Research Progress on Catalytic Oxidation of Volatile Organic Compounds by Perovskite Oxides

doi:10.15541/jim20240333

Abstract

Abstract:

Control and removal of volatile organic compounds (VOCs) have always been critical issues in the environmental field. Catalytic oxidation has emerged as one of the most promising technologies for VOCs removal due to its low operational temperature, high efficiency, and non-toxic by-products. Perovskite oxides (ABO₃) are recognized as efficient and stable catalysts for the catalytic oxidation of VOCs. To enhance the catalytic efficiency of perovskite-based catalysts, it is necessary to systematically analyze and optimize the design of perovskite oxides to meet the specific requirements for the removal of different VOCs. This paper comprehensively reviews recent advances in the catalytic oxidation of VOCs using perovskite oxides. Firstly, various design strategies for perovskite oxides in the catalytic oxidation of VOCs, including morphology control, A-site and B-site substitution, defect engineering, and supported perovskite catalysts, are introduced, giving a close link between the catalytic performance of perovskite oxides and their material composition, morphology, surface properties (oxygen species, defects), and intrinsic properties (oxygen vacancy concentration, lattice structure). The reaction mechanisms and degradation pathways involved in the catalytic oxidation of VOCs are analyzed, and the prospects and challenges in the rational design of perovskite oxide catalysts and the exploration of reaction mechanisms are outlined.

Key words: volatile organic compound, perovskite oxide, structure design, catalytic oxidation, review

CLC Number:

O643

ZHU Wenjie, TANG Lu, LU Jichang, LIU Jiangping, LUO Yongming. Research Progress on Catalytic Oxidation of Volatile Organic Compounds by Perovskite Oxides[J]. Journal of Inorganic Materials, 2025, 40(7): 735-746.

Figures/Tables 11

Fig. 1 Design strategies for perovskite oxides

Fig. 2 Catalytic oxidation of CO and toluene by multi-shelled spherical PrMnO3 perovskite[20]

Fig. 3 Water and sulfur resistance over LaFe0.8Cu0.2O3 in the temperature range of 100-600 ℃[25] (a) C3H3N conversion; (b) CO2 yield; (c) CO yield; (d) N2 yield; (e) NH3 yield; (f) N2O yield; (g) NOx yield

Table 1 A- and B-sites doped perovskite catalysts and their application in catalytic oxidation of VOCs

Catalyst	VOCs	ρ_VOCs/ (mg·L^-1)	^aGHSV/ (mL·g^-1·h^-1)	Preparation method	^bT₅₀/℃	^cT₉₀/℃	^dR/(mol·g^-1·s^-1)	Ref.
La_0.95Ce_0.05CoO₃	Chlorobenzene	4605	60000	Reactive grinding method	377	434	1.083×10^-3 (200 ℃)	[31]
La_0.95Ce_0.05CoO₃	Chlorobenzene	4605	60000	Sol-Gel method	313	425	6.775×10^-9 (200 ℃)	[31]
La_0.9Ce_0.1MnO₃	Styrene	12780	25000	Sol-Gel method	306	328	-	[38]
LaFe_0.8Cu_0.2O₃	Acrylonitrile	6512	120000	Sol-Gel method	-	250	-	[25]
LaFe_0.8Co_0.2O₃	Propylene	1722	60000	Sol-Gel method	293	345	-	[24]
LaMn_0.8Cu_0.2O₃	Formaldehyde	368	12000	Sol-Gel method	138	168	-	[39]
LaMn_0.8Ni_0.2O₃					143	200
LaMn_0.8Zn_0.2O₃					146	200
LaMn_0.7Mg_0.3O₃	Methane	328	50000	Sol-Gel method	450	495	6.90×10^-7 (400 ℃)	[40]
La_0.5Sr_0.5Co_0.8Fe_0.2O₃	Toluene	3770	30000	Sol-Gel method	251	270	8.43×10^-8 (230 ℃)	[36]
La_0.8Ce_0.2Mn_0.8Ni_0.2O₃	Trichloroethylene	806	10000	Sol-Gel method	310	379	-	[35]
La_0.8Ce_0.2Mn_0.8Ni_0.2O₃	Toluene	3770	18000	Sol-Gel method	260	295	-	[34]
La_0.9Sr_0.1Co_0.9Mn_0.1O₃	Benzene	6390	30000	PMMA template method	272	328	-	[18]

Fig. 4 Selective dissolution technique combined with Cu-doping modified LaMnO3 catalyst[37] (a) Synergistically modulating the A- and B-sites of perovskite; (b) XRD patterns of the synthesized catalysts; (c1-c4) Catalytic activities of the synthesized catalysts under different conditions

Fig. 5 Activity and stability tests of LaFeO3 (LxFO) with A-site cation deficiency in catalytic oxidation of toluene[46] (a) Toluene conversion as a function of reaction temperature over LxFO samples (0.80≤x≤1.00) and commercial Fe2O3; (b) Effect of GHSV on the catalytic performance of L0.90FO sample; (c) Arrhenius plots of toluene oxidation over LxFO samples (0.80≤x≤1.00) under the conditions of toluene mass concentration 1000 mg·L−1 and GHSV 20000 mL·g−1·h−1; (d) Thermal stability test of toluene catalytic oxidation over L0.90FO sample at 300 ℃ (toluene mass concentration 1000 mg·L−1 and GHSV 20000 mL·g−1·h−1)

Fig. 6 Structure and characterization of LaxFeO3 (x=1.03, 1, 0.97) perovskite[47] (a) Unit cell of perovskite oxide (ABO3) with an ideal cubic structure (left), corresponding coordination state of bulk (middle) and surface (right) lattice oxygen (perovskite surface terminated with Fe cations); (b-d) EDS mappings and (e-g) corresponding HRTEM images of (b, e) La1.03FeO3, (c, f) LaFeO3, and (d, g) La0.97FeO3; (h) H2-TPR profiles of LaxFeO3 (x=1.03, 1, 0.97) oxides

Table 2 Perovskite-based supported catalysts and their application in catalytic oxidation of VOCs

Catalyst	VOCs	ρ_VOCs/ (mg·L⁻¹)	^aGHSV/ (mL·g⁻¹·h⁻¹)	^bT₅₀/℃	^cT₉₀/℃	^dR	Ref.
Ag/LaCoO₃-250	Toluene	3770	30000	231	239	4.19×10⁻⁹ mol·m⁻²·s⁻¹ (225 ℃)	[53]
Ag/LaCoO₃-450				260	278	3.09×10⁻⁹ mol·m⁻²·s⁻¹ (225 ℃)
Ag/LaCoO₃-700				252	267	3.44×10⁻⁹ mol·m⁻²·s⁻¹ (225 ℃)
LaMnO₃/CeO₂	1,2-Dichloropropane	4622	15000	171	260	-	[54]
LaMnO₃/Al₂O₃				178	243
LaMnO₃/TiO₂				183	249
LaMnO₃/YSZ				189	243
2%(in mass)Pd@N-L_0.8S_0.2MO	Toluene	188	36000	-	166	9.61×10⁻⁹ mol·g⁻¹·s⁻¹ (105 ℃)	[56]
20%(in mass)LaCoO₃/Ce_0.9Zr_0.1O₂	Toluene	6406	60000	200	-	1.6×10⁻⁶ mol·g⁻¹·s⁻¹ (300 ℃)	[58]
NiMnO₃/Ce_xZr_1-_xO₂/cordierite	Benzene	1834	15000	-	275 (^eT₉₅)	-	[59]
CeO₂-LaCo_0.25Fe_0.75O₃	Toluene	3770	18000	150	205	-	[60]
CeO₂-LaMn_0.25Fe_0.75O₃	Toluene	3770	18000	155	215	-	[60]

Fig. 7 Schematic diagrams of (a) MvK mechanism, (b) L-H mechanism and (c) E-R mechanism[62]

Fig. 8 Isothermal C16O oxidation reaction on perovskite with time-resolved isotopic 18O2[67]

Fig. 9 Comparison between experimental and simulated data for the LH-OS-ND model[69]

References 72

[1]	GUO Y, WEN M, LI G, et al. Recent advances in VOC elimination by catalytic oxidation technology onto various nanoparticles catalysts: a critical review. Applied Catalysis B: Environmental, 2021, 281: 119447.
[2]	ALMAIE S, VATANPOUR V, RASOULIFARD M H, et al. Volatile organic compounds (VOCs) removal by photocatalysts: a review. Chemosphere, 2022, 306: 135655.
[3]	ZHAO Z, MA S, GAO B, et al. A systematic review of intermediates and their characterization methods in VOCs degradation by different catalytic technologies. Separation and Purification Technology, 2023, 314: 123510.
[4]	ZHANG Y, LU J, ZHANG L, et al. Investigation into the catalytic roles of oxygen vacancies during gaseous styrene degradation process via CeO₂ catalysts with four different morphologies. Applied Catalysis B: Environmental, 2022, 309: 121249.
[5]	ZHAO R, WANG H, ZHAO D, et al. Review on catalytic oxidation of VOCs at ambient temperature. International Journal of Molecular Sciences, 2022, 23(22): 13739.
[6]	ZHANG Y, ZHU W, LU J, et al. Induced synthesis of CeO₂ with abundant crystal boundary for promoting catalytic oxidation of gaseous styrene. Applied Catalysis B: Environmental, 2024, 342: 123461.
[7]	LIAO W, ZHU W, LU J, et al. Revealing the equilibrium relationship between lattice oxygen mobility and styrene removal: sources of adsorption and activation by in situ experiments. Applied Surface Science, 2023, 629: 157434.
[8]	SU Y, FU K, PANG C, et al. Recent advances of chlorinated volatile organic compounds' oxidation catalyzed by multiple catalysts: reasonable adjustment of acidity and redox properties. Environmental Science & Technology, 2022, 56(14): 9854.
[9]	PEÑA M A, FIERRO J L. Chemical structures and performance of perovskite oxides. Chemical Reviews, 2001, 101(7): 1981. PMID
[10]	GRABOWSKA E. Selected perovskite oxides: characterization, preparation and photocatalytic properties—a review. Applied Catalysis B: Environmental, 2016, 186: 97.
[11]	WANG K, HAN C, SHAO Z, et al. Perovskite oxide catalysts for advanced oxidation reactions. Advanced Functional Materials, 2021, 31(30): 2102089.
[12]	YANG L, LI Y, SUN Y, et al. Perovskite oxides in catalytic combustion of volatile organic compounds: recent advances and future prospects. Energy & Environmental Materials, 2022, 5(3): 751.
[13]	HUMAYUN M, ULLAH H, USMAN M, et al. Perovskite-type lanthanum ferrite based photocatalysts: preparation, properties, and applications. Journal of Energy Chemistry, 2022, 66: 314. DOI
[14]	ARANDIYAN H, WANG Y, SUN H, et al. Ordered meso- and macroporous perovskite oxide catalysts for emerging applications. Chemical Communications, 2018, 54(50): 6484. DOI PMID
[15]	WEI Y, LENG Y, WANG R, et al. Peroxydisulfate activation by LaNiO₃ nanoparticles with different morphologies for the degradation of organic pollutants. Water Science and Technology, 2022, 85(1): 39.
[16]	WU M, LI H, MA S, et al. Boosting the surface oxygen activity for high performance iron-based perovskite oxide. Science of the Total Environment, 2021, 795: 148904.
[17]	郭晓青.钙钛矿催化剂的结构优化与掺杂改性及其对含甲烷废气的催化氧化性能研究. 青岛: 青岛科技大学硕士学位论文, 2022.
[18]	SHI Z, DONG F, TANG Z, et al. Design Sr, Mn-doped 3DOM LaCoO₃ perovskite catalysts with excellent SO₂ resistance for benzene catalytic combustion. Chemical Engineering Journal, 2023, 473: 145476.
[19]	LIU L, JIA J, SUN T, et al. A facile method for scalable preparation of mesoporous structured SmMnO₃ perovskites sheets for efficient catalytic oxidation of toluene. Materials Letters, 2018, 212: 107.
[20]	CHEN S, HAO Y, CHEN R, et al. Hollow multishelled spherical PrMnO₃ perovskite catalyst for efficient catalytic oxidation of CO and toluene. Journal of Alloys and Compounds, 2021, 861: 158584.
[21]	LIU J, WANG J, ZHAO Z, et al. Synthesis of La_xK_1-_xCoO₃ nanorod and their catalytic performances for CO oxidation. Journal of Rare Earths, 2014, 32(2): 170.
[22]	ŞAHIN R Z Y, DUPLANČIĆ M, TOMAŠIĆ V, et al. Essential role of B metal species in perovskite type catalyst structure and activity on toluene oxidation. International Journal of Environmental Science and Technology, 2022, 19(1): 553.
[23]	TARJOMANNEJAD A, FARZI A, NIAEI A, et al. An experimental and kinetic study of toluene oxidation over LaMn_1-_xB_xO₃ and La_0.8A_0.2Mn_0.3B_0.7O₃ (A=Sr, Ce and B=Cu, Fe) nano-perovskite catalysts. Korean Journal of Chemical Engineering, 2016, 33(9): 2628.
[24]	PAN F, ZHANG W, FERRONATO C, et al. Boosting propene oxidation activity over LaFeO₃ perovskite catalysts by cobalt substitution. Applied Catalysis A: General, 2022, 643: 118779.
[25]	ZHANG R, LI P, XIAO R, et al. Insight into the mechanism of catalytic combustion of acrylonitrile over Cu-doped perovskites by an experimental and theoretical study. Applied Catalysis B: Environmental, 2016, 196: 142.
[26]	CAO X, LU J, ZHENG X, et al. Regulation of the reaction pathway to design the high sulfur/coke-tolerant Ce-based catalysts for decomposing sulfur-containing VOCs. Chemical Engineering Journal, 2022, 429: 132473.
[27]	LI X, ZHAO H, LIANG J, et al. A-site perovskite oxides: an emerging functional material for electrocatalysis and photocatalysis. Journal of Materials Chemistry A, 2021, 9(11): 6650.
[28]	CHANG H, BJØRGUM E, MIHAI O, et al. Effects of oxygen mobility in La-Fe-based perovskites on the catalytic activity and selectivity of methane oxidation. ACS Catalysis, 2020, 10(6): 3707.
[29]	ANSARI A A, AHMAD N, ALAM M, et al. Physico-chemical properties stalytic activity of the Sol-Gel prepared Ce-ion doped LaMnO₃ perovskites. Scientific Reports, 2019, 9: 7747.
[30]	ANSARI A A, ADIL S F, ALAM M, et al. Catalytic performance of the Ce-doped LaCoO₃ perovskite nanoparticles. Scientific Reports, 2020, 10: 15012.
[31]	PÉREZ H A, LÓPEZ C A, CADÚS L E, et al. Catalytic feasibility of Ce-doped LaCoO₃ systems for chlorobenzene oxidation: an analysis of synthesis method. Journal of Rare Earths, 2022, 40(6): 897.
[32]	SHIN H, BAEK M, KIM D H. Sulfur resistance of Ca-substituted LaCoO₃ catalysts in CO oxidation. Molecular Catalysis, 2019, 468: 148.
[33]	LI X, LI M, MA X, et al. Nonstoichiometric perovskite for enhanced catalytic oxidation through excess A-site cation. Chemical Engineering Science, 2020, 219: 115596.
[34]	YUAN B, TAO Y, QI S, et al. Effect of A, B-site cation on the catalytic activity of La_1-_xA_xMn_1-_yB_yO₃ (A=Ce, B=Ni) perovskite-type oxides for toluene oxidation. Environmental Science and Pollution Research International, 2023, 30(13): 36993.
[35]	HE C B, PAN K L, CHANG M B. Catalytic oxidation of trichloroethylene from gas streams by perovskite-type catalysts. Environmental Science and Pollution Research International, 2018, 25(12): 11584. DOI PMID
[36]	LI Y, LIU S, YIN K, et al. Understanding the mechanisms of catalytic enhancement of La-Sr-Co-Fe-O perovskite-type oxides for efficient toluene combustion. Journal of Environmental Chemical Engineering, 2023, 11(1): 109050.
[37]	WANG D, LUO K, TIAN H, et al. Transforming plain LaMnO₃ perovskite into a powerful ozonation catalyst: elucidating the mechanisms of simultaneous A and B sites modulation for enhanced toluene degradation. Environmental Science & Technology, 2024, 58(27): 12167.
[38]	辛松.改性钙钛矿催化燃烧苯乙烯的稳定性与耐久性研究. 武汉: 华中科技大学硕士学位论文, 2020.
[39]	丁俊彦.镧锰钙钛矿掺杂改性对甲醛催化氧化脱除的实验与机理研究. 武汉: 华中科技大学博士学位论文, 2022.
[40]	FENG M, LIN J, LI J, et al. Magnesium-enhanced redox property and surface acidity-basicity of LaMnO₃ perovskites for efficient methane purification. Separation and Purification Technology, 2024, 330: 125391.
[41]	WEXLER R B, GAUTAM G S, STECHEL E B, et al. Factors governing oxygen vacancy formation in oxide perovskites. Journal of the American Chemical Society, 2021, 143(33): 13212. DOI PMID
[42]	LI S F, ZHENG J, YAN D. Cationic defect engineering in perovskite La₂CoMnO₆ for enhanced electrocatalytic oxygen evolution. Inorganic Chemistry, 2023, 62(28): 11009.
[43]	LUO Y, WU Y. Defect engineering of nanomaterials for catalysis. Nanomaterials, 2023, 13(6): 1116.
[44]	FENG C, GAO Q, XIONG G, et al. Defect engineering technique for the fabrication of LaCoO₃ perovskite catalyst via urea treatment for total oxidation of propane. Applied Catalysis B: Environmental, 2022, 304: 121005.
[45]	XU Y, DHAINAUT J, DACQUIN J P, et al. On the role of cationic defects over the surface reactivity of manganite-based perovskites for low temperature catalytic oxidation of formaldehyde. Applied Catalysis B: Environmental, 2024, 342: 123400.
[46]	WU M, CHEN S, XIANG W. Oxygen vacancy induced performance enhancement of toluene catalytic oxidation using LaFeO₃ perovskite oxides. Chemical Engineering Journal, 2020, 387: 124101.
[47]	HE J, WANG T, BI X, et al. Subsurface A-site vacancy activates lattice oxygen in perovskite ferrites for methane anaerobic oxidation to syngas. Nature Communications, 2024, 15: 5422. DOI PMID
[48]	YANG J, SHI L, LI L, et al. Surface modification of macroporous La_0.8Sr_0.2CoO₃ perovskite oxides integrated monolithic catalysts for improved propane oxidation. Catalysis Today, 2021, 376: 168.
[49]	DAI L, LU X B, CHU G H, et al. Surface tuning of LaCoO₃ perovskite by acid etching to enhance its catalytic performance. Rare Metals, 2021, 40(3): 555.
[50]	BAI S, ZHANG N, GAO C, et al. Defect engineering in photocatalytic materials. Nano Energy, 2018, 53: 296.
[51]	FANG Z, BUEKEN B, DE VOS D E, et al. Defect-engineered metal-organic frameworks. Angewandte Chemie International Edition, 2015, 54(25): 7234.
[52]	ARANDIYAN H, MOFARAH S S, SORRELL C C, et al. Defect engineering of oxide perovskites for catalysis and energy storage: synthesis of chemistry and materials science. Chemical Society Reviews, 2021, 50(18): 10116. DOI PMID
[53]	CHEN H, WEI G, LIANG X, et al. The distinct effects of substitution and deposition of Ag in perovskite LaCoO₃ on the thermally catalytic oxidation of toluene. Applied Surface Science, 2019, 489: 905.
[54]	ZHANG C H, WANG C, GIL S, et al. Catalytic oxidation of 1,2-dichloropropane over supported LaMnO_x oxides catalysts. Applied Catalysis B: Environmental, 2017, 201: 552.
[55]	CHEN B, WEN Y, GAO S, et al. Mechanistic insights into the role of acidity to activity and anti-poisoning over Nb based catalysts for CVOCs combustion. Applied Catalysis A: General, 2022, 636: 118581.
[56]	LI X, CHEN D, LI N, et al. Highly efficient Pd catalysts loaded on La_1-_xSr_xMnO₃ perovskite nanotube support for low-temperature toluene oxidation. Journal of Alloys and Compounds, 2021, 871: 159575.
[57]	GIROIR-FENDLER A, ALVES-FORTUNATO M, RICHARD M, et al. Synthesis of oxide supported LaMnO₃ perovskites to enhance yields in toluene combustion. Applied Catalysis B: Environmental, 2016, 180: 29.
[58]	ALIFANTI M, FLOREA M, SOMACESCU S, et al. Supported perovskites for total oxidation of toluene. Applied Catalysis B: Environmental, 2005, 60(1/2): 33.
[59]	DENG L, HUANG C, KAN J, et al. Effect of coating modification of cordierite carrier on catalytic performance of supported NiMnO₃ catalysts for VOCs combustion. Journal of Rare Earths, 2018, 36(3): 265.
[60]	QI S, TAO Y, JIANG S, et al. CeO₂ supported MOFs derived LaB_xFe_yO₃ (B=Mn, Co) perovskite catalysts for degradation of toluene. Environmental Science and Pollution Research, 2023, 30(15): 45414.
[61]	耿俊, 柯权力, 周文茜, 等. 催化燃烧催化剂抗硫性的研究进展. 燃料化学学报, 2022, 50(5): 564.
[62]	YANG C, MIAO G, PI Y, et al. Abatement of various types of VOCs by adsorption/catalytic oxidation: a review. Chemical Engineeing Journal, 2019, 370: 1128.
[63]	HE C, LI P, CHENG J, et al. A comprehensive study of deep catalytic oxidation of benzene, toluene, ethyl acetate, and their mixtures over Pd/ZSM-5 catalyst: mutual effects and kinetics. Water, Air, & Soil Pollution, 2010, 209: 365.
[64]	MARS P, VAN KREVELEN D W. Oxidations carried out by means of vanadium oxide catalysts. Chemical Engineering Science, 1954, 3: 41.
[65]	BEHAR S, GÓMEZ-MENDOZA N A, GÓMEZ-GARCÍA M Á, et al. Study and modelling of kinetics of the oxidation of VOC catalyzed by nanosized Cu-Mn spinels prepared via an alginate route. Applied Catalysis A: General, 2015, 504: 203.
[66]	LENG Y, CAO X, SUN X, et al. Catalytic oxidation mechanism of toluene on the Ce_0.875Zr_0.125O₂ (110) surface. Catalysts, 2023, 14(1): 22.
[67]	LI X, WANG X, DING J, et al. Engineering active surface oxygen sites of cubic perovskite cobalt oxides toward catalytic oxidation reactions. ACS Catalysis, 2023, 13(9): 6338.
[68]	ZHANG Z, JIANG Z, SHANGGUAN W. Low-temperature catalysis for VOCs removal in technology and application: a state-of-the-art review. Catalysis Today, 2016, 264: 270.
[69]	ZONOUZ P R, NIAEI A, TARJOMANNEJAD A. Kinetic modeling of CO oxidation over La_1-_xA_xMn_0.6Cu_0.4O₃ (A=Sr and Ce) nanoperovskite-type mixed oxides. International Journal of Environmental Science and Technology, 2016, 13(7): 1665.
[70]	ZABIHI M, KHORASHEH F, SHAYEGAN J. Studies on the catalyst preparation methods and kinetic behavior of supported cobalt catalysts for the complete oxidation of cyclohexane. Reaction Kinetics, Mechanisms and Catalysis, 2015, 114(2): 611.
[71]	ARANZABAL A, AYASTUY-ARIZTI J L, GONZÁLEZ- MARCOS J A, et al. The reaction pathway and kinetic mechanism of the catalytic oxidation of gaseous lean TCE on Pd/alumina catalysts. Journal of Catalysis, 2003, 214(1): 130.
[72]	AO R, MA L, GUO Z, et al. NO oxidation performance and kinetics analysis of BaMO₃ (M=Mn, Co) perovskite catalysts. Environmental Science and Pollution Research International, 2021, 28(6): 6929.