用于消除挥发性有机物的有序多孔金属氧化物催化剂的研究进展

doi:10.7503/cjcu20131271

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (6): 1119.doi: 10.7503/cjcu20131271

用于消除挥发性有机物的有序多孔金属氧化物催化剂的研究进展

邓积光^1,², 何胜男², 谢少华², 杨黄根², 刘雨溪², 戴洪兴^1,²()

1. 北京工业大学区域大气复合污染防治北京市重点实验室
2.环境与能源工程学院化学化工系, 北京 100124

收稿日期:2013-12-25 出版日期:2014-06-10 发布日期:2014-04-21
作者简介:联系人简介: 戴洪兴, 男, 博士, 教授, 博士生导师, 主要从事多相催化、光催化及纳米孔材料合成等方面的研究. E-mail:hxdai@bjut.edu.cn
基金资助:
国家自然科学基金(批准号: 21103005, 21377008)、北京市自然科学基金(批准号: 2132015)和教育部高等学校博士学科点专项科研基金(新教师类)(批准号: 20111103120006)资助

Research Advancements of Ordered Porous Metal Oxide Catalysts for the Oxidative Removal of Volatile Organic Compounds^†

DENG Jiguang^1,², HE Shengnan², XIE Shaohua², YANG Huanggen², LIU Yuxi², DAI Hongxing^1,^2,^*()

1. Beijing Key Laboratory on Regional Air Pollution Prevention and Control
2. Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering,Beijing University of Technology, Beijing 100124, China

Received:2013-12-25 Online:2014-06-10 Published:2014-04-21
Contact: DAI Hongxing E-mail:hxdai@bjut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21103005, 21377008), the Natural Science Foundation of Beijing Municipality, China(No.2132015) and the Doctoral Fund of the Ministry of Education of China(No.20111103120006)

摘要/Abstract

摘要：

综述了近年来国内外用于消除挥发性有机物的有序多孔金属氧化物催化剂的研究进展, 主要包括有序多孔氧化铈、氧化锰、氧化钴、氧化铁、氧化铬和钙钛矿型氧化物及其负载贵金属或过渡金属氧化物. 讨论了这些催化剂对典型挥发性有机物氧化的催化性能, 并展望了新型高效消除挥发性有机物催化剂的研发前景及技术发展趋势.

关键词: 三维有序多孔材料, 金属氧化物, 钙钛矿型氧化物, 负载型催化剂, 挥发性有机物的催化氧化

Abstract:

Ordered porous metal oxide catalysts(mainly including ceria, manganese oxides, cobalt oxides, iron oxides, chromia, perovskite-type oxides and supported noble metals or transition-metal oxides) investigated in recent years were reviewed. The catalytic behavior of these materials for the oxidative removal of typical volatile organic compounds(VOCs) was discussed. The design and development of novel catalysts with high performance and related technologies for VOCs removal were envisioned.

Key words: Three-dimensional ordered porous material, Metal oxide, Perovskite-type oxide, Supported catalyst, Catalytic volatile organic compound oxidation

中图分类号:

O643

TrendMD:

邓积光, 何胜男, 谢少华, 杨黄根, 刘雨溪, 戴洪兴. 用于消除挥发性有机物的有序多孔金属氧化物催化剂的研究进展. 高等学校化学学报, 2014, 35(6): 1119.

DENG Jiguang, HE Shengnan, XIE Shaohua, YANG Huanggen, LIU Yuxi, DAI Hongxing. Research Advancements of Ordered Porous Metal Oxide Catalysts for the Oxidative Removal of Volatile Organic Compounds^†. Chem. J. Chinese Universities, 2014, 35(6): 1119.

图/表 4

Fig.1 TEM images of ordered mesoporous transition metal oxides[23,24,26] (A) CrOx; (B) Fe2O3; (C) Co3O4; (D) MnO2.

Table 1 Catalytic activities of the bulk and ordered mesoporous metal oxides for the oxidation of VOC

Sample	Volume fraction of VOC	Molar ratio of VOC/O₂	SV/( mL·g^-1·h^-1)	$T 50 % a$ /℃	$T 90 % b$ /℃	Ref.
3DOMeso CeO₂	0.045% Naphthalene	1∶445	75000	230	270	[19]
3DOMeso CeO₂	0.045% Naphthalene	1∶445	50000	220	245	[27]
3DOMeso MnO₂	0.1% Toluene	1∶200	20000	190	240	[26]
3DOMeso MnO₂	0.1% Toluene	1∶400	20000	203	217	[28]
Co₃O₄ nanoparticle	0.04% Formaldehyde	1∶500	30000	202	220	[22]
2DOMeso Co₃O₄	0.04% Formaldehyde	1∶500	30000	122	140	[22]
3DOMeso Co₃O₄	0.04% Formaldehyde	1∶500	30000	105	120	[22]
Bulk Co₃O₄	0.1% Toluene	1∶20	20000	200		[25]
3DOMeso Co₃O₄	0.1% Toluene	1∶20	20000	140	180	[25]
Bulk Co₃O₄	0.1% Methanol	1∶20	20000	142		[25]
3DOMeso Co₃O₄	0.1% Methanol	1∶20	20000	105	139	[25]
3DOMeso Co₃O₄	0.1% Toluene	1∶200	20000	160	200	[26]
3DOMeso Co₃O₄	0.1% Toluene	1∶400	20000	228	233	[28]
Bulk Fe₂O₃	0.1% Acetone	1∶20	20000	235		[24]
3DOMeso Fe₂O₃	0.1% Acetone	1∶20	20000	151	208	[24]
Bulk Fe₂O₃	0.1% Methanol	1∶20	20000	264		[24]
3DOMeso Fe₂O₃	0.1% Methanol	1∶20	20000	170	204	[24]
3DOMeso Cr₂O₃	0.04862% Toluene		30000	200	300	[20]
Bulk CrO_x	0.1% Toluene	1∶400	20000	190		[23]
3DOMeso CrO_x	0.1% Toluene	1∶400	20000	140	234	[23]
Bulk CrO_x	0.1% Ethyl acetate	1∶400	20000	172		[23]
3DOMeso CrO_x	0.1% Ethyl acetate	1∶400	20000	137	190	[23]
3DOMeso CrO_x	0.05% Formaldehyde	1∶300	30000	92	117	[29]
3DOMeso CrO_x	0.05% Acetone	1∶300	30000	75	124	[29]
3DOMeso CrO_x	0.05% Methanol	1∶300	30000	98	130	[29]
3DOMeso CrO_x	0.01% Toluene	1∶1800	20000	160	250	[30]

Table 1 Catalytic activities of the bulk and ordered mesoporous metal oxides for the oxidation of VOC

Sample	Volume fraction of VOC	Molar ratio of VOC/O₂	SV/( mL·g^-1·h^-1)	$T 50 % a$ /℃	$T 90 % b$ /℃	Ref.
3DOMeso CeO₂	0.045% Naphthalene	1∶445	75000	230	270	[19]
3DOMeso CeO₂	0.045% Naphthalene	1∶445	50000	220	245	[27]
3DOMeso MnO₂	0.1% Toluene	1∶200	20000	190	240	[26]
3DOMeso MnO₂	0.1% Toluene	1∶400	20000	203	217	[28]
Co₃O₄ nanoparticle	0.04% Formaldehyde	1∶500	30000	202	220	[22]
2DOMeso Co₃O₄	0.04% Formaldehyde	1∶500	30000	122	140	[22]
3DOMeso Co₃O₄	0.04% Formaldehyde	1∶500	30000	105	120	[22]
Bulk Co₃O₄	0.1% Toluene	1∶20	20000	200		[25]
3DOMeso Co₃O₄	0.1% Toluene	1∶20	20000	140	180	[25]
Bulk Co₃O₄	0.1% Methanol	1∶20	20000	142		[25]
3DOMeso Co₃O₄	0.1% Methanol	1∶20	20000	105	139	[25]
3DOMeso Co₃O₄	0.1% Toluene	1∶200	20000	160	200	[26]
3DOMeso Co₃O₄	0.1% Toluene	1∶400	20000	228	233	[28]
Bulk Fe₂O₃	0.1% Acetone	1∶20	20000	235		[24]
3DOMeso Fe₂O₃	0.1% Acetone	1∶20	20000	151	208	[24]
Bulk Fe₂O₃	0.1% Methanol	1∶20	20000	264		[24]
3DOMeso Fe₂O₃	0.1% Methanol	1∶20	20000	170	204	[24]
3DOMeso Cr₂O₃	0.04862% Toluene		30000	200	300	[20]
Bulk CrO_x	0.1% Toluene	1∶400	20000	190		[23]
3DOMeso CrO_x	0.1% Toluene	1∶400	20000	140	234	[23]
Bulk CrO_x	0.1% Ethyl acetate	1∶400	20000	172		[23]
3DOMeso CrO_x	0.1% Ethyl acetate	1∶400	20000	137	190	[23]
3DOMeso CrO_x	0.05% Formaldehyde	1∶300	30000	92	117	[29]
3DOMeso CrO_x	0.05% Acetone	1∶300	30000	75	124	[29]
3DOMeso CrO_x	0.05% Methanol	1∶300	30000	98	130	[29]
3DOMeso CrO_x	0.01% Toluene	1∶1800	20000	160	250	[30]

Fig.2 SEM images of 3DOMacro LaMnO377(A), 3DOMacro La0.6Sr0.4MnO390(B), 8%CoOx/ 3DOMacro La0.6Sr0.4CoO386(C) and 6.4%Au/3DOMacro La0.6Sr0.4MnO390(D)

Table 2 Catalytic activities and activation energies(Ea) for toluene oxidation over the as-prepared 3DOMacro ABO3 samplesa

Sample	$T 50 % b$ /℃	$T 90 % c$ /℃	E_a/(kJ·mol^-1)	Ref.
LaMnO₃	222	243	58	[77]
SrFeO₃	292	340		[79]
EuFeO₃	322	353	96.0	[81]
Eu_0.6Sr_0.4FeO₃	278	305	81.1	[81]
La_0.6Sr_0.4FeO₃	271	312		[82]
La_0.6Sr_0.4Fe_0.8Bi_0.2O₃	220	242	45.9	[83]
3%Co₃O₄/Eu_0.6Sr_0.4FeO₃	251	270	72.3	[85]
La_0.6Sr_0.4CoO₃	240	260	57.8	[86]
8%Co₃O₄/La_0.6Sr_0.4CoO₃	210	227	43.3	[86]
12%MnO_x/LaMnO₃	193	215	61	[87]
LaCoO₃	217	231	38.6	[89]
7.63%Au/LaCoO₃	188	202	31.4	[89]
La_0.6Sr_0.4MnO₃	203	219	59	[90]
6.4%Au/La_0.6Sr_0.4MnO₃	150	170	44	[90]

Table 2 Catalytic activities and activation energies(Ea) for toluene oxidation over the as-prepared 3DOMacro ABO3 samplesa

Sample	$T 50 % b$ /℃	$T 90 % c$ /℃	E_a/(kJ·mol^-1)	Ref.
LaMnO₃	222	243	58	[77]
SrFeO₃	292	340		[79]
EuFeO₃	322	353	96.0	[81]
Eu_0.6Sr_0.4FeO₃	278	305	81.1	[81]
La_0.6Sr_0.4FeO₃	271	312		[82]
La_0.6Sr_0.4Fe_0.8Bi_0.2O₃	220	242	45.9	[83]
3%Co₃O₄/Eu_0.6Sr_0.4FeO₃	251	270	72.3	[85]
La_0.6Sr_0.4CoO₃	240	260	57.8	[86]
8%Co₃O₄/La_0.6Sr_0.4CoO₃	210	227	43.3	[86]
12%MnO_x/LaMnO₃	193	215	61	[87]
LaCoO₃	217	231	38.6	[89]
7.63%Au/LaCoO₃	188	202	31.4	[89]
La_0.6Sr_0.4MnO₃	203	219	59	[90]
6.4%Au/La_0.6Sr_0.4MnO₃	150	170	44	[90]

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用于消除挥发性有机物的有序多孔金属氧化物催化剂的研究进展

Research Advancements of Ordered Porous Metal Oxide Catalysts for the Oxidative Removal of Volatile Organic Compounds^†

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用于消除挥发性有机物的有序多孔金属氧化物催化剂的研究进展

Research Advancements of Ordered Porous Metal Oxide Catalysts for the Oxidative Removal of Volatile Organic Compounds†

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Research Advancements of Ordered Porous Metal Oxide Catalysts for the Oxidative Removal of Volatile Organic Compounds^†