二氧化钛基催化剂催化氧化甲醛的研究进展

doi:10.16085/j.issn.1000-6613.2022-0681

化工进展 ›› 2022, Vol. 41 ›› Issue (12): 6310-6318.DOI: 10.16085/j.issn.1000-6613.2022-0681

二氧化钛基催化剂催化氧化甲醛的研究进展

崔维怡¹^,²(), 丁国敏³, 谭乃迪²()

^1.吉林化工学院化工清洁生产技术吉林省高校重点实验室，吉林吉林 132022
^2.吉林化工学院化学与制药工程学院，吉林吉林 132022
^3.中国石油吉林石化公司乙二醇厂，吉林吉林 132021

收稿日期:2022-04-18 修回日期:2022-07-27 出版日期:2022-12-20 发布日期:2022-12-29
通讯作者: 谭乃迪
作者简介:崔维怡（1977—），女，副教授，研究方向为环境催化。E-mail：cuiweiyi0119@163.com。
基金资助:
国家自然科学基金(51805207);吉林省教育厅2021科学技术研究规划(JJKH20210235KJ)

Research progress on titanium dioxide based catalysts for catalytic oxidation of formaldehyde

CUI Weiyi¹^,²(), DING Guomin³, TAN Naidi²()

^1.The Key Laboratory of Chemical Cleaner Production Technology of Jilin Province, Jilin Institute of Chemical Technology, Jilin 132022, Jilin, China
^2.College of Chemical and Pharmaceutical Engineering, Jilin Institute of Chemical and Technology, Jilin 132022, Jilin, China
^3.Ethylene Glycol Plant of Jilin Petrochemical Company, PetroChina, Jilin 132021, Jilin, China

Received:2022-04-18 Revised:2022-07-27 Online:2022-12-20 Published:2022-12-29
Contact: TAN Naidi

摘要/Abstract

摘要：

甲醛（HCHO）是一种主要的室内空气污染物，具有高致癌性和致突变性，催化氧化是一种理想而有效的室内消除甲醛的方法。二氧化钛作为载体负载贵金属催化剂在甲醛催化氧化反应中表现出优良的催化性能。本文综述了近年来二氧化钛基催化剂催化氧化甲醛的研究进展，主要总结了二氧化钛的吸附机理，二氧化钛晶体结构、表面形貌及微观结构、表面活性氧物种和还原性等对二氧化钛基负载贵金属催化剂催化氧化甲醛性能的影响，重点关注了催化剂的化学结构性质与甲醛氧化活性的关系，并归纳了一部分甲醛催化氧化反应机理。最后指出二氧化钛基催化剂在甲醛催化氧化反应中未来研究方向为：合理设计TiO₂各种缺陷和晶面暴露，同时提高贵金属的分散性和原子利用效率，继而进一步提高催化剂的性能；在保持催化剂高活性、高稳定性的同时，推进设计实际应用整体式催化剂的研究进程。

关键词: 甲醛, 催化剂, 二氧化钛基催化剂, 活性

Abstract:

Formaldehyde (HCHO) is a primary indoor air pollutant with high carcinogenicity and mutagenicity. Catalytic oxidation is an ideal and effective method for indoor HCHO removal. Titanium dioxide as a carrier to support noble metal catalyst has showed excellent catalytic performance in the catalytic oxidation of formaldehyde. This review introduces recent progress of titanium dioxide based catalysts for catalytic oxidation of HCHO, summarizes the adsorption mechanisms of titanium dioxide, and analyzes the effects of titanium dioxide crystal structure, surface morphology and microstructure, surface active oxygen species and reducibility on the catalytic oxidation performance of HCHO with the focus on the relationship between the chemical and structural properties of catalysts and HCHO oxidation activity. Finally, the future research directions of titanium dioxide based catalysts in HCHO catalytic oxidation are given, namely, to further enhance the catalytic activity by reasonably designing various defects and crystal surface exposure of TiO₂, to improve the dispersion of precious metals and atomic utilization efficiency, and to speed up the designing and practical application of monolithic catalyst while maintaining the high activity and stability of the catalyst.

Key words: formaldehyde, catalyst, titanium dioxide based catalysts, activity

中图分类号:

TQ426

崔维怡, 丁国敏, 谭乃迪. 二氧化钛基催化剂催化氧化甲醛的研究进展[J]. 化工进展, 2022, 41(12): 6310-6318.

CUI Weiyi, DING Guomin, TAN Naidi. Research progress on titanium dioxide based catalysts for catalytic oxidation of formaldehyde[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6310-6318.

图/表 7

图1 一维TiO2/CeO2纳米线催化剂的微观结构[23](a)TiO2/CeO2纳米线在碳布上生长过程示意图；(b)碳布上制备的TiO2/CeO2纳米线的扫描电镜（SEM）图；(c)TiO2/CeO2纳米线的透射电镜（TEM）图像；(d) CeO2纳米线的选区电子衍射（SAED）图；(e) CeO2纳米线的高分辨透射电镜（HRTEM）图；(g) TiO2纳米线的SAED图；(f)TiO2纳米线HRTEM图

图2 Pt/TiO2的电镜图和甲醛消除浓度变化[26]

图3 Pt/TiO2超薄2D纳米片的合成示意图[32]

图4 Pt/TiO2/γ-Al2O3纳米纤维纸合成示意图[37]

图5 2Na-Pd/TiO2催化剂合成示意图及甲醛转化率[40]

图6 不同Ag/TiO2催化剂在室温下对甲醛的去除效率及催化剂上甲醛氧化的可能途径[46]

图7 Pt/TiO2催化剂上甲醛室温氧化反应机理示意图[29]

参考文献 49

1	HE Chi, CHENG Jie, ZHANG Xin, et al. Recent advances in the catalytic oxidation of volatile organic compounds: a review based on pollutant sorts and sources[J]. Chemical Reviews, 2019, 119 (7): 4471-4568.
2	HUANG Haibao, XU Ying, FENG Qiuyu, et al. Low temperature catalytic oxidation of volatile organic compounds: a review[J]. Catalysis Science & Technology, 2015, 5: 2649-2669.
3	SALTHAMMER Tunga, MENTESE Sibel, MARUTZKY Rainer. Formaldehyde in the indoor environment[J]. Chemical Reviews, 2010, 110: 2536-2572.
4	LIU Lumeng, LIU Junjie, ZENG Yonghong, et al. Formaldehyde adsorption in carbon nanopores—New insights from molecular simulation[J]. Chemical Engineering Journal, 2019, 370: 866-874.
5	DIAO Wenyu, CAI Hongyue, WANG Lu, et al. Efficient photocatalytic degradation of gas-phase formaldehyde by Pt/TiO₂ nanowires in a continuous flow reactor[J]. ChemCatChem, 2020, 12 (21): 5420-5429.
6	VELLINGIRI Kowsalya, VIKRANT Kumar, KUMAR Vanish, et al. Advances in thermocatalytic and photocatalytic techniques for the room/low temperature oxidative removal of formaldehyde in air[J]. Chemical Engineering Journal, 2020, 399: 125759.
7	WAN Yajuan, FAN Xing, ZHU Tianle. Removal of low-concentration formaldehyde in air by DC corona discharge plasma[J]. Chemical Engineering Journal, 2011, 171(1): 314-319.
8	TORRES Jhonquiroz, ROYER Sébastien, BELLAT Jean-pierre, et al. Formaldehyde: catalytic oxidation as a promising soft way of elimination[J]. ChemSusChem, 2013, 6 (4): 578-592.
9	NIE Long Hui, YU Jia Guo, JARONIEC Mietek, et al. Room-temperature catalytic oxidation of formaldehyde on catalysts[J]. Catalysis Science & Technology, 2016, 6 (11): 3649-3669.
10	BAI Bingyang, QIAO Qi, LI Junhua, et al. Progress in research on catalysts for catalytic oxidation of formaldehyde[J]. Chinese Journal of Catalysis, 2016, 37:102-122.
11	GUO Jiahong, LIN Chuxia, JIANG Chuanjia, et al. Review on noble metal-based catalysts for formaldehyde oxidation at room temperature[J]. Applied Surface Science, 2019, 475: 237-255.
12	YUSUF Abubakar, SNAPE Colin, HE Jun, et al. Advances on transition metal oxides catalysts for formaldehyde oxidation: a review[J]. Catalysis Reviews-Science and Engineering, 2017, 59 (3): 189-233.
13	MIAO Lei, WANG Jinlong, ZHANG Pengyi. Review on manganese dioxide for catalytic oxidation of airborne formaldehyde[J]. Applied Surface Science, 2019, 466: 441-453.
14	ZHANG Changbin, HE Hong, TANAKA K. Perfect catalytic oxidation of formaldehyde over a Pt/TiO₂ catalyst at room temperature[J]. Catalysis Communications, 2005, 6: 211-214.
15	THOMPSON TL, YATES JT. Surface science studies of the photoactivation of TiO₂-new photochemical processes[J]. Chemical Reviews, 2006, 106(10): 4428-4453.
16	HAUBRICH Jan, KAXIRAS Efthimions, FRIEND Cynthia M. The role of surface and subsurface point defects for chemical model studies on TiO₂: a first-principles theoretical study of formaldehyde bonding on rutile TiO₂(110) [J]. Chemistry-a European Journal, 2011, 17: 4496-4506.
17	LIU Huazhong, ZHAO Mingtian, LEI Yinkai, et al. Formaldehyde on TiO₂ anatase (101): a DFT study[J]. Computational Materials Science, 2012, 51: 389-395.
18	LIU Huazhong, LIEW K M, PAN Chunxu. Influence of hydroxyl groups on the adsorption of HCHO on TiO₂-B(100) surface by first-principles study[J]. Physical Chemistry Chemical Physics, 2013, 15: 3866-3880.
19	LIU Huazhong, WANG Xiao, PAN Chunxu, et al. First-principles study of formaldehyde adsorption on TiO₂ rutile (110) and anatase (001) surfaces[J]. Journal of Physical Chemistry C, 2012, 116: 8044-8053.
20	何运兵, 纪红兵. 温和条件下甲醛在 Pt/TiO₂上催化氧化反应的原位漫反射红外光谱研究[J].催化学报，2010, 31:171-175.
	HE Yunbing, JI Hongbing. In-situ DRIFTS study on catalytic oxidation of formaldehyde over Pt/TiO₂ under mild conditions[J]. Chinese Journal of Catalysis, 2010, 31: 171-175.
21	HE Miao, JI Jian, LIU Biyuan, et al. Reduced TiO₂ with tunable oxygen vacancies for catalytic oxidation of formaldehyde at room temperature[J]. Applied Surface Science, 2019, 473: 934-942.
22	ZENG Lei, SONG Wulin, LI Minghui, et al. Catalytic oxidation of formaldehyde on surface of H-TiO₂/H-C-TiO₂ without light illumination at room temperature[J]. Applied Catalysis B: Environmental, 2014,147: 490-498.
23	HUANG Yongchao, LI Haibao, BALOGUN Muhammad-Sadeeq, et al. Three-dimensional TiO₂/CeO₂ nanowire composite for efficient formaldehyde oxidation at low temperature[J]. RSC Advances, 2015, 5: 7729-7733.
24	ZHANG Changbin, LIU Fudong, ZHAI Yanping, et al. Alkali-metal-promoted Pt/TiO₂ opens a more efficient pathway to formaldehyde oxidation at ambient temperatures[J]. Angewandte Chemie International Edition, 2012, 51: 9628-9632.
25	NIE Longhui, YU Jiaguo, LI Xinyang, et al. Enhanced performance of NaOH-modified Pt/TiO₂ toward room temperature selective oxidation of formaldehyde[J]. Environmental Science Technology, 2013, 47: 2777-2783.
26	QI Lifang, CHENG Bei, YU Jiaguo, et al. High-surface area mesoporous Pt/TiO₂ hollow chains for efficient formaldehyde decomposition at ambient temperature[J]. Journal of Hazardous Materials, 2016, 301: 522-530.
27	CHEN Huayao, RUI Zebao, JI Hongbing. Monolith-like TiO₂ nanotube array supported Pt catalyst for HCHO removal under mild conditions[J]. Industrial & Engineering Chemistry Research, 2014, 53: 7629-7636.
28	CUI Weiyi, XUE Dan, YUAN Xiaoling, et al. Acid-treated TiO₂ nanobelt supported platinum nanoparticles for the catalytic oxidation of formaldehyde at ambient conditions[J]. Applied Surface Science, 2017, 411: 105-112.
29	XU Feiyan, LE Yao, CHENG Bei, et al. Effect of calcination temperature on formaldehyde oxidation performance of Pt/TiO₂ nanofiber composite at room temperature[J]. Applied Surface Science, 2017, 426: 333-341.
30	SU Yuan, JI Keming, XUN Jiayao, et al. Catalytic oxidation of low concentration formaldehyde over Pt/ TiO₂ catalyst[J]. Chinese Journal of Chemical Engineering, 2021, 29: 190-195.
31	AHMAD Waleed, PARK Eunseuk, LEE Heehyeon, et al. Defective domain control of TiO₂ support in Pt/TiO₂ for room temperature formaldehyde (HCHO) remediation[J]. Applied Surface Science, 2021, 538: 147504.
32	SUN Shaodi, WU Xiaomin, HUANG Zhiwei, et al. Engineering stable Pt nanoclusters on defective two-dimensional TiO₂ nanosheets by introducing SMSI for efficient ambient formaldehyde oxidation[J]. Chemical Engineering Journal, 2022, 435: 135035.
33	CHEN Huayao, TANG Minni, RUI Zebao, et al. MnO₂ promoted TiO₂ nanotube array supported Pt catalyst for formaldehyde oxidation with enhanced efficiency[J]. Industrial & Engineering Chemistry Research, 2015, 54(36): 8900-8907.
34	PENG Honggen, YING Jiawei, ZHANG Jingyan, et al. La‐doped Pt/TiO₂ as an efficient catalyst for room temperature oxidation of low concentration HCHO[J]. Chinese Journal of Catalysis, 2017, 38: 39-47.
35	SHI Yuanyuan, QIAO Zhiwei, LIU Zili, et al. Cerium doped Pt/TiO₂ for catalytic oxidation of low concentration formaldehyde at room temperature[J]. Catalysis Letters, 2019, 149: 1319-1325.
36	CHEN Jin, JIANG Mingzhu, XU Wenjian, et al. Incorporating Mn cation as anchor to atomically disperse Pt on TiO₂ for low temperature removal of formaldehyde[J]. Applied Catalysis B: Environmental, 2019, 259: 118013.
37	ZHU Silong, ZHENG Jianfei, XIN Sitian, et al. Preparation of flexible Pt/TiO₂/γ-Al₂O₃ nanofiber paper for room-temperature HCHO oxidation and particulate filtration[J]. Chemical Engineering Journal, 2022, 427: 130951.
38	NIE Longhui, WANG Jie, YU Jiaguo. Preparation of a Pt/TiO₂/cotton fiber composite catalyst with low air resistance for efficient formaldehyde oxidation at room temperature[J]. RSC Advances, 2017, 7: 21389-21397.
39	LIU Wei, GONG Yutao, LI Xueping, et al. A TiO₂/C catalyst having biomimetic channels and extremely low Pt loading for formaldehyde oxidation[J]. RSC Advances, 2019, 9: 3965-3971.
40	ZHANG Changbin, LI Yaobin, WANG Yafei, et al. Sodium-promoted Pd/TiO₂ for catalytic oxidation of formaldehyde at ambient temperature[J]. Environmental Science Technology, 2014, 48: 5816-5822.
41	LI Yaobin, WANG Chunying, ZHANG Changbin, et al. Formaldehyde oxidation on Pd/TiO₂ catalysts at room temperature: the effects of surface oxygen vacancies[J]. Topics in Catalysis, 2020, 63: 810-816.
42	WANG Chunying, LI Yaobin, ZHANG Changbin, et al. A simple strategy to improve Pd dispersion and enhance Pd/TiO₂ catalytic activity for formaldehyde oxidation: the roles of surface defects[J]. Applied Catalysis B: Environmental, 2021, 282: 119540.
43	WANG Xuyu, RUI Zebao, ZENG Yingqing, et al. Synergetic effect of oxygen vacancy and Pd site on the interaction between Pd/Anatase TiO2(101) and formaldehyde: a density functional theory study[J]. Catalysis Today, 2017, 297: 151-158.
44	Y C Leung DENNIS, FU Xiaoliang, YE Daiqi, et al. Effect of oxygen mobility in the lattice of Au/TiO₂ on formaldehyde oxidation[J]. Kinetics and Catalysis, 2012, 53(2): 239-246.
45	LI Yaobin, CHEN Xueyan, WANG Chunying, et al. Sodium enhances Ir/TiO₂ activity for catalytic oxidation of formaldehyde at ambient temperature[J]. ACS Catalysis. 2018, 8: 11377-11385.
46	FANG Ruimei, HE Miao, HUANG Haibao, et al. Effect of redox state of Ag on indoor formaldehyde degradation over Ag/TiO₂ catalyst at room temperature[J]. Chemosphere, 2018, 213: 235-243.
47	BAO Wen, WANG Nan, HE Zhanhang. Ag@Fe-TiO₂ catalysts for catalytic oxidation of formaldehyde indoor: a further improvement of Fe-TiO₂ [J]. Research on Chemical Intermediates, 2021, 47: 3005-3023.
48	ZHANG Changbin, HE Hong, TANAKA Ken-ichi. Catalytic performance and mechanism of a Pt/TiO₂ catalyst for the oxidation of formaldehyde at room temperature[J]. Applied Catalysis B: Environmental, 2006, 65: 37-43.
49	DING Junyan, YANG Yingju, LIU Jing, et al. Catalytic reaction mechanism of formaldehyde oxidation by oxygen species over Pt/TiO₂ catalyst[J]. Chemosphere, 2020, 248: 12598.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[6]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[7]	赵景超, 谭明. 表面活性剂对电渗析减量化工业含盐废水的影响[J]. 化工进展, 2023, 42(S1): 529-535.
[8]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[9]	王谨航, 何勇, 史伶俐, 龙臻, 梁德青. 气体水合物阻聚剂研究进展[J]. 化工进展, 2023, 42(9): 4587-4602.
[10]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[11]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[12]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[13]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[14]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[15]	林晓鹏, 肖友华, 管奕琛, 鲁晓东, 宗文杰, 傅深渊. 离子聚合物-金属复合材料（IPMC）柔性电极的研究进展[J]. 化工进展, 2023, 42(9): 4770-4782.

二氧化钛基催化剂催化氧化甲醛的研究进展

Research progress on titanium dioxide based catalysts for catalytic oxidation of formaldehyde

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 49

相关文章 15

编辑推荐

Metrics

本文评价