UV-Vis DRS、荧光光谱（PL）等表征了材料的结构及光电性能。结果表明，制备的 CuO-SiO 2 @TiO 2 对可见光有明显
吸收，且荧光强度较商用 TiO 2 （P25）大幅降低，光生电子-空穴对更加稳定。再在纳米纤维上负载 CuO，所得
CuO-SiO 2 @TiO 2 /CuO 在可见光区的荧光强度进一步增强。以 300 W 氙灯为光源，分别以 CuO-SiO 2 @TiO 2 及
CuO-SiO 2 @TiO 2 /CuO 为催化剂，无牺牲剂条件下光催化还原 CO 2 ，4 h 后甲醇产率分别为 1304.0 及 1589.0 μmol/g-cat，
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转换频率（TOF）分别为 0.038 及 0.046 h 。循环实验表明，纳米纤维具有较好的光催化稳定性，经过 4 次光催
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化循环实验后，CuO-SiO 2 @TiO 2 /CuO 的保留率~94%，甲醇产率可达 1472.0 μmol/g-cat，TOF 为 0.042 h 。
关键词：TiO 2 纳米纤维；光催化；CO 2 还原；无牺牲剂；可见光；催化技术
中图分类号：O69；TQ032 文献标识码：A 文章编号：1003-5214 (2021) 05-0981-07

CuO-SiO 2 aerogel@TiO 2 nanofibers photocatalyzing reduction of

CO 2 without sacrificial agent

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WEN Man , REN Beibei , YE Xiangzhi , HE Jianxiong , XIONG Chunrong
（1. Skate Key Laboratory of Marine Resource Utilization in South China Sea, Special Glass Key Laboratory of Hainan
Province, Hainan University, Haikou 570228, Hainan, China; 2. Hainan Special Glass Technology Co., Ltd., Chengmai
571900, Hainan, China）
Abstract: CuO-SiO 2 composite aerogel was prepared by sol-gel method and then TiCl 4 was filled in the
channel of composite aerogel. TiO 2 nanofibers growth on the surface of CuO-SiO 2 (CuO-SiO 2@TiO 2) with
high crystallinity were obtained with a diameter of about 16 nm by hydrolyzing TiCl 4 in gas phase. The
structure and photoelectric properties of the materials were characterized by XPS, UPS, UV-Vis DRS and
PL. The results showed that compared with the commercial TiO 2 nanoparticles (P25), the prepared
CuO-SiO 2@TiO 2 nanofibers had much lower fluorescence intensity and slower recombination rate of
photogenerated election-hole pairs. CuO was loaded onto the CuO-SiO 2@TiO 2 nanofibers to obtain
CuO-SiO 2@TiO 2/CuO nanofibers. The fluorescence intensity of the CuO-SiO 2@TiO 2/CuO was further
increased. Photocatalytic reduction of CO 2 was carried out in the absence of sacrificial agent using a 300 W
xenon lamp as light source for 4 h. CuO-SiO 2@TiO 2 and CuO-SiO 2@TiO 2/CuO were used as
photocatalysts, the corresponding methanol yield was 1304.0 and 1589.0 μmol/g-cat. Turnover frequency

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(TOF) was 0.038 and 0.046 h , respectively. The cyclic experiments indicated that the nanofibers had good
photocatalytic stability. After 4 cycles, the retention rate of CuO-SiO 2@TiO 2/CuO was ~94%, and the
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methanol yield was 1472.0 μmol/g-cat, TOF was 0.042 h .
Key words: TiO 2 nanofibers; photocatalysis; reduction of CO 2; without sacrificial agent; visible light;
catalysis technology

收稿日期：2021-02-01; 定用日期：2021-03-25; DOI: 10.13550/j.jxhg.20210119
基金项目：国家自然科学基金（ZDYF2020015，51761010）；海南大学科研平台建设（ZY2019HN09）
作者简介：文 曼（1995—），女，硕士生，E-mail：247876601@qq.com。联系人：熊春荣（1973—），男，教授，E-mail：bearcr@hainanu.edu.cn。