原位法制备石墨相碳/TiO<sub>2</sub>复合光催化剂及其高效降解新兴酚类污染物性能

引用本文: 刘云庆, 夏培玉, 李凌宇, 王欣月, 孟佳琪, 杨雨昕, 郭伊荇. 原位法制备石墨相碳/TiO₂复合光催化剂及其高效降解新兴酚类污染物性能[J]. 催化学报, 2020, 41(9): 1378-1392. doi: 10.1016/S1872-2067(20)63565-3 shu

Citation: Yunqing Liu, Peiyu Xia, Lingyu Li, Xinyue Wang, Jiaqi Meng, Yuxin Yang, Yihang Guo. In-situ route for the graphitized carbon/TiO₂ composite photocatalysts with enhanced removal efficiency to emerging phenolic pollutants[J]. Chinese Journal of Catalysis, 2020, 41(9): 1378-1392. doi: 10.1016/S1872-2067(20)63565-3 shu

原位法制备石墨相碳/TiO₂复合光催化剂及其高效降解新兴酚类污染物性能

东北师范大学环境学院, 吉林长春 130117
基金项目:
国家自然科学基金（21573038，51608102）.

摘要: 绿色光催化技术在可持续水处理和环境修复领域具有广阔的应用前景.光催化效率在很大程度上取决于光催化剂，其中二氧化钛（TiO₂）因具有超强的光氧化能力、化学稳定性和低成本等优点而广泛应用于光催化降解水中各类有机污染物.然而，TiO₂的光催化效率仍然受限于其自身比表面积小、太阳光利用率低以及光生载流子复合速率快等缺点.
为了克服以上缺点，进一步提高TiO₂的光催化效率，本研究采用简单易行的原位共缩合结合水热处理技术，以葡萄糖为碳源，四异丙氧基钛（TTIP）为钛源，成功制备了一系列由锐钛矿相TiO₂与石墨相碳组成的TiO₂/C复合光催化剂，它们在水中新兴酚类污染物的降解中表现出了优异的可见光光催化活性.通过X射线衍射、热重分析、X射线光电子能谱、孔隙率分析、扫描电镜、透射电镜、紫外-可见漫反射光谱等表征手段对催化剂的组成和结构、形貌、孔隙率性质及光吸收特性进行了表征.结果显示，TiO₂/C复合光催化剂具有独特的微孔/介孔结构，以及比TiO₂更大的比表面积（222-263m² g^-1）和更窄的带隙能（2.50-2.77eV）.
通过水中新兴酚类污染物如乙酰氨基酚（APAP）和对羟基苯甲酸甲酯（MPB）的可见光光催化降解实验研究了TiO₂/C的光催化性能.结果显示，TiO₂/C复合光催化剂表现出优于纯TiO₂和商用P25-TiO₂的可见光光催化活性.其中，性能最佳的TiO₂/C-10.3（碳掺杂量为10.3%）在可见光照射下20min即可完全降解APAP，180min可降解90%以上的MPB；TiO₂/C-10.3光催化降解APAP和MPB的表观速率常数分别是纯TiO₂的7.6和2.8倍，是商用P25-TiO₂的6.2和2.6倍.TiO₂/C复合光催化剂表现出良好的稳定性，能够在完成五次光催化循环实验后仍然保持其良好的光催化活性.
通过光电化学实验、间接化学探针测试和电子自旋共振光谱分析并结合表征结果，揭示了TiO₂/C可见光光催化活性提高的原因.首先，石墨相碳的掺入降低了材料的带隙能，拓宽了材料的可见光吸收范围，同时石墨相碳可作为电子阱促进光生电子从TiO₂的价带转移到自身，从而有效抑制光生载流子的复合；其次，在复合催化剂中，锐钛矿相TiO₂与石墨相碳密切接触有利于光生载流子的有效分离，也可起到抑制光生载流子复合的作用；最后，复合催化剂较大的比表面积和独特的微孔/介孔双孔结构为APAP和MPB降解反应提供了充足活性位点，同时入射光在孔道内多次反射又进一步提高了催化剂对光能的利用率.在TiO₂/C光催化降解体系中检测到的主要活性物种有羟基自由基、光生空穴和超氧自由基，三者共同参与APAP和MPB的降解和矿化过程.通过对光催化降解中间产物的分析，分别提出了TiO₂/C复合光催化剂可见光催化降解APAP和MPB的路径.
本研究为设计高效降解水中有机污染物的碳掺杂TiO₂光催化材料提供了新思路.

关键词:

English

In-situ route for the graphitized carbon/TiO₂ composite photocatalysts with enhanced removal efficiency to emerging phenolic pollutants

School of Environment, Northeast Normal University, Changchun 130117, Jilin, China
Received Date: 17 January 2020
Revised Date: 23 February 2020
Fund Project:
This work was supported by the National Natural Science Foundation of China (21573038 and 51608102).

Abstract: TiO₂ is the most photoactive material because of its superstrong photooxidizing ability, and TiO₂ photocatalysis has been widely applied in sustainable water treatment and environmental remediation. However, poor sunlight or visible-light harvesting efficiency and fast recombination rate of the photogenerated charge carriers severely limit the practical applications of TiO₂. To overcome these problems, the present work demonstrates a facile in-situ co-condensation method combined with hydrothermal treatment to prepare a series of graphitized carbon/TiO₂ composite photocatalysts, and anatase TiO₂ phase and p-p-conjugated polycyclic aromatic carbon structure are created simultaneously. As-prepared TiO₂/C composites exhibit remarkably high visible-light photocatalytic activity in the degradation of aqueous emerging phenolic pollutants, acetaminophen (APAP) and methylparaben (MPB), and apparent rate constant of the TiO₂/C composite with carbon doping level of 10.3% for APAP and MPB removal is 7.6 and 2.8 times higher than that of bare TiO₂, and 6.2 and 2.6 times higher than that of Degussa P25 TiO₂. Based on the results of photoelectrochemical experiments, indirect chemical probe measurements, and ESR spectroscopy, it is verified that doping TiO₂ with graphitized carbon is responsible for this enhanced photocatalytic activity, which renders the improved visible-light harvesting ability, the accelerated separation of the photogenerated charge carriers, and enlarged BET surface areas. Through analyzing the intermediates yielded in the photodegradation process, the pathway of visible-light photocatalytic degradation of APAP and MPB over the TiO₂/C composite is proposed.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

原位法制备石墨相碳/TiO₂复合光催化剂及其高效降解新兴酚类污染物性能

English

In-situ route for the graphitized carbon/TiO₂ composite photocatalysts with enhanced removal efficiency to emerging phenolic pollutants

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中国化学会秘书处

原位法制备石墨相碳/TiO2复合光催化剂及其高效降解新兴酚类污染物性能

English

In-situ route for the graphitized carbon/TiO2 composite photocatalysts with enhanced removal efficiency to emerging phenolic pollutants

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原位法制备石墨相碳/TiO₂复合光催化剂及其高效降解新兴酚类污染物性能

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