三维有序大孔钙钛矿金属氧化物作为高效燃烧催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2020-1434

摘要/Abstract

摘要：

三维有序大孔（3DOM）材料因为具有独特的结构、可调的组成、高稳定性、高电子传递能力以及高比表面积而引起很多学者的研究兴趣。本文主要介绍了3DOM钙钛矿材料作为催化剂或载体在催化碳烟、挥发性有机物和甲烷燃烧方面取得的成果，分析了制备条件、结构特征对催化性能的影响；指出了3DOM钙钛矿材料具有优异的催化燃烧稳定性、高分子吸附和扩散能力以及高氧迁移率，能够显著降低氧化还原温度和表观活化能，因此可以作为高效燃烧催化剂。最后提出了未来研究重点和发展方向，在未来的研究中应该开发出更多可以与贵金属相媲美的廉价的新型3DOM材料以拓展3DOM材料应用范围。另外，3DOM 材料表面性能的提升以及用于催化燃烧的作用机理需进一步深入研究。

关键词: 三维有序大孔, 钙钛矿, 催化剂, 载体, 多相反应

Abstract:

Three-dimensional ordered macroporous (3DOM) materials have attracted great interests because of their unique structure, adjustable composition, high stability, high electron transport capability, and high specific surface area. In present work, the applications of 3DOM perovskite catalysts or carriers in the catalytic combustion of soot, volatile organic compounds and methane are introduced. The relationship of preparation conditions and structural characteristics to catalytic performance is discussed. The results show that 3DOM perovskite materials have excellent catalytic combustion stability, high molecular adsorption and diffusion capacity and high oxygen mobility, allowing them to be good combustion catalyst. Moreover, they can significantly decrease the redox temperature and apparent activation energy. Therefore, more novel and cost-effective 3DOM materials should be developed. Additionally, the improvement of the surface properties and the catalytic combustion mechanism of 3DOM materials still need further study.

Key words: three-dimensional ordered macroporous, perovskite, catalyst, carrier, multiphase reaction

中图分类号:

O643

李翠翠, 张婷, 安静, 曾见有, 马海霞. 三维有序大孔钙钛矿金属氧化物作为高效燃烧催化剂的研究进展[J]. 化工进展, 2021, 40(6): 3181-3190.

LI Cuicui, ZHANG Ting, AN Jing, ZENG Jianyou, MA Haixia. Research progress of three-dimensional ordered macroporous perovskite metal oxides as highly efficient combustion catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3181-3190.

图/表 9

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催化剂	反应物进料^①	加热速率/℃·min^-1	碳烟和催化剂质量比^②	T₅₀或T_m/℃	参考文献
LaFeO₃	0.2%NO+5%O₂+He	2	1∶10	412	［29］
LaMn_0.95Fe_0.05O₃	0.2%NO+5%O₂+Ar	2	1∶10	392^④	［31］
La_0.9K_0.1CoO₃	0.2%NO+5%O₂+Ar	2	1∶10	398	［44］
La_0.95K_0.05NiO₃	0.2%NO+5%O₂+N₂	2	1∶10	338	［32］
Sr_0.8K_0.2TiO₃	0.05%NO+20%O₂+N₂	5	1∶9	367	［33］
La_0.5Sr_0.5MnO₃	0.05%NO+20%O₂+N₂	5	1∶9	385	［34］
KNO₃/La_0.8Ce_0.2Mn_0.6Fe_0.4O₃	20%O₂+80%N₂+N₂	2	1∶9	379	［35］
Au0.04/ LaFeO₃	0.2%NO+5%O₂+Ar	2	1∶10	368^④	［38］
Au1.25/LaFeO₃	0.2%NO+5%O₂+Ar	2	1∶10	387	［39］
NiCo₂O₄	0.1%NO+5%O₂	2	1∶10	379	［40］
Co50Ce50^③	0.25%NO+5%O₂+N₂	2	1∶10	406^④	［41］

催化剂	反应物进料^①	加热速率/℃·min^-1	碳烟和催化剂质量比^②	T₅₀或T_m/℃	参考文献
LaFeO₃	0.2%NO+5%O₂+He	2	1∶10	412	［29］
LaMn_0.95Fe_0.05O₃	0.2%NO+5%O₂+Ar	2	1∶10	392^④	［31］
La_0.9K_0.1CoO₃	0.2%NO+5%O₂+Ar	2	1∶10	398	［44］
La_0.95K_0.05NiO₃	0.2%NO+5%O₂+N₂	2	1∶10	338	［32］
Sr_0.8K_0.2TiO₃	0.05%NO+20%O₂+N₂	5	1∶9	367	［33］
La_0.5Sr_0.5MnO₃	0.05%NO+20%O₂+N₂	5	1∶9	385	［34］
KNO₃/La_0.8Ce_0.2Mn_0.6Fe_0.4O₃	20%O₂+80%N₂+N₂	2	1∶9	379	［35］
Au0.04/ LaFeO₃	0.2%NO+5%O₂+Ar	2	1∶10	368^④	［38］
Au1.25/LaFeO₃	0.2%NO+5%O₂+Ar	2	1∶10	387	［39］
NiCo₂O₄	0.1%NO+5%O₂	2	1∶10	379	［40］
Co50Ce50^③	0.25%NO+5%O₂+N₂	2	1∶10	406^④	［41］

催化剂	质量/g	反应物进料	空速/mL?g^-1?h^-1	T₅₀/℃^①	T₉₀/℃^②	活化能/kJ?mol^-1	参考文献
LaMnO₃	0.1~0.2	0.1%甲苯+O₂	20000	2223	243	58	［42-43］
SrFeO_3-_δ	0.1	0.1%甲苯+O₂	20000	292	340	—	［44］
3Co_x/ Eu_0.6Sr_0.4FeO₃	0.1	0.1%甲苯+O₂	20000	250	270	72	［45］
3Co₃O₄/Eu_0.6Sr_0.4FeO₃	0.1	0.1%甲苯+O₂	20000	251	269	72.3	［46］
La_0.6Sr_0.4FeO_3-_δ	0.1	0.1%甲苯+O₂	20000	225	280	—	［47］
La_0.6Sr_0.4Fe_0.8Bi_0.2O_3-_δ	0.1	0.1%甲苯+O₂	20000	220	242	45.9	［48］
12% MnO_x/LaMnO₃（质量分数）	0.1	0.1%甲苯+O₂	20000	193	215	61	［49］
MnO₂/LaMnO₃	0.05	0.2%甲苯+O₂	120000	263	279	57	［50］
7.63Au/LaCoO₃	0.1	0.1%甲苯+O₂	20000	188	202	31.4	［51］
6.4Au/La_0.6Sr_0.4MnO₃	0.05	0.1%甲苯+O₂	20000	150	170	44	［52］
1.67Mn₃O₄-2Au/La_0.6Sr_0.4CoO₃	0.05	0.1%甲苯+O₂	20000	214	230	41.7	［54］
5.92Au/8MnO_x/La_0.6Sr_0.4MnO₃	0.05	0.1%甲苯+O₂	20000	205	220	52.8	［55］
Au/Co₃O₄	0.05	0.1%甲苯+O₂	20000	244	256	74	［56］
1.99Au-Pd/Co₃O₄	0.05	0.1%甲苯+O₂	40000	168	168	33	［57］

催化剂	质量/g	反应物进料	空速/mL?g^-1?h^-1	T₅₀/℃^①	T₉₀/℃^②	活化能/kJ?mol^-1	参考文献
LaMnO₃	0.1~0.2	0.1%甲苯+O₂	20000	2223	243	58	［42-43］
SrFeO_3-_δ	0.1	0.1%甲苯+O₂	20000	292	340	—	［44］
3Co_x/ Eu_0.6Sr_0.4FeO₃	0.1	0.1%甲苯+O₂	20000	250	270	72	［45］
3Co₃O₄/Eu_0.6Sr_0.4FeO₃	0.1	0.1%甲苯+O₂	20000	251	269	72.3	［46］
La_0.6Sr_0.4FeO_3-_δ	0.1	0.1%甲苯+O₂	20000	225	280	—	［47］
La_0.6Sr_0.4Fe_0.8Bi_0.2O_3-_δ	0.1	0.1%甲苯+O₂	20000	220	242	45.9	［48］
12% MnO_x/LaMnO₃（质量分数）	0.1	0.1%甲苯+O₂	20000	193	215	61	［49］
MnO₂/LaMnO₃	0.05	0.2%甲苯+O₂	120000	263	279	57	［50］
7.63Au/LaCoO₃	0.1	0.1%甲苯+O₂	20000	188	202	31.4	［51］
6.4Au/La_0.6Sr_0.4MnO₃	0.05	0.1%甲苯+O₂	20000	150	170	44	［52］
1.67Mn₃O₄-2Au/La_0.6Sr_0.4CoO₃	0.05	0.1%甲苯+O₂	20000	214	230	41.7	［54］
5.92Au/8MnO_x/La_0.6Sr_0.4MnO₃	0.05	0.1%甲苯+O₂	20000	205	220	52.8	［55］
Au/Co₃O₄	0.05	0.1%甲苯+O₂	20000	244	256	74	［56］
1.99Au-Pd/Co₃O₄	0.05	0.1%甲苯+O₂	40000	168	168	33	［57］

催化剂	质量/g	反应物进料^①	空速/mL·g^-1·h^-1	T₅₀/℃	T₉₀/℃	活化能/kJ·mol^-1	参考文献
La₂CuO₄	0.05	2%CH₄+20%O₂	50000	560	672	—	［58］
La_0.6Sr_0.4MnO₃	0.02	2%CH₄+20%O₂	30000	566	661	56.6	［36］
La_0.7Ce_0.3CoO₃	0.02	2%CH₄+20%O₂	30000	479	555	53	［59］
LaMn_0.97Pd_0.03O₃	0.05	1%CH₄+17%O₂	32000	412	504	51.5	［61］
1.18% Pd/La_0.6Sr_0.4MnO₃（质量分数）	0.05	0.5%CH₄+20%O₂	40000	489	583	—	［62］
3.63% Ag/La_0.6Sr_0.4MnO₃（质量分数）	0.02	2%CH₄+20%O₂	30000	454	524	37.5	［63-64］
3% Au-Pd/La_0.6Sr_0.4MnO₃（质量分数）	0.02	5%CH₄+30%O₂	50000	331	354	46.3	［65］
1.93% Au-Pd1.95/CoCr₂O₄（质量分数）	0.05	2.5%CH₄+20%O₂	20000	353	394	—	［66］
Au-Pd-0.4% CoO/Co₃O₄（质量分数）	0.05	2.5%CH₄+20%O₂	20000	312	341	63	［67］