催化法治理挥发性有机物污染的研究进展

doi:10.1016/S1872-2067(24)60043-4

催化学报 ›› 2024, Vol. 61: 71-96.DOI: 10.1016/S1872-2067(24)60043-4

催化法治理挥发性有机物污染的研究进展

张红红, 王治伟, 隗陆, 刘雨溪, 戴洪兴, 邓积光^*()

北京工业大学材料科学与工程学院, 区域大气复合污染防治北京市重点实验室, 绿色催化与分离北京市重点实验室, 北京 100124

收稿日期:2024-02-25 接受日期:2024-04-10 出版日期:2024-06-18 发布日期:2024-06-20
通讯作者: * 电子信箱: jgdeng@bjut.edu.cn (邓积光).
基金资助:
国家自然科学基金项目(22106007);国家自然科学基金项目(21961160743);国家自然科学基金项目(21622701);北京市教委科技计划重点项目(KZ202210005011);河北省自然科学基金重点项目(B2021208033)

Recent progress on VOC pollution control via the catalytic method

Honghong Zhang, Zhiwei Wang, Lu Wei, Yuxi Liu, Hongxing Dai, Jiguang Deng^*()

Beijing Key Laboratory for Green Catalysis and Separation, Key Laboratory of Beijing on Regional Air Pollution Control, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China

Received:2024-02-25 Accepted:2024-04-10 Online:2024-06-18 Published:2024-06-20
Contact: * E-mail: jgdeng@bjut.edu.cn (J. Deng).
About author:Jiguang Deng (College of Materials Science and Engineering, Beijing University of Technology (BJUT)) received his Ph.D. degree from BJUT (China) in 2010. Since then, he has been working at BJUT and is currently a professor. His research interests focus on low carbon environmental chemistry, environmental catalysis and photothermal catalysis technologies for the elimination or utilization of typical gaseous pollutants (VOCs, NO_x, CH₄, CO₂, and NH₃). He has published more than 260 refereed journal papers with citation over 13000 and H-index of 67.
Supported by:
Natural Science Foundation of China(22106007);Natural Science Foundation of China(21961160743);Natural Science Foundation of China(21622701);Key Science and Technology Projects of Beijing Municipal Education Commission(KZ202210005011);Natural Science Foundation of Hebei(B2021208033)

摘要/Abstract

摘要：

挥发性有机物(VOCs)具有毒性、刺激性、致癌性和致畸作用, 主要来源于石油化工、制药、制鞋业、电子制造和餐饮油烟等人类活动. VOCs和NO_x是生成细颗粒物(PM_2.5)和臭氧(O₃)等二次污染物的重要前体物, 严重制约了社会的可持续发展, 并对人类健康构成了严重威胁. 因此, 治理VOCs污染对于降低环境风险至关重要. 鉴于实际工况条件复杂, 多种VOCs(烷烃、芳香烃、卤代烃、醛酮和醇酯等)共存, 它们的极性和浓度存在差异, 在催化剂上的吸附、活化和转化过程不同, 因此, 对催化剂高效消除多组分VOCs的能力提出了挑战. 目前, 在众多净化VOCs的技术中, 催化氧化法因其高效率、低能耗等优势在末端污染控制中越来越受到重视.
本文主要介绍了近十年来通过热催化或光热催化消除污染物的代表性研究工作. 首先, 系统地总结了用于热催化消除单一VOC和典型多组分VOCs (例如, 医药行业: 甲苯和丙酮; 家具涂料行业: 甲苯和异己烷等)、协同消除VOCs和NO_x, 以及VOCs资源化利用(选择催化转化VOCs为高附加值产品)而设计和制备的各种具有独特形貌和结构的过渡金属氧化物纳米催化剂、贵金属颗粒纳米催化剂、贵金属单原子催化剂等, 并探讨了其氧化还原性、酸性、氧物种、载体孔结构、贵金属分散度等对催化活性和稳定性的影响机制及优化策略. 其次, 鉴于化石燃料的日益减少, 本文还概述了光热协同催化技术, 该技术结合了光催化和热催化技术, 通过太阳光的光热转换, 能够在较低的温度下高效催化消除VOCs, 并介绍了其效率和转化机制. 此外, 文中还深入分析了H₂O, CO₂和SO₂等气体对催化稳定性的影响机制. 最后, 考虑到我国当前大气污染防治面临更为复杂的复合污染问题等挑战, 对未来发展趋势提出了展望: (1) 利用活性空间和活性位点分离策略协同催化净化VOCs和NO_x, 从而实现催化氧化和还原反应的高效进行. (2) 聚焦于大气污染物和温室气体的协同处理, 探究CO₂和VOCs协同转化的路径和效率, 为减污降碳和实现碳中和提供新思路. (3) 设计合成新型串联催化剂用于安全转化含CVOCs的多组分污染物, 以实现VOCs污染广谱性控制. (4) 发展先进的原位表征技术(如原位电子显微镜、同位素示踪技术、原位拉曼光谱、原位X射线光电子能谱等)以实时检测催化剂的原子结构变化、吸附VOCs分子降解的中间体变化等, 并结合理论计算确定最优反应路径, 从而指导催化剂的设计与优化. (5) 深入研究外场(例如, 光能、电能、磁能)耦合热催化降解VOCs的技术, 以期实现反应条件更温和、反应速率更高的催化过程.
综上, 本文综述了通过实验和理论计算手段揭示催化剂消除VOCs污染的性能与构效关系的研究进展, 系统地呈现了治理VOCs污染研究的基本逻辑和框架体系, 以期为后续开发高活性、高稳定性和高选择性的催化剂及其工业化应用提供借鉴.

关键词: 挥发性有机物, 纳米催化剂, 催化氧化, 协同催化, 资源化利用

Abstract:

Volatile organic compounds (VOCs) can cause atmospheric environmental problems such as haze and photochemical smog, which seriously restrict the sustainable development of the environment and threaten human health. Effective and comprehensive implementation of VOC prevention is an arduous task. Catalytic oxidation can achieve VOC removal with low energy costs and high efficiency. This review presents representative research progress in thermal or photothermal catalysis over the past ten years, concentrating on various catalysts with distinctive morphologies and structures designed and prepared for investigating single- or multi-component VOC purification, synergetic elimination of VOCs and NO_x, and VOCs resource utilization. Furthermore, the influence mechanisms of H₂O, CO₂, and SO₂ on the catalytic stability are summarized. The activity and stability of the catalysts affect their lifespan and cost of use. In particular, for supported noble-metal catalysts with poor stability, some unique design strategies have been summarized for the efficient removal of VOCs while balancing low noble-metal usage and optimized catalytic performance. Finally, the scientific problems and future research directions are presented. Coordinated treatment of atmospheric pollutants and greenhouse gases should be considered. This study is expected to provide profound insights into the design of catalysts with high activity, selectivity, and stability, as well as air pollution control via catalytic methods.

Key words: Volatile organic compound, Nanocatalyst, Catalytic oxidation, Synergetic purification, Resource utilization

张红红, 王治伟, 隗陆, 刘雨溪, 戴洪兴, 邓积光. 催化法治理挥发性有机物污染的研究进展[J]. 催化学报, 2024, 61: 71-96.

Honghong Zhang, Zhiwei Wang, Lu Wei, Yuxi Liu, Hongxing Dai, Jiguang Deng. Recent progress on VOC pollution control via the catalytic method[J]. Chinese Journal of Catalysis, 2024, 61: 71-96.

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图/表 25

Table 1 Catalytic performance of different sorts of catalysts for typical VOC oxidation.

VOCs type	Catalyst	VOCs concentration (vol%)	Oxygen concentration (vol%)	Space velocity (mL/(g·h))	T_90% (°C)	E_a (kJ/mol)	Ref.
Methane	Pd_2.41Pt	2.5	20	100000	322	—	[46]
	0.97 wt% Pd/3DOM LaMnAl₁₁O₁₉	2.5	20	20000	343	—	[47]
	Pd-GaO_x/Al₂O₃	0.5	4	80000	372	—	[48]
	1.81Pd_2.1Pt/6.70MnO_x/3DOM CoFe₂O₄	2.5	20	20000	372	59	[49]
	0.44PtPd_2.20/ZrO₂	2.5	20	20000	408	59	[50]
	Au-Pd-0.40CoO/3DOM Co₃O₄	2.5	10	20000	341	63	[51]
	2.94Au_0.50Pd/meso-Co₃O₄	2.5	20	20000	324	44.4	[52]
	Co_3.5Pd/3DOM CeO₂	2.5	20	40000	480	58	[53]
Propane	CoCeO_x-70	0.2	5	120000	310	97	[54]
	Pt₁Co₁/meso-Na_xMnO_y	0.2	20	30000	282	76.0	[55]
	Pd₁/AlCo₂O₄-Al₂O₃	0.5	20	40000	358	-	[56]
Benzene	6.5Au/meso-Co₃O₄	0.1	40	20000	189	55	[57]
	0.93Pd/meso-CoO	0.1	20	40000	189	—	[58]
	0.56Pt/meso-CoO	0.1	40	80000	186	—	[59]
	0.25Pt₁/meso-Fe₂O₃	0.1	20	20000	198	—	[60]
	0.0383Pt₁/OMS-2	0.1	20	20000	189	41.8	[61]
	Pd₁Co₁/Al₂O₃	0.1	20	40000	250	57	[62]
	PtW/Al₂O₃-2	0.1	20	40000	140	72	[63]
	TiO₂/PdW-S1	0.1	20	40000	200	56	[64]
Toluene	0.28Pd/S-1-H	0.1	20	40000	189	41	[65]
	0.2 wt% Pt/TiO₂	0.1	40	40000	183	—	[66]
	1.3Pt/8.9Co₃O₄/3DOM Al₂O₃	0.1	40	20000	160	42.6	[67]
	6.5Au/meso-Co₃O₄	0.1	40	20000	138	45	[57]
	0.37Pt-0.16MnO_x/meso-CeO₂	0.1	20	40000	171	—	[68]
	3.8AuPd_1.92/3DOM Mn₂O₃	0.1	40	40000	162	26	[69]
	0.96(AuPd_1.92)/Co₃O₄	0.1	40	40000	180	—	[70]
	1.99AuPd/3DOM Co₃O₄	0.1	40	40000	168	33	[71]
1,2-Dichloroethane	Ru/WO₃	0.1	20	40000	340	—	[72]
	RuP/3DOM WO_x	0.1	20	40000	353	—	[73]
	RuCo/HZSM-5	0.1	20	20000	281	36	[74]
	RuCo/Al₂O₃	0.1	20	20000	391	104	[74]
	10CrO_x-TiO₂	0.1	20	40000	284	35	[75]
Trichloroethylene	0.98Ru/3DOM SnO₂	0.1	20	40000	300	44	[76]
	0.93Ru_2.87Pd/3DOM CeO₂	0.1	20	20000	298	41	[77]
	0.91Au_0.51Pd/3DOM TiO₂	0.075	20	20000	400	51.7	[78]
	2.85AuPd_1.87/3DOM CeO₂	0.075	20	20000	415	33	[79]
	3DOM 5.5Cr₂O₃-CeO₂	0.075	20	20000	255	81	[80]

Table 1 Catalytic performance of different sorts of catalysts for typical VOC oxidation.

VOCs type	Catalyst	VOCs concentration (vol%)	Oxygen concentration (vol%)	Space velocity (mL/(g·h))	T_90% (°C)	E_a (kJ/mol)	Ref.
Methane	Pd_2.41Pt	2.5	20	100000	322	—	[46]
	0.97 wt% Pd/3DOM LaMnAl₁₁O₁₉	2.5	20	20000	343	—	[47]
	Pd-GaO_x/Al₂O₃	0.5	4	80000	372	—	[48]
	1.81Pd_2.1Pt/6.70MnO_x/3DOM CoFe₂O₄	2.5	20	20000	372	59	[49]
	0.44PtPd_2.20/ZrO₂	2.5	20	20000	408	59	[50]
	Au-Pd-0.40CoO/3DOM Co₃O₄	2.5	10	20000	341	63	[51]
	2.94Au_0.50Pd/meso-Co₃O₄	2.5	20	20000	324	44.4	[52]
	Co_3.5Pd/3DOM CeO₂	2.5	20	40000	480	58	[53]
Propane	CoCeO_x-70	0.2	5	120000	310	97	[54]
	Pt₁Co₁/meso-Na_xMnO_y	0.2	20	30000	282	76.0	[55]
	Pd₁/AlCo₂O₄-Al₂O₃	0.5	20	40000	358	-	[56]
Benzene	6.5Au/meso-Co₃O₄	0.1	40	20000	189	55	[57]
	0.93Pd/meso-CoO	0.1	20	40000	189	—	[58]
	0.56Pt/meso-CoO	0.1	40	80000	186	—	[59]
	0.25Pt₁/meso-Fe₂O₃	0.1	20	20000	198	—	[60]
	0.0383Pt₁/OMS-2	0.1	20	20000	189	41.8	[61]
	Pd₁Co₁/Al₂O₃	0.1	20	40000	250	57	[62]
	PtW/Al₂O₃-2	0.1	20	40000	140	72	[63]
	TiO₂/PdW-S1	0.1	20	40000	200	56	[64]
Toluene	0.28Pd/S-1-H	0.1	20	40000	189	41	[65]
	0.2 wt% Pt/TiO₂	0.1	40	40000	183	—	[66]
	1.3Pt/8.9Co₃O₄/3DOM Al₂O₃	0.1	40	20000	160	42.6	[67]
	6.5Au/meso-Co₃O₄	0.1	40	20000	138	45	[57]
	0.37Pt-0.16MnO_x/meso-CeO₂	0.1	20	40000	171	—	[68]
	3.8AuPd_1.92/3DOM Mn₂O₃	0.1	40	40000	162	26	[69]
	0.96(AuPd_1.92)/Co₃O₄	0.1	40	40000	180	—	[70]
	1.99AuPd/3DOM Co₃O₄	0.1	40	40000	168	33	[71]
1,2-Dichloroethane	Ru/WO₃	0.1	20	40000	340	—	[72]
	RuP/3DOM WO_x	0.1	20	40000	353	—	[73]
	RuCo/HZSM-5	0.1	20	20000	281	36	[74]
	RuCo/Al₂O₃	0.1	20	20000	391	104	[74]
	10CrO_x-TiO₂	0.1	20	40000	284	35	[75]
Trichloroethylene	0.98Ru/3DOM SnO₂	0.1	20	40000	300	44	[76]
	0.93Ru_2.87Pd/3DOM CeO₂	0.1	20	20000	298	41	[77]
	0.91Au_0.51Pd/3DOM TiO₂	0.075	20	20000	400	51.7	[78]
	2.85AuPd_1.87/3DOM CeO₂	0.075	20	20000	415	33	[79]
	3DOM 5.5Cr₂O₃-CeO₂	0.075	20	20000	255	81	[80]

Fig. 1. Methane conversion varied with the temperature when the reaction temperature rose (solid) or dropped (hollow) over 3DOM Co3O4 loaded Au-Pd-3.61CoO (a), Au-Pd (b), and Pd-3.61CoO (c). Reproduced with permission from Ref. [51]. Copyright 2017, American Chemical Society.

Fig. 2. Diagram of the Pd/Al2O3 and Pd-GaOx/Al2O3 catalysts after calcination, hydrothermal aging treatments, and catalytic CH4 oxidation process. Reproduced with permission from Ref. [48]. Copyright 2018, Wiley-VCH Verlag GmbH & Co. KgaA, Weinheim.

Fig. 3. (a) Diagram for transforming PdCo nanocrystals to single atoms. (b) TEM images and EDX element mapping for PdCo nanocrystals. (c) Ac-HAADF-STEM image of Pd1/AlCo2O-Al2O3. Bright spots represent individual Pd atoms. (d) EDX element mapping of Pd1/AlCo2O4-Al2O3. Reproduced with permission from Ref. [56]. Copyright 2023, American Chemical Society.

Fig. 4. TEM (a) and HAADF-STEM (b,c) images, EDX line scan (d), and EDX elemental mappings (e) of PtW-2 NPs. (f) Benzene conversion as a function of temperature over different samples (solid line and dotted line represent the absence and presence of 100 ppm DCE, respectively). Reproduced with permission from Ref. [63]. Copyright 2020, Elsevier.

Fig. 6. SEM images of 3DOM Mn2O3 (a), 0.2Pt/3DOM Mn2O3 (b,c), 0.5Pt/3DOM Mn2O3 (d,e), 1.6 Pt/3DOM Mn2O3 (f,g), 2.3Pt/3DOM Mn2O3 (h,i), and 2.0Pt/3DOM Mn2O3-imp (j). Reproduced with permission from Ref. [106]. Copyright 2019, Elsevier.

Fig. 7. HAADF-STEM images (a-d), Pt NPs size distributions (e,f), and toluene conversion (g,h) of 2.3Pt/3DOM Mn2O3 (a,c,e,g) and 2.0Pt/3DOM Mn2O3-imp (b,d,f,h) before and after calcination treatments in air at 650 °C. Reproduced with permission from Ref. [106]. Copyright 2019, Elsevier.

Fig. 8. SEM and TEM images of MOF-74 (a), Co3O4-R (b,c), MOF-39 (d), and Co3O4-S (e,f). (g) Diagram illustrating the catalytic mechanism involved in the catalytic o-xylene oxidation over Co3O4 with different shapes. Reproduced with permission from Ref. [123]. Copyright 2021, American Chemical Society.

Fig. 9. Investigated L-H (a) and E-R (b) mechanisms of HCHO oxidation reaction on Ti/Ti3C2O2 surface. Reproduced with permission from Ref. [137]. Copyright 2020, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

Fig. 12. 1,2-DCE conversion (a) and C2H3Cl concentration (b) as a function of temperature over the WO3 and Ru/WO3 samples in the presence or absence of water vapor. Reproduced with permission from Ref. [72]. Copyright 2021, Elsevier.

Fig. 13. Toluene (a) and iso-hexane (b) conversion as a function of time over different samples. (c) Schematic diagram of catalytic stability process of toluene oxidation on Pt1/MnOx and H2-Pt1/MnOx-200. Reproduced with permission from Ref. [153]. Copyright 2021, Elsevier.

Fig. 15. NO conversion and N2 selectivity (a), CB conversion (b), and CO2 selectivity (c) in the SCR/CBCO over different samples. (d) The energy and optimal structure of CB or NH3 adsorbed on the Al-CeO2, CeO2, and Ta-CeO2 structures. Blue, white, green, and gray are the colors of N, H, Cl, and C atoms, respectively. Reproduced with permission from Ref. [165]. Copyright 2021, Elsevier.

Fig. 16. (a) Schematic diagram of the preparation process of Ru/Cu-SZ-13 and the reaction route of NO and CB. (b) TEM images and particle size distribution of RuO2 nanoparticles. (c) HRTEM images of RuO2 NPs. (d) HRTEM images of CHA zeolite in Ru/Cu SZ-13. (e) Schematic diagram of the reaction mechanism of synergistic catalysis of NO and CB. Reproduced with permission from Ref. [167]. Copyright 2023, Wiley-VCH GmbH.

Fig. 17. (a) Toluene conversion and CO2 yield over different samples. (b) Toluene conversion and CO2 yield over 0.5 Pt1/Fe2O3 at varying light intensities. Reproduced with permission from Ref. [171]. Copyright 2021, Elsevier. Toluene oxidation (c) and CO2 yield (d) on 0.39Pt1/CuO-CeO2 and CuO-CeO2 catalysts in the dark or under simulated solar illumination. Reproduced with permission from Ref. [173]. Copyright 2022, American Chemical Society.

Fig. 18. (a) Effect of H2O concentration on catalytic stability over the Pt/CeO2/TiO2. (b) The structure diagram of Pt/CeO2/TiO2 and Pt/TiO2 and the reaction mechanism of photocatalytic oxidation of heptane and hexanal. Reproduced with permission from Ref. [174]. Copyright 2022, American Chemical Society.

Fig. 19. (a) Diagrammatic sketch of the 1.1 wt% AuCu0.75/Al2O3 preparation process. (b) HAADF-STEM image of AuCu NPs. (c) Product selectivity over 1.1 wt% AuCu0.75/Al2O3. Reproduced with permission from Ref. [180]. Copyright 2022, Wiley-VCH GmbH.

Fig. 20. (a) Isopropanol-selective oxidation process. (b) Energy diagrams of isopropanol-selective oxidation. (c) Adsorption energy of isopropanol, acetone, and O2, respectively. (d) Partial density of states (PDOS). Reproduced with permission from Ref. [181]. Copyright 2023, American Chemical Society.

Table 2 Summary of the effect of H2O, CO2, and SO2 on the reaction in the different catalytic oxidation reaction.

VOCs type	Catalyst	H₂O content (vol%)	Effect of H₂O on catalytic activity	CO₂ content (vol%)	Effect of CO₂ on catalytic activity	SO₂ content (ppm)	Effect of SO₂ on catalytic activity	Ref.
Methane	Pd_2.41Pt	2.5 or 5	catalytically stable	2.5 or 5	no significant decline	100	dropped sharply	[46]
Methane	1.14Pd_2.8Pt/ 3DOM LMAO	5	decreased slightly	5	without decline	100	decreased significantly	[83]
Methane	0.44PtPd_2.20/ ZrO₂	10	decreased significantly	—	—	100	decreased significantly	[50]
Methane	1.93AuPd_1.95/3DOM CoCr₂O₄	5	decreased slightly	—	—	100	decreased slightly	[188]
n-Hexane	Co₁Ni₁/meso-Cr₂O₃	10	minor negative effect	5	not changed distinctly	—	—	[95]
Acetylene	0.59IrFe_0.90/meso-CeO₂	1 or 5	no significant changes	5	not altered significantly	50	decreased significantly	[189]
Benzene	0.25 Pt₁/meso-Fe₂O₃	1 or 3	enhancement effect	2.5	not change obviously	—	—	[60]
Benzene	0.0383Pt₁/OMS-2	1.5, 3, or 5	decreased significantly	5	no obvious changes	—	—	[61]
Benzene	TiO₂/PdW-S1	1 or 5	almost does not affect	5	not change obviously	—	—	[64]
Toluene	0.28Pd/S-1-H	2 or 5	decreased slightly	5	decreased slightly	50	declined sharply	[65]
Toluene	0.2 wt% Pt/TiO₂	2, 5, or 10	decreased slightly	2.5, 5, or 10	weak negative influence	50	decreased rapidly	[66]
Toluene	2.3 wt% Pt/3DOM Mn₂O₃	3 or 5	decreased slightly	3	decreased slightly	40	decreased gradually	[106]
Toluene	0.46PdPt_2.10/V₂O₅-TiO₂	5	no significant changes	5	no significant decrease	50	decreased slightly	[186]
Toluene	0.37Pt−0.16MnO_x/meso-CeO₂	1, 3 or 5	no considerable changes	5	decreased slightly	—	—	[68]
Toluene	1.98PtRu@3DOM CZO	5	decreased slightly	10	no significant changes	40	declined considerably	[107]
Methanol	0.70Pt_2.42Co/meso-MnO_y	3	obviously inhibited	5	obviously inhibited	—	—	[131]
Methanol	0.68Ag_0.75Au_1.14Pd/meso-Co₃O₄	3	decreased slightly	5	decreased slightly	—	—	[130]
Acetone	0.57 wt% CeO₂-0.05 wt% Pt/TiO₂	2.5, 5, 10, or 20	obviously inhibited	5 or 10	obviously inhibited	100	decreased significantly	[139]
Trichloroethylene	0.91Au_0.51Pd/3DOM TiO₂	3 or 5	slight decrease	5 or 10	slight decrease	—	—	[78]
Trichloroethylene	2.85AuPd_1.87/3DOM CeO₂	3 or 5	slight decrease	3 or 7	slight decrease	—	—	[79]
Trichloroethylene	0.93Ru_2.87Pd/3DOM CeO₂	3 or 5	obviously inhibited	5 or 10	obviously inhibited	—	—	[77]
1,2-Dichloroethane	RuCo/HZSM-5	5	slight decrease	—	—	100	marked decline	[74]
1,2-Dichloroethane	Ru/WO₃	5	enhancement effect	—	—	—	—	[72]
1,2-Dichloroethane	Ru/TiO₂-HPW	5	enhancement effect	—	—	—	—	[150]
Toluene	0.5Pt₁/Fe₂O₃	5 or 10	slight decrease	5 or 10	negligible effect	20	slight decrease	[171]
Heptane and hexane	Pt/CeO₂/TiO₂	5, 10, or 20	enhancement effect	—	—	—	—	[174]
Ethyl acetate	0.26Pd/3.2 N-TiO₂	5	enhancement effect	10	negligible effect	—	—	[176]

Table 2 Summary of the effect of H2O, CO2, and SO2 on the reaction in the different catalytic oxidation reaction.

VOCs type	Catalyst	H₂O content (vol%)	Effect of H₂O on catalytic activity	CO₂ content (vol%)	Effect of CO₂ on catalytic activity	SO₂ content (ppm)	Effect of SO₂ on catalytic activity	Ref.
Methane	Pd_2.41Pt	2.5 or 5	catalytically stable	2.5 or 5	no significant decline	100	dropped sharply	[46]
Methane	1.14Pd_2.8Pt/ 3DOM LMAO	5	decreased slightly	5	without decline	100	decreased significantly	[83]
Methane	0.44PtPd_2.20/ ZrO₂	10	decreased significantly	—	—	100	decreased significantly	[50]
Methane	1.93AuPd_1.95/3DOM CoCr₂O₄	5	decreased slightly	—	—	100	decreased slightly	[188]
n-Hexane	Co₁Ni₁/meso-Cr₂O₃	10	minor negative effect	5	not changed distinctly	—	—	[95]
Acetylene	0.59IrFe_0.90/meso-CeO₂	1 or 5	no significant changes	5	not altered significantly	50	decreased significantly	[189]
Benzene	0.25 Pt₁/meso-Fe₂O₃	1 or 3	enhancement effect	2.5	not change obviously	—	—	[60]
Benzene	0.0383Pt₁/OMS-2	1.5, 3, or 5	decreased significantly	5	no obvious changes	—	—	[61]
Benzene	TiO₂/PdW-S1	1 or 5	almost does not affect	5	not change obviously	—	—	[64]
Toluene	0.28Pd/S-1-H	2 or 5	decreased slightly	5	decreased slightly	50	declined sharply	[65]
Toluene	0.2 wt% Pt/TiO₂	2, 5, or 10	decreased slightly	2.5, 5, or 10	weak negative influence	50	decreased rapidly	[66]
Toluene	2.3 wt% Pt/3DOM Mn₂O₃	3 or 5	decreased slightly	3	decreased slightly	40	decreased gradually	[106]
Toluene	0.46PdPt_2.10/V₂O₅-TiO₂	5	no significant changes	5	no significant decrease	50	decreased slightly	[186]
Toluene	0.37Pt−0.16MnO_x/meso-CeO₂	1, 3 or 5	no considerable changes	5	decreased slightly	—	—	[68]
Toluene	1.98PtRu@3DOM CZO	5	decreased slightly	10	no significant changes	40	declined considerably	[107]
Methanol	0.70Pt_2.42Co/meso-MnO_y	3	obviously inhibited	5	obviously inhibited	—	—	[131]
Methanol	0.68Ag_0.75Au_1.14Pd/meso-Co₃O₄	3	decreased slightly	5	decreased slightly	—	—	[130]
Acetone	0.57 wt% CeO₂-0.05 wt% Pt/TiO₂	2.5, 5, 10, or 20	obviously inhibited	5 or 10	obviously inhibited	100	decreased significantly	[139]
Trichloroethylene	0.91Au_0.51Pd/3DOM TiO₂	3 or 5	slight decrease	5 or 10	slight decrease	—	—	[78]
Trichloroethylene	2.85AuPd_1.87/3DOM CeO₂	3 or 5	slight decrease	3 or 7	slight decrease	—	—	[79]
Trichloroethylene	0.93Ru_2.87Pd/3DOM CeO₂	3 or 5	obviously inhibited	5 or 10	obviously inhibited	—	—	[77]
1,2-Dichloroethane	RuCo/HZSM-5	5	slight decrease	—	—	100	marked decline	[74]
1,2-Dichloroethane	Ru/WO₃	5	enhancement effect	—	—	—	—	[72]
1,2-Dichloroethane	Ru/TiO₂-HPW	5	enhancement effect	—	—	—	—	[150]
Toluene	0.5Pt₁/Fe₂O₃	5 or 10	slight decrease	5 or 10	negligible effect	20	slight decrease	[171]
Heptane and hexane	Pt/CeO₂/TiO₂	5, 10, or 20	enhancement effect	—	—	—	—	[174]
Ethyl acetate	0.26Pd/3.2 N-TiO₂	5	enhancement effect	10	negligible effect	—	—	[176]

Fig. 21. (a) Schematic diagram of the preparation process of W1/PdO NPs. Effect of H2O content on CH4 conversion and CO2 selectivity over PdW1/Al2O3 (b) and Pd/Al2O3 (c). Reproduced with permission from Ref. [184]. Copyright 2022, Wiley-VCH GmbH.

Fig. 22. (A) CH4 conversion as a function of reaction time over different samples in the absence and presence of H2O. Reproduced with permission from Ref. [51]. Copyright 2017, American Chemical Society. (B) Propane conversion as a function of on-stream reaction time in the presence or absence of CO2 and H2O over PtNPCoNP/meso-NaxMnOy (c), Co1/meso-NaxMnOy (d), Pt1/meso-NaxMnOy (e), and Pt1Co1/meso-NaxMnOy (f). Reproduced with permission from Ref. [55]. Copyright 2022, American Chemical Society. (C) Benzene conversion as a function of on-stream reaction time in the presence or absence of SO2 in Pd/Al2O3 and Pd1Co1/Al2O3. Reproduced with permission from Ref. [62]. Copyright 2020, Elsevier.

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催化法治理挥发性有机物污染的研究进展

Recent progress on VOC pollution control via the catalytic method

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