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

doi:10.1016/S1872-2067(20)63565-3

摘要/Abstract

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: 二氧化钛, 碳, 可见光光催化, 复合材料, 酚类化合物, 水处理

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: Titanium dioxide, Carbon, Visible-light photocatalysis, Composite, Phenolic compound, Water treatment

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.

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.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63565-3

https://www.cjcatal.com/CN/Y2020/V41/I9/1378

参考文献

[1] M. Nasr, C. Eid, R. Habchi, P. Miele, M. Bechelany, ChemSusChem, 2018, 11, 3023-3047.
[2] P. Rokicka-Konieczna, A. Markowska-Szczupak, E. Kusiak-Nejman, A. W. Morawski, Chem. Eng. J, 2019, 372, 203-215.
[3] M. Baca, W. Kuku?ka, K. Cendrowski, E. Mijowska, R. J. Kaleńczuk, B. Zielińska, ChemSusChem, 2019, 12, 612-620.
[4] M. D. Hernández-Alonso, F. Fresno, S. Suárez, J. M. Coronado, Energy Environ. Sci., 2009, 2, 1231-1257.
[5] W. Guo, Q. Qin, L. Geng, D. Wang, Y. H. Guo, Y. X. Yang, J. Hazard. Mater., 2016, 308, 374-385.
[6] W. J. Ong, L. L. Tan, Y. H. Ng, S. T. Yong, S. P. Chai, Chem. Rev., 2016, 116, 7159-7329.
[7] K. S. Lakhi, D. H. Park, K. Al-Bahily, W. Cha, B. Viswanathan, J. H. Choy, A. Vinu, Chem. Soc. Rev., 2017, 46, 72-101.
[8] J. Q. Meng, X. Y. Wang, X. Yang, A. Hu, Y. H. Guo, Y. X. Yang, Appl. Catal. B, 2019, 251, 168-180.
[9] G. Liu, L. Wang, H. G. Yang, H. M. Cheng, G. Q. M. Lu, J. Mater. Chem., 2010, 20, 831-843.
[10] B. Liu, J. Yang, X. Zhao, J. Yu, Phys. Chem. Chem. Phys., 2017, 19, 8866-8873.
[11] K. Qi, B. Cheng, J. Yu, W. Ho, Chin. J. Catal., 2017, 38, 1936-1955.
[12] B. Liu, X. Zhao, C. Terashima, A. Fujishima, K. Nakata, Phys. Chem. Chem. Phys., 2014, 16, 8751-8760.
[13] M. Nasrollahzadeh, S. M. Sajadi, J. Colloid Interface Sci., 2016, 465, 121-127.
[14] Z. Jiang, X. Liang, Y. Liu, T. Jing, Z. Wang, X. Zhang, B. Huang, Appl. Catal. B, 2017, 211, 252-257.
[15] Z. Jiang, D. Jiang, Z. Yan, D. Liu, K. Qian, J. Xie, Appl. Catal. B, 2015, 170, 195-205.
[16] Y. He, L. Zhang, B. Teng, M. Fan, Environ. Sci. Technol., 2014, 49, 649-656.
[17] H. Wang, Y. Wu, M. Feng, W. Tu, T. Xiao, T. Xiong, H. X. Ang, X. Z. Yuan, J. W. Chew, Water Res., 2018, 144, 215-225.
[18] R. Hao, G. Wang, H. Tang, L. Sun, C. Xu, D. Han, Appl. Catal. B, 2016, 187, 47-58.
[19] B. Chai, T. Peng, J. Mao, K. Li, L. Zan, Chem. Chem. Phys., 2012, 14, 16745-16752.
[20] E. Kusiak-Nejman, A. W. Morawski, Appl. Catal. B, 2019, 253, 179-186.
[21] X. Y. Wang, Y. N. Sun, L. Yang, Q. K. Shang, D. Wang, T. T. Guo, Y. H. Guo, Sci. Total Environ., 2019, 656, 1010-1020.
[22] Q. Xiang, J. Yu, M. Jaroniec, J. Phys. Chem. C, 2011, 115, 7355-7363.
[23] B. Chai, X. Liao, F. Song, H. Zhou, Dalton Trans., 2014, 43, 982-989.
[24] S. Liu, J. Ke, H. Sun, J. Liu, M. O. Tade, S. Wang, Appl. Catal. B, 2017, 204, 358-364.
[25] Q. Huang, S. Tian, D. Zeng, X. Wang, W. Song, Y. Li, C. Xie, ACS Catal., 2013, 3, 1477-1485.
[26] A. Yadav, M. Yadav, S. Gupta, Y. Popat, A. Gangan, B. Chakraborty, L. M. Ramaniah, R. Fernandes, A. Miotello, M. R. Press, N. Patel, Carbon, 2019, 143, 51-62.
[27] Y. Huang, D. L. Huang, L. Qin, G. M. Zeng, C. Lai, M. Cheng, S. J. Ye, B. Song, X. Y. Ren, X. Y. Guo, Appl. Catal. B, 2019, 239, 408-424.
[28] Q. Bu, B. Wang J. Huang, S. Deng, G. Yu, J. Hazard. Mater., 2013, 262, 189-211.
[29] W. L. Chen, J. Y. Cheng, X. Q. Lin, Sci. Total Environ., 2018, 637, 253-263.
[30] A. Alsbaiee, B. J. Smith, L. Xiao, Y. Ling, D. E. Helbling, W. R. Dichtel, Nature, 2016, 529, 190.
[31] F. Zhang, Q. Wen, M. Hong, Z. Zhuang, Y. Yu, Chem. Eng. J., 2017, 307, 593-603.
[32] G. Zeng, Y. He, Y. Zhan, L. Zhang, Y. Pan, C. Zhang, Z. Yu, J. Hazard. Mater., 2016, 317, 60-72.
[33] G. He, J. Zhang, Y. Hu, Z. Bai, C. Wei, Appl. Catal. B, 2019, 250, 301-312.
[34] W. H. Abdelraheem, M. K. Patil, M. N. Nadagouda, D. D. Dionysiou, Appl. Catal. B, 2019, 241, 598-611.
[35] H. Tong, Y. Zhou, G. Chang, P. Li, R. Zhu, Y. He, Appl. Surf. Sci., 2018, 444, 267-275.
[36] Z. Liang, X. Bai, P. Hao, Y. Guo, Y. Xue, J. Tian, H. Cui, Appl. Catal. B, 2019, 243, 711-720.
[37] Y. Zhou, C. Chen, N. Wang, Y. Li, H. Ding, J. Phys. Chem. C, 2016, 120, 6116-6124.
[38] Á. Tolosana-Moranchel, A. Manassero, M. L. Satuf, O. M. Alfano, J. A. Casas, A. Bahamonde, Appl. Catal. B, 2019, 246, 1-11.
[39] W. Wang, D. Xu, B. Cheng, J. Yu, C. Jiang, J. Mater. Chem. A, 2017, 5, 5020-5029.
[40] M. Nawaz, W. Miran, J. Jang, D. S. Lee, Appl. Catal. B, 2017, 203, 85-95.
[41] H. Sohn, D. Kim, J. Lee, S. Yoon, RSC Adv., 2016, 6, 39484-39491.
[42] Z. Yao, Y. Meng, Y. Zhao, G. Liu, Q. Xia, J. Wang, Z. Jiang, Electrochim. Acta, 2017, 254, 320-327.
[43] B. Li, Z. Zhao, F. Gao, X. Wang, J. Qiu, Appl. Catal. B, 2014, 147, 958-964.
[44] V. Etacheri, G. Michlits, M. K. Seery, S. J. Hinder, S. C. Pillai, ACS Appl. Mater. Interfaces, 2013, 5, 1663-1672.
[45] J. Shao, W. Sheng, M. Wang, S. Li, J. Chen, Y. Zhang, S. Cao, Appl. Catal. B, 2017, 209, 311-319.
[46] J. Zhao, L. Zhang, X. Y. Xie, X. Li, Y. Ma, Q. Liu, X. Sun, J. Mater. Chem. A, 2018, 6, 24031-24035.
[47] X. Ding, Y. Li, C. Li, W. Wang, L. Wang, L. Feng, D. Han, J. Mater. Sci., 2019, 54, 9385-9396.
[48] H. Wei, E. F. Rodriguez, A. S. Best, A. F. Hollenkamp, D. Chen, R. A. Caruso, ACS Appl. Mater. Interfaces, 2019, 11, 13194-13204.
[49] M. A. Mahadadalkar, S. W. Gosavi, B. B. Kale, J. Mater. Chem. A, 2018, 6, 16064-16073.
[50] Z. Ai, Y. Shao, B. Chang, B. Huang, Y. Wu, X. Hao, Appl. Catal. B, 2019, 242, 202-208.
[51] S. S. Yi, J. M. Yan, B. R. Wulan, S. J. Li, K. H. Liu, Q. Jiang, Appl. Catal. B, 2017, 200, 477-483.
[52] G. Ai, H. Li, S. Liu, R. Mo, J. Zhong, Adv. Funct. Mater., 2015, 25, 5706-5713.
[53] D. Vidyasagar, N. Manwar, A. Gupta, S. G. Ghugal, S. S. Umare, R. Boukherroub, Catal. Sci. Technol., 2019, 9, 822-832.
[54] S. Samanta, S. Khilari, D. Pradhan, R. Srivastava, ACS Sustain. Chem. Eng., 2017, 5, 2562-2577.
[55] G. Sun, S. Mao, D. Ma, Y. Zou, Y. Lv, Z. Li, J. W. Shi, J. Mater. Chem. A, 2019, 7, 15278-15287.
[56] J. Shen, R. Wang, Q. Liu, X. Yang, H. Tang, J. Yang, Chin. J. Catal., 2019, 40, 380-389.
[57] Y. Zhang, H. Hu, M. Chang, H. Wei, D. Chen, M. Zhang, X. Li, J. Mater. Sci., 2018, 53, 2102-2114.
[58] J. Cai, J. Huang, Y. Lai, J. Mater. Chem. A, 2017, 5, 16412-16421.
[59] X. Y. Wang, J. Q. Meng, X. Yang, A. Hu, Y. X. Yang, Y. H. Guo, ACS Appl. Mater. Interfaces, 2019, 11, 588-602.
[60] Y. C. Pu, H. Y. Chou, W. S. Kuo, K. H. Wei, Y. J. Hsu, Appl. Catal. B, 2017, 204, 21-32.
[61] J. Jiang, H. Wang, X. Chen, S. Li, T. Xie, D. Wang, Y. Lin, J. Colloid Interface Sci., 2017, 494, 130-138.
[62] M. Pan, J. Ding, L. Duan, G. Gao, Chemosphere, 2017, 167, 353-359.
[63] W. Zhang, Y. Gao, Y. Qin, M. Wang, J. Wu, G. Li, T. An, Environ. Pollut., 2019, 247, 362-370.

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

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

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	卢明佳, 梁乐程, 冯彬彬, 常译文, 黄志宏, 宋慧宇, 杜丽, 廖世军, 崔志明. 燃料电池多孔碳载体高石墨化的超快速碳热冲击策略[J]. 催化学报, 2023, 52(9): 228-238.
[2]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[3]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[4]	关志朋, 杨东锋, 刘钊, 朱书祥, 仲星星, 王华敏, 李向伟, 戚孝天, 易红, 雷爱文. 区域选择性地电化学氧化自由基参与的邻位-(4 + 2)/原位-(3 + 2)环化[J]. 催化学报, 2023, 52(9): 144-153.
[5]	邹心仪, 顾均. 酸性条件下二氧化碳高效电还原策略[J]. 催化学报, 2023, 52(9): 14-31.
[6]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.
[7]	刘海峰, 黄祥, 陈加藏. 电子态调控促进氢气无损耗纯化中CO的光致富集和氧化[J]. 催化学报, 2023, 51(8): 49-54.
[8]	乔秀清, 李晨, 王紫昭, 侯东芳, 李东升. TiO_2-_x@C/MoO₂肖特基结: 合理设计及高效电荷分离提升光催化性能[J]. 催化学报, 2023, 51(8): 66-79.
[9]	肖汉至, 于博, 颜思顺, 章炜, 李茜茜, 鲍莹, 罗书平, 叶剑衡, 余达刚. 可见光催化二氧化碳参与非活化烯烃1,3-双羧基化反应[J]. 催化学报, 2023, 50(7): 222-228.
[10]	刘敬祥, 张超, Ferdi Karadas, 熊宇杰. 地外光催化CO₂转化[J]. 催化学报, 2023, 50(7): 1-5.
[11]	余治晗, 关晨, 岳晓阳, 向全军. 碳环渗入的结晶氮化碳S型同质结及其光催化析氢[J]. 催化学报, 2023, 50(7): 361-371.
[12]	李轩, 蒋兴星, 孔艳, 孙建桔, 胡琪, 柴晓燕, 杨恒攀, 何传新. GaN/In₂O₃的界面工程用于高效电催化CO₂还原制备甲酸[J]. 催化学报, 2023, 50(7): 314-323.
[13]	李慧珍, 陈艳蕾, 牛青, 王小凤, 刘哲源, 毕进红, 于岩, 李留义. 具有定向电荷传递能力的晶态线型聚酰亚胺材料驱动光催化CO₂还原[J]. 催化学报, 2023, 49(6): 152-159.
[14]	李孜孜, 王嘉蔚, 黄衍钧, 欧阳钢锋. 钴(II)酞菁全氟化策略用于提升非贵金属体系中光催化还原CO₂性能[J]. 催化学报, 2023, 49(6): 160-167.
[15]	杨文倩, 薛自前, 杨俊, 冼家慧, 刘庆林, 范雅楠, 郑凯, 廖锫钦, 苏徽, 刘庆华, 李光琴, 苏成勇. 氮掺杂多孔碳负载Fe纳米颗粒用于高性能电催化还原CO₂与Zn-CO₂电池[J]. 催化学报, 2023, 48(5): 185-194.