Rod-Shaped Metal Organic Framework Structured PCN-222(Cu)/TiO<sub>2</sub> Composites for Efficient Photocatalytic CO<sub>2</sub> Reduction

Citation: Duan Shuhua, Wu Shufeng, Wang Lei, She Houde, Huang Jingwei, Wang Qizhao. Rod-Shaped Metal Organic Framework Structured PCN-222(Cu)/TiO₂ Composites for Efficient Photocatalytic CO₂ Reduction[J]. Acta Physico-Chimica Sinica, 2020, 36(3): 1905086-0. doi: 10.3866/PKU.WHXB201905086 shu

棒状金属有机框架结构PCN-222(Cu)/TiO₂复合材料的制备及其高效光催化CO₂还原性能

段树华 ^1, ,
巫树锋 ^2, ,
王磊 ^{1,
,} ,
佘厚德 ^1, ,
黄静伟 ^1, ,
王其召 ^{1,
,}

1.
西北师范大学化学化工学院，生态环境相关高分子材料教育部重点实验室，兰州 730070
2.
中国石油兰州化工研究中心，石油石化污染控制与处理国家重点实验室，兰州 730060

通讯作者: 王磊, wanglei030@hotmail.com
王其召, wangqizhao@163.com

基金项目:
国家自然科学基金(21663027, 21808189)资助项目

国家自然科学基金 21663027

国家自然科学基金 21808189

摘要: 受环境污染和能源短缺的双重压迫，光催化CO₂还原技术引起了人们的广泛关注。低成本光催化材料的开发对于实现有效的太阳能-燃料转换至关重要。TiO₂作为光催化剂在光催化CO₂还原中被广泛采用。然而，较宽的禁带宽度和光生载流子的复合限制了它的进一步应用。在这项工作中，我们使用棒状PCN-222(Cu)/TiO₂复合材料作为光催化剂，使用简单的水热法报告了二氧化碳的光化学还原。经过对PCN-222(Cu)/TiO₂进行一系列X射线衍射(XRD)，扫描电子显微镜(SEM)，紫外-可见漫反射光谱(DRS)，傅里叶变换红外光谱(FT-IR)，光电化学(PEC)和光致发光光谱(PL)等表征结果证明成功制备了该复合材料。SEM证实，TiO₂颗粒均匀分布在棒状PCN-222(Cu)/TiO₂的表面上。XRD结果表明，成功制备了具有良好晶体结构的PCN-222(Cu)和PCN-222(Cu)/TiO₂复合光催化剂。DRS显示制备的PCN-222(Cu)/TiO₂复合材料在可见光区域出现金属卟啉的特征吸收峰。PL和瞬态光电流响应和电化学阻抗谱(EIS)进一步证实了棒状PCN-222(Cu)/TiO₂具有更好的电子-空穴对分离效率。通过控制PCN-222(Cu)和TiO₂的质量比，经CO₂还原性能测试表明，10% PCN-222(Cu)/TiO₂复合材料具有最佳的催化活性。在氙灯照射下，棒状PCN-222(Cu)/TiO₂表现出比TiO₂纳米颗粒更好的光催化CO₂活性，这归因于电荷传输和较好的电子-空穴分离能力。10% PCN-222(Cu)/TiO₂复合材料的催化效率最高，产率分别为13.24 μmol·g⁻¹·h⁻¹ CO和1.73 μmol·g⁻¹·h⁻¹ CH₄。此外，经过三个循环的测试，PCN-222(Cu)/TiO₂光催化剂的催化活性基本保持不变，在连续8小时光照下，催化剂的还原产率持续增加，表明PCN-222(Cu)/TiO₂复合材料具有好的稳定性。禁带宽度和Mote-Schottky (M-S)曲线结果表明，PCN-222(Cu)的LUMO位比TiO₂的导带(CB)更负，因此提出了PCN-222(Cu)/TiO₂复合材料可能的光催化反应机理。该研究为金属有机骨架和氧化物半导体复合材料光催化体系提供了新的策略。

关键词:

English

Rod-Shaped Metal Organic Framework Structured PCN-222(Cu)/TiO₂ Composites for Efficient Photocatalytic CO₂ Reduction

Duan Shuhua ^1, ,
Wu Shufeng ^2, ,
Wang Lei ^{1,
,} ,
She Houde ^1, ,
Huang Jingwei ^1, ,
Wang Qizhao ^{1,
,}

1.
College of Chemistry and Chemical Engineering, Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of China, Northwest Normal University, Lanzhou 730070, P. R. China
2.
State Key Laboratory of Petroleum and Petrochemical Pollution Control and Processing, Lanzhou Petrochemical Research Center, PetroChina, Lanzhou 730060, P. R. China

Corresponding author: Wang Lei, wanglei030@hotmail.com Wang Qizhao, wangqizhao@163.com

Received Date: 31 May 2019
Accepted Date: 24 June 2019
Revised Date: 24 June 2019
Available Online: 15 March 2020
Fund Project:
the National Natural Science Foundation of China (21663027, 21808189)

the National Natural Science Foundation of China 21663027

the National Natural Science Foundation of China 21808189

Abstract: The photocatalytic reduction of CO₂ has attracted considerable attention owing to the dual suppression of environmental pollution and energy shortage. The technology uses solar energy to convert carbon dioxide into hydrocarbon fuel, which is of great significance for achieving the carbon cycle. The development of low-cost photocatalytic materials is critical to achieving efficient solar energy to fuels conversion. One of the most commonly employed photocatalysts is TiO₂. However, it suffers from broad band gap as well as the recombination of photo-excited holes and electron. Hence, in this work, we report the photochemical reduction of CO₂ using rod-like PCN-222(Cu)/TiO₂ composites as photocatalyst through a simple hydrothermal method, in which TiO₂ nanoparticles are anchored at the interface of the SiC rod PCN-222(Cu). Multiple characterization techniques were used to analyze the structure, morphology, and properties of the PCN-222(Cu)/TiO₂ composite. A series of characterizations including X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), Fourier-transform infrared spectroscopy, photo-electrochemical, and photoluminescence (PL) confirm the successful preparation of PCN-222(Cu)/TiO₂ composites. SEM reveals that the TiO₂ nanoparticles are uniformly distributed on the surface of the rod-shaped PCN-222(Cu)/TiO₂. XRD results show that PCN-222(Cu) and PCN-222(Cu)/TiO₂ composite photocatalysts with good crystal structure were successfully synthesized. According to the DRS results, the prepared PCN-222(Cu)/TiO₂ composite samples exhibit characteristic absorption peaks of metalloporphyrins in the visible region. PL spectroscopy, transient photocurrent response, and electrochemical impedance spectroscopy further confirm that the rod-like PCN-222(Cu)/TiO₂ samples have high electron-hole pair separation efficiency. By controlling the mass ratio of PCN-222(Cu) and TiO₂, the photocatalytic CO₂ reduction performance test shows that the 10% PCN-222(Cu)/TiO₂ composite achieves optimal catalytic performance, yielding 13.24 μmol·g⁻¹·h⁻¹ CO and 1.73 μmol·g⁻¹·h⁻¹ CH₄, respectively. All the rod-like PCN-222(Cu)/TiO₂ composites exhibit better photocatalytic CO₂ activity than that of TiO₂ nanoparticles or PCN-222(Cu) under the illumination of xenon lamps, which is attributed to charge transport and electron-hole separation capabilities. After three test cycles, the catalytic activity of PCN-222(Cu)/TiO₂ photocatalyst was virtually unchanged. The reduction yield of the catalyst increased for 8 h under continuous illumination, indicating that PCN-222(Cu)/TiO₂ composites have acceptable stability. The estimation of the band gap curve and the Mote-Schottky curve test show that the lowest unoccupied molecular orbital position of PCN-222(Cu) is more negative than the TiO₂ of the conduction band; hence, a possible photocatalytic reaction mechanism of the PCN-222(Cu)/TiO₂ composite is proposed. This study provides a new strategy for the integration of metal-organic frameworks and oxide semiconductors to construct efficient photocatalytic systems.

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