燃料化学学报（中英文）

Type	Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Crystal plane	α-MnO₂(100)	HCHO	0.01	60000	150	[9]
α-MnO₂(110)	130	[9]
α-MnO₂(310)	60	[9]
α-MnO₂(110)	toluene	0.05	15000	170	[10]
α-MnO₂(210)	109	[10]
α-MnO₂(310)	172	[10]
δ-MnO₂(310)	toluene	0.05	60000	163	[11]
δ-MnO₂(001)	198	[11]
Crystal phase	α-MnO₂	toluene	0.1	60000	225	[12]
β-MnO₂	295	[12]
γ-MnO₂	260	[12]
δ-MnO₂	245	[12]
α/β-MnO₂	toluene	0.1	48000	210	[13]
Mn₃O₄/Mn₂O₃	propene	0.05	20000	220	[14]
Morphology	nanosphere MnO_x	toluene	0.1	60000	258	[15]
hollow ball MnO_x	toluene	0.1	60000	226	[15]
spherical β-MnO₂	toluene	0.1	60000	240	[16]
dice-shaped β-MnO₂	225	[16]
peach-shaped Mn₂O₃	255	[16]
bundle Mn₂O₃	240	[16]

Type	Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Crystal plane	α-MnO₂(100)	HCHO	0.01	60000	150	[9]
α-MnO₂(110)	130	[9]
α-MnO₂(310)	60	[9]
α-MnO₂(110)	toluene	0.05	15000	170	[10]
α-MnO₂(210)	109	[10]
α-MnO₂(310)	172	[10]
δ-MnO₂(310)	toluene	0.05	60000	163	[11]
δ-MnO₂(001)	198	[11]
Crystal phase	α-MnO₂	toluene	0.1	60000	225	[12]
β-MnO₂	295	[12]
γ-MnO₂	260	[12]
δ-MnO₂	245	[12]
α/β-MnO₂	toluene	0.1	48000	210	[13]
Mn₃O₄/Mn₂O₃	propene	0.05	20000	220	[14]
Morphology	nanosphere MnO_x	toluene	0.1	60000	258	[15]
hollow ball MnO_x	toluene	0.1	60000	226	[15]
spherical β-MnO₂	toluene	0.1	60000	240	[16]
dice-shaped β-MnO₂	225	[16]
peach-shaped Mn₂O₃	255	[16]
bundle Mn₂O₃	240	[16]

Type	Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Doping	Cu_0.05-MnO₂	toluene	0.05	36000	190	[5]
0.3MoMnO₂	benzene	0.048	60000	235	[29]
Fe₁Mn₅	toluene	0.1	30000	209	[30]
Cu₁Mn₁O	toluene	0.1	60000	214	[31]
10Co/OMS-2	toluene	0.2	60000	245	[32]
Pd/OMS-2	toluene	0.1	90000	247	[33]
Pd/OMS-2	acetone	0.1	90000	231	[33]
Cu/OMS-2	acetone	0.1	90000	207	[33]
Ir/OMS-2	dichloromethane	0.02	90000	293	[33]
Compositing	Co₁Mn₁O	toluene	0.4	24000	310	[34]
5Co1Mn	toluene	0.1	60000	237	[35]
CoMn₂O_x	toluene	0.1	40000	265	[36]
Ce_0.25Mn_0.75O_x	propane	0.5	45000	350	[37]
MC-TPAOH	toluene	0.1	60000	221	[38]
MnCe-7%	toluene	0.07	40000	195	[39]
chlorobenzene	0.03	174	[39]
toluene in mixture	0.07	240	[39]
chlorobenzene in mixture	0.03	260	[39]
LCMO	benzene	0.05	100000	240	[40]
toluene	0.05	50000	207	[40]
o-xylene	0.02	50000	227	[40]
RCMO	toluene	0.05	50000	240	[40]
GCMO	toluene	0.05	50000	280	[40]
MnCu	toluene	0.1	40000	214	[41]

Type	Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Doping	Cu_0.05-MnO₂	toluene	0.05	36000	190	[5]
0.3MoMnO₂	benzene	0.048	60000	235	[29]
Fe₁Mn₅	toluene	0.1	30000	209	[30]
Cu₁Mn₁O	toluene	0.1	60000	214	[31]
10Co/OMS-2	toluene	0.2	60000	245	[32]
Pd/OMS-2	toluene	0.1	90000	247	[33]
Pd/OMS-2	acetone	0.1	90000	231	[33]
Cu/OMS-2	acetone	0.1	90000	207	[33]
Ir/OMS-2	dichloromethane	0.02	90000	293	[33]
Compositing	Co₁Mn₁O	toluene	0.4	24000	310	[34]
5Co1Mn	toluene	0.1	60000	237	[35]
CoMn₂O_x	toluene	0.1	40000	265	[36]
Ce_0.25Mn_0.75O_x	propane	0.5	45000	350	[37]
MC-TPAOH	toluene	0.1	60000	221	[38]
MnCe-7%	toluene	0.07	40000	195	[39]
chlorobenzene	0.03	174	[39]
toluene in mixture	0.07	240	[39]
chlorobenzene in mixture	0.03	260	[39]
LCMO	benzene	0.05	100000	240	[40]
toluene	0.05	50000	207	[40]
o-xylene	0.02	50000	227	[40]
RCMO	toluene	0.05	50000	240	[40]
GCMO	toluene	0.05	50000	280	[40]
MnCu	toluene	0.1	40000	214	[41]

Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Pt/H-MnO₂	toluene	0.1	60000	180	[56]
Pt/γ-MnO₂	190	[56]
Pt/α-MnO₂	170	[56]
Pt/β-MnO₂	185	[56]
Pt/MnO₂-r-WI	toluene	0.15	40000	224	[57]
Pd/MnO₂	toluene	0.1	60000	200	[58]
0.91Au_0.48Pd/α-MnO₂	toluene	0.1	40000	185	[59]
m-xylene	0.1	200	[59]
toluene in mixture	0.1	40000	212	[59]
m-xylene in mixture	0.1	210	[59]
Pt/Mn₃O₄-R	toluene	0.1	48000	183	[60]
Pt/Mn₃O₄-C	226	[60]
Pt/Mn₂O₃	toluene	0.1	120000	202	[61]
acetone	0.1	120000	169	[61]
H₂-Pt₁/MnO_x-200	toluene	0.1	40000	219	[62]
Ag/HMO	benzene	0.02	23000	200	[63]
0.0383Pt₁/OMS-2	benzene	0.1	20000	189	[64]

Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Pt/H-MnO₂	toluene	0.1	60000	180	[56]
Pt/γ-MnO₂	190	[56]
Pt/α-MnO₂	170	[56]
Pt/β-MnO₂	185	[56]
Pt/MnO₂-r-WI	toluene	0.15	40000	224	[57]
Pd/MnO₂	toluene	0.1	60000	200	[58]
0.91Au_0.48Pd/α-MnO₂	toluene	0.1	40000	185	[59]
m-xylene	0.1	200	[59]
toluene in mixture	0.1	40000	212	[59]
m-xylene in mixture	0.1	210	[59]
Pt/Mn₃O₄-R	toluene	0.1	48000	183	[60]
Pt/Mn₃O₄-C	226	[60]
Pt/Mn₂O₃	toluene	0.1	120000	202	[61]
acetone	0.1	120000	169	[61]
H₂-Pt₁/MnO_x-200	toluene	0.1	40000	219	[62]
Ag/HMO	benzene	0.02	23000	200	[63]
0.0383Pt₁/OMS-2	benzene	0.1	20000	189	[64]

锰基催化剂用于VOCs催化燃烧的研究进展

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罗光峻 ¹ , 陈爽 ¹^,^* , 殷宏 ¹ , 曾嘉 ² , 谢红梅 ²^,^* , 周桂林 ¹^,²

燃料化学学报（中英文） | 2026,54(6): 20250254-1007-20250254-1022

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燃料化学学报（中英文） 2026 , 54 (6) : 20250254-1007 -20250254-1022

锰基催化剂用于VOCs催化燃烧的研究进展

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罗光峻¹, 陈爽¹^,^*, 殷宏¹, 曾嘉², 谢红梅²^,^*, 周桂林¹^,²

作者信息

¹重庆工商大学废油资源化技术与装备教育部工程研究中心, 重庆 400072

²重庆工商大学环境与资源学院, 重庆 400072

通讯作者:

陈爽, 谢红梅

Research progress on Mn-based catalysts for catalytic combustion of VOCs

Guangjun LUO¹, Shuang CHEN¹^,^*, Hong YIN¹, Jia ZENG², Hongmei XIE²^,^*, Guilin ZHOU¹^,²

Affiliations

¹Chongqing Technology and Business University, Engineering Research Center for Waste Oil Recycling Technology and Equipment, Ministry of Education, Chongqing 400072, China

²Chongqing Technology and Business University, School of Environment and Resources, Chongqing 400072, China

Corresponding Author:

Tel: +86-23-62769785, E-mail: chenshuang@ctbu.edu.cn

xiehongmei@ctbu.edu.cn

出版时间: 2026-06-10 doi: 10.1016/S1872-5813(26)60645-7

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摘要

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挥发性有机物(VOCs)来源广泛，对大气环境影响突出，可对人体健康造成严重危害。锰(Mn)基催化剂因其结构多样、类型丰富，在VOCs催化燃烧领域应用广泛。本综述总结了多种锰基催化剂的催化性能，重点讨论了高性能锰基催化剂的制备策略，解析了活性位点的构筑对锰基催化剂催化燃烧性能的影响，并阐述了VOCs的催化氧化机理，对VOCs的污染治理具有一定的借鉴作用。

关键词

锰基催化剂 / 催化燃烧 / 金属复合 / 金属负载 / 反应机理

Abstract

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Volatile organic compounds (VOCs) originating from diverse sources, exert a profound detrimental impact on the atmospheric environment and pose grave threats to human health. Manganese (Mn)-based catalysts, celebrated for their exceptional structural diversity and abundant redox versatility, are extensively employed in the catalytic combustion of VOCs. This review summarizes the catalytic performance of diverse Mn-based catalysts. It emphasizes strategies for preparing high-performance Mn-based catalysts and provides a systematic analysis of how the construction of active sites influences their catalytic combustion performance for VOCs. Furthermore, the catalytic oxidation mechanisms of VOCs are expounded in detail. This work offers valuable insights and practical guidance for the remediation of VOCs pollution.

Key words

Mn-based catalysts / catalytic oxidation / metal composite / metal support / reaction mechanisms

引用本文

罗光峻, 陈爽, 殷宏, 曾嘉, 谢红梅, 周桂林. 锰基催化剂用于VOCs催化燃烧的研究进展. 燃料化学学报（中英文）, 2026 , 54 (6) : 20250254-1007 -20250254-1022 . DOI: 10.1016/S1872-5813(26)60645-7

Guangjun LUO, Shuang CHEN, Hong YIN, Jia ZENG, Hongmei XIE, Guilin ZHOU. Research progress on Mn-based catalysts for catalytic combustion of VOCs[J]. Journal of Fuel Chemistry and Technology, 2026 , 54 (6) : 20250254-1007 -20250254-1022 . DOI: 10.1016/S1872-5813(26)60645-7

正文

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Volatile organic compounds (VOCs) denote organic chemicals that readily volatilize into the gaseous phase under ambient temperature and pressure^[1]. VOCs can infiltrate the human body and induce pulmonary diseases, while also serving as precursors to secondary organic aerosols (SOA) and ozone (O₃) in photochemical reactions, thereby exacerbating environmental pollution^[2−4]. Given the enormous market demand for VOCs control, there is an urgent need for treatment technologies that are stable, highly efficient, and economically feasible. Currently, common VOCs removal technologies include catalytic combustion, adsorption, biodegradation, and photocatalysis^[5−8]. Catalytic combustion exhibits superior application potential owing to its exceptional versatility and simple reaction process.

Among them, noble metal catalysts (e.g., Pt, Pd, Rh, Au and Ru) demonstrate excellent catalytic combustion activity at relatively low temperatures; however, their high cost and susceptibility to poisoning limit large-scale industrial application^[9−12]. Transition metal oxide catalysts, such as MnO_x, Co₃O₄, CuO and CeO₂, have become research hotspots in catalytic combustion owing to their low cost, excellent thermal stability, and robust resistance to poisoning^[13−14]. Manganese oxides (MnO_x), with their variable valence states, diverse morphologies and crystal phases, and their capacity to yield multifaceted manganese-based catalysts, exhibit immense potential in catalytic combustion of VOCs. This review summarizes the effects of structural characteristics and surface chemical composition of manganese-based catalysts on their catalytic efficacy, outlines the deactivation mechanisms and anti-poisoning strategies, and compares various performance-enhancement approaches, including doping, composite formation, and support modification.

1　MnO_x-based catalysts

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A wide variety of MnO_x materials exist, exhibiting multifaceted crystal facets, phases, and morphologies, alongside configurations such as distorted coordination, multiphase mixtures, and amorphous structures. The five crystal-phase structures of MnO₂ and their subtypes possess advantages including low cost, structural versatility, strong reducibility, and abundant oxygen species, and—together with Mn₂O₃ and Mn₃O₄ etc.—exhibit exceptional potential in the catalytic combustion of VOCs. The morphology and crystal structure of manganese oxides can be precisely tailored through the selection of synthesis routes and optimization of preparation parameters, enabling the directional design of catalysts. For example, deliberate exposure of specific crystal facets or the controlled synthesis of designated crystal phases or morphologies (Figure 1) can effectively enhance the catalytic activity of the catalysts toward VOCs, as summarized in Table 1.

Crystal facets are an important factor governing catalytic activity. Rong et al.^[9] synthesized α-MnO₂ nanowires with exposed {310} facets via a hydrothermal approach. Compared with the {110} and {100} facets, the {310} facet more readily promotes the formation of oxygen vacancies, thereby facilitating the generation of surface-active oxygen species and enhancing formaldehyde oxidation. Huang et al.^[10] synthesized α-MnO₂ exposing {110}, {210} and {310} facets, and discovered that in the catalytic oxidation of toluene, the α-MnO₂ enriched with {210} facets exhibited superior activity, achieving a t₉₀ (temperature required for 90% conversion) of 109 °C, whereas the t₉₀ values for the {110} and {310} facets were around 170 °C. This advantage arises from the unique surface electronic structure formed by the alternating arrangement of Mn and O atoms on the {210} facet, which promotes more uniform charge distribution between Mn⁴⁺ and O^2– and strengthens surface redox capability. Moreover, the adsorption energy barriers for toluene (−0.451 eV) and O₂ (−0.200 eV) reach their lowest values on the {210} facet, indicating more favorable adsorption of both toluene and oxygen molecules. Another study revealed that δ-MnO₂ exposing {310} facets can be synthesized via ultrasound assistance. During MnO₂ formation, ultrasonic treatment disrupts the thermodynamically stable facets, thereby promoting selective growth of the {310} facet and enhancing catalytic activity for toluene combustion; compared with the {001} facet, the t₉₀ was lowered by 25 °C^[11]. In catalytic combustion reactions, facet engineering enables the selection of highly active exposed facets, allowing regulation of oxygen vacancy concentration and surface adsorption properties, which profoundly governs overall catalytic performance.

Crystal structure determines the intrinsic properties of materials. Yang et al.^[12] synthesized α-MnO₂, β-MnO₂, γ-MnO₂ and δ-MnO₂ catalysts. The layered structure of δ-MnO₂ facilitates the formation of low-valence Mn species and provides more adsorbed oxygen species (O_ads), which promoting profound oxidation of toluene and achieving a t₉₀ of merely 245 °C. In contrast, β-MnO₂ lacks sufficient O_ads, preventing the oxidation of large amounts of toluene and its intermediates. Another study revealed that the mechanism by which mixed-phase α/δ-MnO₂ or Mn₃O₄/Mn₂O₃ enhances catalytic activity differs between systems. The α/δ-MnO₂ catalyst benefits from the synergistic effect between the two phases: the α-phase provides abundant active sites, while the δ-phase, owing to its layered structure, facilitates oxygen migration. As a result, the t₉₀ of α/δ-MnO₂ decreases to 210 °C, lower than 220 °C for α-MnO₂ and 245 °C for δ-MnO₂. In contrast, the lattice distortion at the heterojunctions of Mn₃O₄/Mn₂O₃ induces a higher density of oxygen vacancies, which also enhances catalytic performance^[13−14]. Zeng et al.^[17] conducted an in-depth investigation of the role of oxygen vacancies, demonstrating-using various α-MnO₂ samples rich in oxygen vacancies-that these defects profoundly modulate active oxygen species, surface structure, and reactant adsorption. In addition, directly designing defect engineering to regulate lattice defects has become another research focus for manganese oxides. Zeng et al.^[18] identified the critical role of the Mn 3d electronic structure in catalytic performance. Through experimental characterization and DFT calculations, they demonstrated that compared with Mn₂O₃ and Mn₃O₄, the interaction between Mn 3d and O 2p electronic states in MnO₂ weakens the Mn−O bond strength, thereby modulating catalytic activity. This study provides deeper insight into defect formation from the perspective of electronic structure. Bai et al.^[19] synthesized ε-MnO₂ with different degrees of lattice disorder, finding that the most disordered sample, MnO₂-R, displayed the weakest Mn−O bonds, which were more prone to break to form oxygen vacancies and generate more active oxygen species. It also exhibited superior low-temperature reducibility; consequently, its toluene t₉₀ (222 °C) was 37 °C lower than that of the most ordered sample, MnO₂-H. In reactions involving mixed toluene and acetone gases, these two molecules share active sites and oxygen species, thereby enhancing their catalytic combustion. Similarly, MnO_x with low crystallinity prepared by Li et al.^[20] exhibited the strongest catalytic performance. Lattice defects exert a profound influence on catalytic activity, and the number of defects can be precisely tuned simply by adjusting the precursor ratio of (NH₄)₂CO₃ to Mn(NO₃)₂, resulting in excellent low-temperature reducibility. These findings collectively demonstrate that lattice disorder enhances both the low-temperature reducibility and oxygen-species activity of the catalysts.

Feng et al.^[15] synthesized hollow-sphere and nanospherical MnO_x and the former exhibited a larger specific surface area that exposed more active sites, resulting in a t₉₀ for toluene oxidation that was 32 °C lower than that of the latter. Mo et al.^[16] controlled the micro-morphology of manganese oxides by altering the precipitation method. Using ammonium bicarbonate in an ethanol-water solution as the mineralizer yielded a spherical MnO_x-ET catalyst, which had the largest specific surface area among diverse morphologies-including cubic, rough spheres, peach-like shapes, nanobundle, and carved bell-like structures—thereby exhibiting markedly superior catalytic activity (t₉₀ = 225 °C). Moreover, the abundant oxygen vacancies on MnO_x-ET facilitated the formation of adsorbed oxygen and the activation of lattice oxygen. Through multiple reaction pathways (Figure 2), the surface-adsorbed-oxygen route follows: toluene → benzyl species → benzyl alcohol → benzoic acid → carbonates → CO₂ and H₂O; while the lattice-oxygen pathway advances via: benzoic acid → phenol → maleic anhydride, both contributing to deep oxidation of toluene. Zheng et al.^[21] enhanced the exposure of active sites by confining the particle size of MnO_x; carbon species derived from MOFs inhibited MnO_x agglomeration during N₂ calcination, thereby enabling the MnO_x nanoparticles to retain a small size. Zhou et al.^[22−23] further employed KIT-6 as a template to precisely regulate the structure of MnO₂-HT, thereby enabling MnO₂-HT to inherit the highly ordered mesoporous framework of KIT-6. The abundant mesopores facilitated the adsorption and diffusion of reactant molecules across the catalyst surface. Other studies have revealed that the precipitation rate in the precipitation method can profoundly influence the surface structure of catalysts. When urea was used as the precipitant, the relatively slow precipitation rate increased the proportion of Mn⁴⁺ and enhanced the activity of surface-active oxygen species in MnO₂, thereby dramatically enhancing its catalytic activity performance for toluene oxidation (t₉₀ = 178 °C)^[24]. Additionally, both calcination temperature^[25] and precursor concentration^[26] emerge as important factors that profoundly modulate catalytic performance from multiple aspects.

In summary, the complex valence states and multifaceted morphologies of manganese oxides allow their catalytic performance to be improved through modulation of crystal facets, crystal structures, and morphological features. However, relying solely on manganese oxides makes it difficult to further enhance performance, and their stability still requires improvement. Challenges such as the scarcity of active sites and weak adsorption capacity also remain unresolved. To address these challenges, the strategic integration of manganese oxides with other metals has emerged as a highly strategy for catalyst design.

2　Composite Mn-based catalysts

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Combining manganese-based catalysts with other metals is an important strategy for enhancing their catalytic activity toward VOCs, including but not limited to doping, composite formation, and supported structures. Transition metals are extensively employed to dope manganese oxides, and atomic substitution has been demonstrated to elevate the intrinsic catalytic activity of MnO_x, with several studies reporting notable achievements^[27−28]. Composite metal oxides can effectively modulate the morphology of manganese oxides and form distinctive structures or mixed phases such as solid solutions, spinels, or perovskites, thereby exhibiting superior catalytic performance. Table 2 summarizes the VOCs catalytic performance of composite manganese-based catalysts reported in recent literature.

2.1　Transition metal-doped Mn-based catalysts

Transition metal elements can substitute for or be incorporated into the original crystal lattice to form novel chemical bonds, thereby modulating the surface composition dominated by Mn−O bonds and ultimately optimizing the catalytic combustion performance of MnO_x toward VOCs.

Li et al.^[5] synthesized Cu_x-MnO₂ via a two-step hydrothermal doping approach. In the first hydrothermal step, δ-MnO₂ with a unique hollow morphology was fabricated. In the second low-temperature hydrothermal step, this morphology was retained while Cu²⁺ was successfully incorporated into δ-MnO₂. The Cu²⁺ ions substituted K⁺ ions within the interlayers of δ-MnO₂, triggering interlayer contraction, which induced periodic structural disruption and lattice distortion, resulting in the formation of oxygen vacancies. This, in turn, facilitated the adsorption and activation of oxygen species, with Cu_0.05-MnO₂ demonstrating the most significant effect, reducing the t₉₀ for toluene to 190 °C. Similarly, Qiao et al.^[29] fabricated catalysts through hydrothermal synthesis, achieving deeper Mo incorporation into MnO_x.

As shown in Figure 3, the resulting Mo-O_v-Mn active sites promoted oxygen adsorption on the catalyst surface and reduced the energy barrier for oxygen dissociation. However, excessive Mo doping led to the formation of Mo-O_v-Mo sites, where active oxygen species were difficult to release, thereby inhibiting catalytic activity. Therefore, an appropriate amount of Mo doping is necessary to balance oxygen adsorption energy and dissociation barriers, enhancing oxygen transfer efficiency. Co-precipitation methodologies can also uniformly incorporate Ce, Co, or Cu into MnO_x. Different transition metals exert varying influence upon MnO_x, generating additional oxygen vacancies that activate more active oxygen species, among which Ce exerts the most significant effect, markedly enhancing formaldehyde decomposition at room temperature^[42]. Beyond conventional synthesis routes, Fe_xMn_x catalysts have been prepared via a dichloromethane-induced layered interface followed by redox precipitation. In these catalysts, the incorporated Fe not only integrates into the δ-MnO₂ crystal structure but also forms a unique three-dimensional porous structure that increases the specific surface area and exposes more active sites. Simultaneously, the Mn−O bond strength is weakened, promoting the release of lattice oxygen; for the Fe₁Mn₅ catalyst, the t₉₀ for toluene attains 209 °C^[30]. Conventional in situ hydrothermal Cu doping, although not producing special structures, can still increase the surface area and exposed active sites, enhancing gaseous oxygen adsorption and activation and accelerating lattice oxygen migration. Cu substitution also increases the proportion of Mn³⁺ ions, improving the redox properties of the catalyst^[31]. Dong et al.^[32] prepared Co-doped manganese octahedral molecular sieve (OMS-2) through a pre-incorporation method (Figure 4). After Co substituted some surface Mn atoms, the OMS-2 morphology was retained, but the surface electronic structure changed. Electrons from Co²⁺ transferred to Mn⁴⁺, lowering the valence state of Mn, increasing the Mn³⁺/Mn⁴⁺ molar ratio, and substantially enhancing low-temperature reducibility. The Mn−O bond was weakened, and the O_ads/ O_latt molar ratio significantly increased, allowing more active oxygen to participate in reactions and effectively enhancing catalytic performance. The t₉₀ for toluene before and after doping was 280 and 245 °C, respectively. Furthermore, the incorporation of multiple metal elements (Pd, Ir, Cu) into OMS-2 has been explored (Figure 5) using a redox method, successfully substituting Mn sites in the octahedral framework. The incorporation of these heteroatoms strengthened the catalytic combustion of specific VOCs: Pd improved the reducibility and mobility of oxygen species; Cu ions promoted C−C bond cleavage; and Ir ions enhanced the bond-breaking ability of OMS-2. In the catalytic oxidation of different VOCs, this “metal doping-structure regulation–function orientation” logic explains the differential promotion effects of various metal dopants. Pd doping reduced the t₉₀ for toluene and acetone to 247 and 231 °C, respectively, thereby improving OMS-2 performance by 10−20 °C. Cu notably enhanced acetone oxidation, and Ir significantly promoted dichloromethane oxidation, lowering the t₉₀ to 207 and 293 °C, decreases of 44 and 82 °C, respectively^[33].

Besides transition metals, alkali metals such as Na and K are also commonly used in defect engineering of manganese-based catalysts. Wang et al.^[43] employed a molten salt method to insert Na, K and Cs into the interlayers of δ-MnO₂, mainly influencing the formation of oxygen vacancies. Among them, the formation energy of oxygen vacancies in CsMnO was 1.94 eV, lower than that of KMnO (1.97 eV) and NaMnO (2.07 eV), indicating that Cs insertion promotes the generation of abundant oxygen vacancies, thereby enhancing the adsorption and activation of active oxygen species in formaldehyde catalytic oxidation. The catalytic performance of formaldehyde combustion was consistent with these results: CsMnO (65 °C) > KMnO (90 °C) > NaMnO (100 °C). Zhao et al.^[44] incorporated Na and Cs into MnO_x via citric acid chelation, and the 5%Cs/MnO_x catalyst exhibited a t₉₀ decrease of 28 °C. Cs existed as CsNO₃ on the MnO_x surface, increasing both the number and mobility of surface oxygen species. The doping of alkali metals is highly versatile and can also be applied to A-site substitution in manganese oxide perovskite structures. The substitution La in LaMnO₃ with alkali metals lowered the t₉₀ for toluene by 10−30 °C^[45].

The doping method also affects MnO_x performance. Compared with exogenous doping methods such as impregnation, co-precipitation, and sol-gel, the endogenous doping achieved via hydrothermal synthesis generates more cryptomelane-type MnO_x, which enhances the redox capability of the catalyst and improves its catalytic combustion performance^[46].

Doping strategies provide a direct and effective approach to optimizing the catalytic oxidation of VOCs over manganese oxides. By altering the surface electronic structure or inducing lattice defects, catalytic performance can be enhanced. However, these methods typically induce only minor structural changes in the catalyst and often result in insufficient atomic utilization.

2.2　Composite metal oxide catalysts

2.2.1　Co-Mn system

Co and Mn have similar electronic structures, which facilitates the formation of composite oxides. Their multiple accessible oxidation states allow adaptation to diverse structures. Through the synergistic effect of the bimetallic system, the redox cycles of Co and Mn ions are accelerated, thereby enhancing catalytic combustion performance by lowering the activation energy of the reaction. Consequently, researchers have long focused on optimizing catalytic performance and elucidating reaction mechanisms in Co-Mn systems.

Hu et al.^[34] synthesized CoMn spinel wherein electron transfer occurs between Co and Mn weakens the Mn−O bonds, thereby promoting the migration and activation of surface oxygen species. The CoMn spinel exhibited superior toluene conversion compared to monometallic oxides across the temperature range of 225−300 °C. This observation is consistent with kinetic modeling of toluene catalytic oxidation, which revealed that oxygen activation is the rate-determining step. Liu et al.^[35] synthesized hollow-structured CoMn composite oxides employing organic ligands as templates. The incorporation of Mn not only significantly increased oxygen vacancies but also effectively regulated the catalyst’s micro-morphology. With increasing Mn content, the catalyst evolved from porous flower-like hollow microspheres to layered particle-stacked microspheres (Figure 6(b)). Changes in the dominant active oxygen species directly influenced the reaction pathway: when surface-active oxygen was abundant, toluene oxidation at 200−250 °C proceeded though the Langmuir-Hinshelwood (L-H) mechanism, whereas above 250 °C, lattice oxygen became activated, triggering the Mars-van Krevelen (MVK) mechanism (Figure 6(a)). The coexistence of multiple pathways is the main reason for the excellent catalytic performance. Li et al.^[36] synthesized CoMn hollow sub-nanospheres using carbon spheres as templates. Electron transfer from Mn³⁺ to Co³⁺ promoted the Co-Mn synergistic redox cycle, thereby accelerating lattice oxygen activation and regeneration. The CoMn₂O_x catalyst, exhibiting the strongest synergistic effect, attained a toluene t₉₀ of 265 °C. Earlier, Zhou et al.^[47] successfully loaded CoMn spinel onto activated carbon via a simple impregnation method, achieving 90% and 87.9% degradation of toluene and ethylbenzene at 235 and 240 °C, respectively. Subsequently, Ren et al.^[48] employed urea to precisely construct oxygen vacancy engineering on CoMn spinel, investigating the roles of adsorbed oxygen and lattice oxygen and their activation in toluene catalytic oxidation. Structurally modified CoMn spinel enabled faster deep oxidation of toluene while maintaining dynamic equilibrium of oxygen species, significantly reducing the light-off temperature to a t₉₀ of merely 230 °C, demonstrating excellent catalytic activity. Co-Mn composite oxides facilitate electron transfer or form new chemical bonds, and the strong synergistic effect of the Co-Mn system significantly enhances catalytic activity, thereby improving the performance of manganese-based catalysts. Song et al.^[49−50]synthesized a CoMn solid solution via a simple method. This unique structure exhibited excellent catalytic performance, achieving 97% toluene removal at 150 °C, comparable to that of some noble metal catalysts.

2.2.2　Ce-Mn system

Ce has properties similar to Co and can improve the low-temperature catalytic activity and stability of manganese-based catalysts, thereby enriching their structural and functional diversity. In addition, cerium oxides possess exceptional oxygen storage capacity.

Shah et al.^[37] prepared a series of CeMn composite oxides employing a sodium carbonate co-precipitation method. The heterojunctions formed by Mn substituting CeO₂ and Mn₂O₃ were identified as the key active sites. The active sites in Mn₂O₃ adsorbed and activated gaseous oxygen, directly participating in VOCs catalytic combustion, while Mn substituting CeO₂ acted as a lattice oxygen reservoir. Under conditions of insufficient gas-phase oxygen or high reaction rates, lattice oxygen could be rapidly released to replenish the reaction sites, thereby synergistically facilitating the catalytic combustion of propane or naphthalene. Furthermore, using urea or nitrate grinding methods at 350 °C increased propane removal by 20%, effectively avoiding deactivation arising from Na atoms covering active sites. This indicates that the incorporation of extraneous atoms should be avoided during synthesis. Chen et al.^[38] modified CeMnO_x solid solutions employing diverse organic solvents. The MC-TPAOH catalyst (Figure 7) derived from modification with tetrapropylammonium hydroxide (TPAOH) solution, exhibited expanded interlayer spacing owing to TPA⁺ intercalation, while pore size slightly decreased and specific surface area increased. This structural adjustment increased the number of active sites and further enhanced oxygen species activity and redox performance, reducing the t₉₀ for toluene to 221 °C, without incorporating extraneous atoms. Gao et al.^[39] synthesized MnCe catalysts via hydrothermal methods. Partial substitution of α-MnO₂ K⁺ and Mn sites by Ce triggered a Jahn-Teller effect, stabilizing Mn³⁺ and oxygen vacancies, thereby increasing the concentration of oxygen vacancies and acidic sites while further enhancing the deep oxidation of VOCs. In the catalytic combustion of mixed toluene and chlorobenzene gases, the two reactants competitively adsorbed on the B acid sites of the catalyst, thereby significantly suppressing catalytic activity. Consequently, the t₉₀ for toluene increased from 195 to 240 °C, while that for chlorobenzene increased from 174 to 250 °C.

Within the Ce-Mn system, Ce can directly substitute Mn within the manganese oxide lattice to form solid solutions, and it can also combine with Mn to form special structures such as perovskites. These structures enrich oxygen species, which, through defect engineering, actively participate in the catalytic combustion of VOCs, thereby improving the catalytic performance of manganese-based catalysts.

2.2.3　Cu-Mn system

Cu⁺/Cu²⁺ exhibits high electron-transfer activity and readily forms redox couples with Mn³⁺/Mn⁴⁺. Compared with other elements, such synergistic interactions occur more readily.

The morphology of catalysts has a significant impact on their catalytic performance. Wang et al.^[40] synthesized CuMn oxides with different morphologies via a hydrothermal method, embedding CuO nanoparticles into layered MnO₂. At the monoclinic-tetragonal (m-t) interface, abundant Cu²⁺-O^2--Mn⁴⁺ bonds were formed through oxygen bridges, promoting electron transfer from O²⁻ to Cu²⁺ and from Mn⁴⁺ to Cu²⁺.

This enhanced the activity of surface oxygen species and facilitated the redox cycle, which explains why layered CuMn oxides exhibited superior catalytic combustion performance for benzene, toluene, and xylene compared to rod-shaped and granular morphologies, with t₉₀ values of 240, 207 and 227 °C, respectively. Cheng et al.^[41] synthesized CuMn₂O₄ and Mn₃O₄ via co-precipitation. Mechanical mixing of these two oxides improved catalytic activity for toluene combustion. As shown in Figure 8, oxygen vacancies formed at the CuMn₂O₄/ Mn₃O₄ interface, effectively activating lattice oxygen within Mn₃O₄, which subsequently migrated to the catalyst surface to participate in VOC oxidation. Replacing CuMn₂O₄ with CuCo₂O₄ or CuFe₃O₄ yielded similar t₉₀ values (~240 °C), indicating that Cu significantly activates lattice oxygen species. However, not all composite oxides facilitate electron transfer; Ramstad et al.^[51] observed that Cu incorporated into OMS-2 tunnels merely produced coordination interactions, leaving the valence states of both Cu and Mn. Introducing composite oxides onto other supports also affects catalytic combustion performance. Rokicińska et al.^[52] impregnated CuMn spinel onto self-prepared dealuminated SiBEA zeolite, filling the interparticle gaps with spinel nanoparticles. During calcination, the Jahn-Teller effect induced partial oxidation-reduction of Cu²⁺ and Mn³⁺ to more stable Cu⁺ and Mn⁴⁺, thereby facilitating the reversible Cu²⁺+Mn³⁺ ↔ Cu⁺+Mn⁴⁺ redox cycle, lowering the reaction activation energy and generating abundant oxygen vacancies. Loading CuMn spinel improved both catalytic performance and economic efficiency. Many studies have concentrated on using diverse synthesis routes to yield varied catalyst structures. Li et al.^[53] synthesized CuMn bimetallic oxides (CM-MW, CM-SG, CM-CP) via microwave heating, sol-gel and co-precipitation, respectively, each manifesting the Cu_1.5Mn_1.5O₄ active phase. CM-MW, with lower crystallinity, generated numerous oxygen vacancies, promoting oxygen species activation and migration, resulting in stronger oxidation ability and higher catalytic activity, achieving a toluene t₉₀ of 213 °C, whereas CM-SG and CM-CP recorded t₉₀ values of 235 and 268 °C, respectively.

Further, Xiang et al.^[54] prepared composite oxides with diverse morphologies through surface modification and hydrothermal methods. Surface modification induced interfacial electron redistribution and structural strain between CuO and MnO₂, creating surface oxygen defects, while Cu²⁺ in hydrothermal CuMnO_x caused charge compensation and lattice distortion, generating bulk oxygen defects. Both types of oxygen defects enhanced toluene catalytic combustion, yielding t₉₀ values of 238 and 259 °C, respectively, significantly better than α-MnO₂ (t₉₀ = 287 °C). Li et al.^[55] systematically studied the effects of CH₃COOH concentration, Cu/Mn molar ratio, and calcination temperature on catalyst morphology and structure, providing insight into active site formation. Optimal Cu and Mn distribution was achieved at low CH₃COOH concentration and Cu/Mn molar ratio of 1, while isolated CuO or MnO₂ weakened the synergistic effect. Appropriate calcination temperature stabilized the structure, resulting in a t₉₀ of 214 °C.

The large difference in solubility products between Cu and Mn ions often leads to the formation of multiphase mixtures in the Cu-Mn system. The heterointerfaces between Cu and Mn enable synergistic interactions, profoundly modulating the electronic structure of surface-active sites and thereby enhancing catalytic performance. Additionally, special composite structures, such as spinels and solid solutions, not only maintain exceptional catalytic activity but also improve VOC adsorption, elevate catalytic efficiency, and further enhance catalyst stability.

3　Supported Mn-based catalysts

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Although composite manganese-based catalysts exhibit good performance in the generation of active oxygen species and catalytic stability due to the synergistic effects among multiple metals, they still face limitations in terms of active component dispersion, precision in reaction site regulation, and the orderliness of interfacial structures. In contrast, supported manganese-based catalysts offer highly controllable structural design and allow mutual interaction between the active components and the manganese-based support, thereby enabling effective modulation of both dispersion and electronic structure of the active sites. Consequently, they have emerged as a key research direction in the field of VOCs catalytic combustion and have attracted widespread attention. Table 3 summarizes the catalytic performance of supported manganese-based catalysts reported in recent years.

3.1　Nanoparticles (NPs) Mn-based catalysts

Mo et al.^[56] observed that H-MnO₂ (hollow spherical γ-MnO₂), γ-MnO₂, α-MnO₂ and β-MnO₂ exhibited modest catalytic activity, achieving toluene t₉₀ values of 230, 238, 263 and 275 °C, respectively. The incorporation of Pt significantly enhanced the catalytic performance of these catalysts, as shown in Table 3. However, notable differences were observed among the catalysts due to variations in the strength of the strong metal-support interaction (SMSI) between Pt and different MnO₂ crystal phases. The intensity of SMSI is closely related to the structure of the support. Although low-crystallinity γ-MnO₂ readily promotes the formation of surface oxygen vacancies, its incomplete crystal planes weaken the electronic structure matching between metal particles and the support, thereby hindering effective SMSI. Strong SMSI profoundly improves catalytic activity. For Pt/α-MnO₂ and Pt/β-MnO₂, MnO₂ migration encapsulating Pt nanoparticles-a typical SMSI feature-was observed, whereas no such phenomenon appeared for Pt/γ-MnO₂. Consequently, the t₉₀ values followed the order Pt/α-MnO₂ (170 °C) > Pt/β-MnO₂ (180 °C) > Pt/γ-MnO₂ (190 °C), consistent with the SMSI strength trend. The morphology and structure of manganese oxides are key factors influencing SMSI strength, and the loading method also affects SMSI. Hu et al.^[57] synthesized Pt/MnO₂-r-WI though deposition in an alkaline medium, resulting in smaller and more uniformly dispersed Pt nanoparticles. In contrast, Pt/MnO₂-r-IW prepared by conventional impregnation exhibited Pt NP agglomeration up to 1.3 nm. The highly dispersed Pt within Pt/MnO₂-r-WI maximized Pt utilization and generated stronger SMSI, thereby reducing toluene t₉₀ to 224 °C, significantly lower than 250 °C for Pt/MnO₂-r-IW. Other factors also affect the catalytic performance of supported manganese-based catalysts. For example, the specific surface area exerts an important role. Li et al.^[58] employed acid etching to create pores in LaPdMO₃ (LPMO), selectively removing inert La sites and exposing Pd active sites, thereby substantially enhancing interfacial between Pd and MnO₂. As shown in Figure 9, the acid-etched catalysts increased the specific surface area from 20 to 180 m²/g, providing abundant active sites and improving mass transfer, thereby reducing the toluene t₉₀ from 248 to 200 °C. Xia et al.^[59] reported that the nanotubular morphology of α-MnO₂ in 0.91Au_0.48Pd/α-MnO₂ could anchor a large number of noble metal nanoparticles, creating more active sites. Sun et al.^[60] discovered that Pt/Mn₃O₄-R exhibited superior catalytic performance compared with Pt/Mn₃O₄-C, attributable to the specific surface area of Mn₃O₄-R (138.2 m²/g) was over ten times that of Mn₃O₄-C (11.7 m²/g), thereby providing richer anchoring sites for Pt, better dispersion, and facilitating the formation of more Mn−O bonds. To further investigate the construction of active sites in supported manganese-based catalysts, Pan et al.^[61] synthesized Pt/Mn₂O₃. As shown in Figure 10, Pt embedded within the Mn₂O₃ surface induced lattice distorted, thereby weakening the Mn−O bonds and generating oxygen vacancies though dissociative oxygen activation. In contrast, Pt⁰ supported on Al₂O₃ participates in toluene catalytic combustion through adsorbed oxygen species (O_ads), indicating that the support properties influence the VOC reaction mechanism. At high temperatures, acetone can adsorb on Pt sites in Pt/Al₂O₃, thereby deactivating reaction sites; consequently, Pt/Al₂O₃ shows excellent catalytic performance only for toluene, with t₉₀ values of 199 and 233 °C for toluene and acetone, respectively. Pt/Mn₂O₃, however, avoids deactivation and achieves efficient catalytic combustion of multiple VOC types, with t₉₀ values of 201 and 169 °C.

Supported manganese-based catalysts realize low-temperature, high-efficiency catalytic oxidation of diverse VOCs through structural design and oxygen species regulation. The construction of active sites in supported manganese-based catalysts requires the synergistic optimization of morphology and noble metal dispersion.

The interaction between noble metal nanoparticles and the manganese oxide support constitutes a key factor in modulating catalyst activity. However, quantitative studies and clear structure-activity relationships regarding the influences of charge transfer, nanoparticle morphology, chemical composition, and SMSI on catalytic performance remain insufficient.

3.2　Single-atom Mn-based catalysts

Although the incorporation of noble metal nanoparticles significantly enhances the catalytic performance for VOCs, practical deployment remains limited by low metal utilization, activity degradation due to particle agglomeration, and unclear correlations between active site structure and reaction mechanisms in complex reaction pathways. To overcome the limitations of nanoparticles, single-atom catalysts anchor noble metals in an atomically dispersed form on the surface of manganese-based supports. This strategy not only maximizes metal atom utilization and prevents agglomeration but also provides well-defined geometric and electronic structures of active sites, thereby offering an ideal model for elucidating structure-activity relationships.

Li et al.^[65] employed a double-solvent method to anchor Pd atoms within the MOF structure of MnO, employing hydrophobic activated carbon as the support, successfully synthesizing Pd-0.5/Mn@C. Under room temperature and 50% humidity, the removal capacity for 53 mg/m³ hexanal reached 388.8 mg/g, which is 2.4 times that of commercial BPL activated carbon (162 mg/g) and 4 times that of lignite-based activated carbon (97.2 mg/g). For pollutant concentrations of 53 mg/m³ pentanal and 53 mg/m³ toluene, the 99% removal capacities were 360 and 137.6 mg/g, respectively, thereby demonstrating high-efficiency removal of multiple VOCs (hexanal, pentanal, toluene). Single-atom catalysts exhibit exceptional catalytic performance in room-temperature oxidation and are also economically viable for low-temperature catalysis at higher reactant concentrations. Feng et al.^[62] employed a molten salt approach to anchor single-atom Pt on MnO₂ nanowires. The electronic interaction between Pt and Mn in Pt/MnO₂ effectively optimized the Mn oxidation state distribution, promoted Mn³⁺/Mn⁴⁺ cycling, weakened Mn−O bonds, and generated abundant oxygen vacancies, which enhanced lattice oxygen activity and mobility. Consequently, the toluene t₉₀ decreased significantly from 277 to 228 °C, and the reaction followed a MVK mechanism. In the catalytic oxidation of toluene and isohexane mixed gas, toluene adsorbed more strongly on the noble metal, with Pt^δ+ causing over-adsorption and blocking active sites. H₂ reduction treatment diminished the Pt-O coordination number and disrupted the lattice order of manganese oxides, thereby increasing lattice oxygen mobility (Figure 11) and further reducing t₉₀ to 219 °C. Chen et al.^[63] anchored Ag atoms within the cavities of 4 nm hollandite-type MnO (HMO) particles, which significantly enhanced the activation and replenishment of lattice oxygen in adjacent Mn−O bonds. Similarly, Zhang et al.^[66] employed a one-pot synthesis to anchor single-atom Pt on sodium birnessite-type MnO₂ nanosheets, resulting in more active lattice oxygen. Hao et al.^[64] reported that OMS-2 catalysts incorporating Pt atom exhibited an increased O_ads/O_latt ratio, thereby effectively enhancing benzene catalytic performance (Table 3) and achieving over 90% benzene conversion at 189 °C. These studies reveal that the incorporation of noble metal single atoms effectively lowers reaction temperatures by enhancing oxygen species activity and other factors. Hao et al.^[67] first alkali-etched a KIT-6 template with NaOH to create a Na-doped MnO₂ phase, thereby enhancing the catalyst’s sulfur resistance; however, excessive alkali doping inhibited molecular oxygen adsorption and activation. Notably, isolated Pt-Co dual-metal atoms were loaded, where Pt promoted lattice oxygen release and Co formed new redox electron pairs, enhancing Mn redox cycling. The synergistic effect of the two metals significantly promoted propane catalytic combustion.

Single-atom catalysts enable more precise regulation of active site electronic structures, dynamic cycling of oxygen species, and the adsorption-activation balance of VOCs, achieving efficient and broad-spectrum VOC removal at low temperature with exceptional atom economy and practical applicability. However, current single-atom anchoring strategies still face challenges such as complex synthesis procedures, low efficiency, and constrained scalability, highlighting the need for the development of simpler synthetic methods to enable large-scale production.

3.3　Supported Mn oxides

Manganese oxides or composite metal oxides are used as active components and supported on porous carriers such as Al₂O₃, SiO₂, TiO₂ and ZSM-5. The porous structure of the support facilitates uniform dispersion of the active components and enhances the atomic utilization of the catalyst.

Soltan et al.^[68] synthesized Fe-Mn/H-ZSM-5 catalysts through a two-step hydrothermal and precipitation method. The Fe-Mn bimetallic species loaded on H-ZSM-5 serve as the active components for toluene catalytic oxidation, while the support does not directly participate in the reaction. The t₉₀ of the Fe₂-Mn₁ catalyst is 362 °C, but when supported on H-ZSM-5, the t₉₀ markedly decreases to 232 °C. This improvement is attributed to the support promoting uniform dispersion of the Fe and Mn metals, stabilizing the active components against aggregation, and providing acidic sites coupled with an excellent pore structure that ensures efficient VOC adsorption and diffusion. Todorova et al.^[69] loaded Co-Mn bimetallic species onto hierarchical mesoporous silica (MMS). After loading, the catalyst retained the mesoporous structure of MMS; however, the CoMn-MMS catalyst exhibited lower activity compared to single-component catalysts. This difference is related to the location of the metal oxide particles: CoMn particles were confined within the mesopores, whereas single-component oxide particles were supported on the external surface, thereby facilitating superior reactant adsorption, diffusion, and interaction with active sites. Moreno-Román et al.^[70] loaded MnO_x on MCM-41 and SBA-15 and investigated the selective oxidation of toluene, isopropanol, and their binary mixture. The study revealed that reaction conditions, catalyst morphology, redox properties, and support acidity significantly influence catalytic activity and selectivity. On MCM-41, MnO_x aggregates on the external surface, making it more accessible to VOCs and actively participating in oxidation, whereas on SBA-15, MnO_x deposits within the larger pores (~9 nm). Zhang et al.^[71] applied Mn-Ce-M (M = Cu, Ni, Co) sol-gel coatings on cordierite, thereby achieving in situ loading that reduced preparation costs. The resulting catalysts exhibited excellent activity toward multiple VOCs. Beyond supports that enhance adsorption and diffusion, even inert supports can facilitate the formation of new structures with active components. Zhang et al.^[72] synthesized MnO_x/SiO₂ composites with a Si-O-Mn hybrid structure, which weakened Mn−O bonds and facilitated the release of lattice oxygen. Consequently, the T₉₀ decreased from 243 to 218 °C upon loading, indicating that the interaction between active components and inert supports can create novel structural features.

The loading of manganese oxides is typically controlled at 10%−20% to ensure high atomic utilization while allowing the support to provide optimal dispersion and stability, which is one of the primary factors enhancing the activity of such catalysts. Additionally, the newly introduced acidic sites from the support, coupled with its active participation in constructing catalytic centers, also contribute positively to the catalytic performance. Overall, these supported manganese-based catalysts amplify existing advantages to further enhance catalytic activity.

4　Deactivation mechanisms and poison-resistance strategies of Mn-based catalysts

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Catalyst deactivation is one of the primary challenges limiting industrial applications. The main mechanisms of deactivation include chemical deactivation, physical deactivation, and loss of active components, which often act in combination.

Chemical deactivation includes sulfur poisoning, halogen poisoning, and hydrothermal deactivation. In the presence of sulfur-containing reactants, irreversible chemical reactions often occur between the sulfur species and the active sites during the reaction. Halogen elements strongly adsorb on the surface of active sites, blocking them and hindering the adsorption and activation of VOCs and oxygen species. Hydrothermal deactivation occurs because high-temperature, humid environments induce phase transitions in manganese oxides, thereby converting the catalyst into less active phases. Physical deactivation results from sintering, hydrothermal effects, and carbon deposition. Sintering causes small crystallites to migrate and aggregate into larger ones, thereby reducing the catalyst’s specific surface area and the number of active sites, which is irreversible. Hydrothermal physical deactivation arises from competitive adsorption between water molecules and VOCs, while carbon deposition, caused by incomplete combustion of VOC molecules, obstructs the pores; both of these processes are reversible, with partial activity can be restored by reducing moisture content or high-temperature calcination. Additionally, active components can be lost as volatile compounds or physically eroded by gas flow. Zhang et al.^[73] reported that incorporating Fe into manganese-based composite oxides suppressed sulfate formation in sulfur-containing atmospheres, thereby protecting the MnO_x active sites. Qiao et al.^[29] demonstrated that moderate Mo doping in MnO_x decreased the formation of sulfates and sulfites, thereby alleviating chemical deactivation and enhancing sulfur resistance. Gao et al.^[39] synthesized CeMn composite oxides, where the synergy of Brønsted acid sites and oxygen vacancies converted chlorine in chlorobenzene into easily desorbable HCl, preventing halogen species from covering active sites. Under extreme preparation conditions, MnO₂ can form thermodynamically more stable crystal planes or phases, which diminished catalytic activity^[9−10,12]; likewise, Xie et al.^[74] observed decreased adsorbed oxygen content in Mn₂O₃ particles after high-temperature hydrothermal treatment. Fan et al.^[25] reported that increasing the calcination temperature led to a rapid decrease in MnO₂ surface area and pore collapse. In manganese-based catalysts, water molecules generally compete with VOCs for adsorption. To address this, Bi et al.^[75] synthesized Mn-Na-1.0 via a non-thermally derived MOF method, which can activate and dissociate introduced water vapor into active adsorbed oxygen species.

In brief, the construction of special morphologies and the introduction of multiple metals can both suppress catalyst deactivation. However, in practical applications, catalysts should be designed specifically according to the nature of the target exhaust gases, while also simplifying the preparation processes.

5　Factors affecting the activity of Mn-based catalysts

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The catalytic performance of manganese-based catalysts for VOCs combustion is influenced by numerous factors, which can be divided into intrinsic and extrinsic factors. Intrinsic factors include the catalyst’s reaction energy barrier, oxygen vacancy concentration, redox properties, and adsorption capacity, all determined by the catalyst’s morphology and structure. Extrinsic factors involve reaction conditions such as water vapor content, space velocity, and the type of VOCs. Modification of manganese oxides often focuses on using novel synthesis methods to disrupt stable, regular crystal planes and phases, thereby generating multivalent manganese-rich interfaces and mixed-valence environments that facilitate the formation of oxygen vacancies and enhance the redox cycling of manganese ions. However, highly active structures are prone to degradation during reactions; for example, δ-MnO₂ may collapse into α-MnO₂ and γ-MnO₂ may transform into β-MnO₂. The unstable morphology of manganese oxides gradually transforms into thermodynamically stable states during prolonged reactions, leading to decreased surface area and pore collapse, which reduces catalytic activity. In composite manganese-based catalysts, the introduction of new metal elements disrupts the original lattice structure, either through doping with minor amounts of other metals or formation of new phases such as spinel, perovskite, or multiphase mixtures, then promoting oxygen vacancy formation. Newly incorporated metal ions such as Co, Ce and Cu synergistically interact with Mn, thereby enhancing redox cycling. Supported manganese-based catalysts can be prepared via two strategies: incorporation of noble metals or inert supports. Noble metal loading enhances catalytic activity primarily through strong metal–support interaction (SMSI) with the manganese oxide carrier, while the dispersion of active components significantly influences catalytic performance and efficiency. The introduction of porous supports further improves the dispersion of active species, thereby enhancing catalytic performance.

Based on the data summarized in Tables 1, 2 and 3, a visual summary is presented in Figure 12. The catalytic activity of manganese-based catalysts exhibits the following sequence: noble metal-supported > transition metal–composite > MnO_x.

Noble metal-supported catalysts exhibit the highest catalytic activity. Additionally, under low gas hourly space velocity (GHSV), some manganese oxides can achieve catalytic performance comparable to that of noble metal-supported catalysts. Both composite and supported catalysts maintain good catalytic activity even under high GHSV conditions.

6　Conclusions and outlook

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VOCs are becoming increasingly complex, placing higher demands on catalysts, and manganese-based catalysts precisely meet the broad requirements for contemporary VOCs removal. Pure manganese oxides have simple composition and minimal toxicity, but their structural tunability remains inherently limited. Multimetallic composites, through synergistic effects, significantly enhance the redox ability of the catalyst, further improving catalytic performance. Meanwhile, diverse morphological structures such as spinel, solid solution, and perovskite exhibit stability under extreme conditions. Supported manganese-based catalysts not only exhibit excellent catalytic activity but also achieve substantial improvements in atomic utilization and cost efficiency.

Although manganese-based catalysts exhibit outstanding performance in catalytic combustion, they still face several challenges. First, industrial waste gases contain complex mixtures of VOCs, yet current research on the catalytic oxidation of multi-component systems and complex pollutants is limited, often focusing only on performance comparisons employing toluene as a probe. The reaction mechanisms for multi-component VOC oxidation remain inadequately understood. Second, broadening the applicability of manganese-based catalysts requires enhanced resistance to poisoning. More studies are needed on the adsorption and deactivation mechanisms induced by sulfur, chlorine and other elements. The long-term stability and regeneration strategies of catalysts under extreme conditions, such as high particulate concentrations and humidity, also require further exploration. Third, reliance on precious metals is a limitation. While manganese-based catalysts modified with precious metals show superior activity, their instability and high cost restrict industrial applications.

Researchers have largely focused on comparing catalytic performance, often neglecting the complexity of VOCs in practical production. Therefore, it is necessary to develop multiple evaluation metrics to enrich the catalyst performance assessment system. With their multifaceted advantages, manganese-based catalysts serve as an ideal platform for establishing a comprehensive catalyst performance evaluation framework.

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2026年第54卷第6期

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doi: 10.1016/S1872-5813(26)60645-7

接收时间：2025-09-24
首发时间：2026-09-23
出版时间：2026-06-10

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收稿日期：2025-09-24
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¹重庆工商大学废油资源化技术与装备教育部工程研究中心, 重庆 400072

²重庆工商大学环境与资源学院, 重庆 400072

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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Type	Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Crystal plane	α-MnO₂(100)	HCHO	0.01	60000	150	[9]
α-MnO₂(110)	130	[9]
α-MnO₂(310)	60	[9]
α-MnO₂(110)	toluene	0.05	15000	170	[10]
α-MnO₂(210)	109	[10]
α-MnO₂(310)	172	[10]
δ-MnO₂(310)	toluene	0.05	60000	163	[11]
δ-MnO₂(001)	198	[11]
Crystal phase	α-MnO₂	toluene	0.1	60000	225	[12]
β-MnO₂	295	[12]
γ-MnO₂	260	[12]
δ-MnO₂	245	[12]
α/β-MnO₂	toluene	0.1	48000	210	[13]
Mn₃O₄/Mn₂O₃	propene	0.05	20000	220	[14]
Morphology	nanosphere MnO_x	toluene	0.1	60000	258	[15]
hollow ball MnO_x	toluene	0.1	60000	226	[15]
spherical β-MnO₂	toluene	0.1	60000	240	[16]
dice-shaped β-MnO₂	225	[16]
peach-shaped Mn₂O₃	255	[16]
bundle Mn₂O₃	240	[16]

Type

Catalyst

VOCs type

Volume fraction/%

Air velocity/(mL·g⁻¹·h⁻¹)

t₉₀/℃

Reference

Crystal plane

α-MnO₂(100)

HCHO

0.01

60000

150

[9]

α-MnO₂(110)

130

[9]

α-MnO₂(310)

[9]

α-MnO₂(110)

toluene

0.05

15000

170

[10]

α-MnO₂(210)

109

[10]

α-MnO₂(310)

172

[10]

δ-MnO₂(310)

toluene

0.05

60000

163

[11]

δ-MnO₂(001)

198

[11]

Crystal phase

α-MnO₂

toluene

0.1

60000

225

[12]

β-MnO₂

295

[12]

γ-MnO₂

260

[12]

δ-MnO₂

245

[12]

α/β-MnO₂

toluene

0.1

48000

210

[13]

Mn₃O₄/Mn₂O₃

propene

0.05

20000

220

[14]

Morphology

nanosphere MnO_x

toluene

0.1

60000

258

[15]

hollow ball MnO_x

toluene

0.1

60000

226

[15]

spherical β-MnO₂

toluene

0.1

60000

240

[16]

dice-shaped β-MnO₂

225

[16]

peach-shaped Mn₂O₃

255

[16]

bundle Mn₂O₃

240

[16]

Type	Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Doping	Cu_0.05-MnO₂	toluene	0.05	36000	190	[5]
0.3MoMnO₂	benzene	0.048	60000	235	[29]
Fe₁Mn₅	toluene	0.1	30000	209	[30]
Cu₁Mn₁O	toluene	0.1	60000	214	[31]
10Co/OMS-2	toluene	0.2	60000	245	[32]
Pd/OMS-2	toluene	0.1	90000	247	[33]
Pd/OMS-2	acetone	0.1	90000	231	[33]
Cu/OMS-2	acetone	0.1	90000	207	[33]
Ir/OMS-2	dichloromethane	0.02	90000	293	[33]
Compositing	Co₁Mn₁O	toluene	0.4	24000	310	[34]
5Co1Mn	toluene	0.1	60000	237	[35]
CoMn₂O_x	toluene	0.1	40000	265	[36]
Ce_0.25Mn_0.75O_x	propane	0.5	45000	350	[37]
MC-TPAOH	toluene	0.1	60000	221	[38]
MnCe-7%	toluene	0.07	40000	195	[39]
chlorobenzene	0.03	174	[39]
toluene in mixture	0.07	240	[39]
chlorobenzene in mixture	0.03	260	[39]
LCMO	benzene	0.05	100000	240	[40]
toluene	0.05	50000	207	[40]
o-xylene	0.02	50000	227	[40]
RCMO	toluene	0.05	50000	240	[40]
GCMO	toluene	0.05	50000	280	[40]
MnCu	toluene	0.1	40000	214	[41]

Type

Catalyst

VOCs type

Volume fraction/%

Air velocity/(mL·g⁻¹·h⁻¹)

t₉₀/℃

Reference

Doping

Cu_0.05-MnO₂

toluene

0.05

36000

190

[5]

0.3MoMnO₂

benzene

0.048

60000

235

[29]

Fe₁Mn₅

toluene

0.1

30000

209

[30]

Cu₁Mn₁O

toluene

0.1

60000

214

[31]

10Co/OMS-2

toluene

0.2

60000

245

[32]

Pd/OMS-2

toluene

0.1

90000

247

[33]

Pd/OMS-2

acetone

0.1

90000

231

[33]

Cu/OMS-2

acetone

0.1

90000

207

[33]

Ir/OMS-2

dichloromethane

0.02

90000

293

[33]

Compositing

Co₁Mn₁O

toluene

0.4

24000

310

[34]

5Co1Mn

toluene

0.1

60000

237

[35]

CoMn₂O_x

toluene

0.1

40000

265

[36]

Ce_0.25Mn_0.75O_x

propane

0.5

45000

350

[37]

MC-TPAOH

toluene

0.1

60000

221

[38]

MnCe-7%

toluene

0.07

40000

195

[39]

chlorobenzene

0.03

174

[39]

toluene in mixture

0.07

240

[39]

chlorobenzene in mixture

0.03

260

[39]

LCMO

benzene

0.05

100000

240

[40]

toluene

0.05

50000

207

[40]

o-xylene

0.02

50000

227

[40]

RCMO

toluene

0.05

50000

240

[40]

GCMO

toluene

0.05

50000

280

[40]

MnCu

toluene

0.1

40000

214

[41]

Catalyst	VOCs type	Volume fraction/%	Air velocity/(mL·g⁻¹·h⁻¹)	t₉₀/℃	Reference
Pt/H-MnO₂	toluene	0.1	60000	180	[56]
Pt/γ-MnO₂	190	[56]
Pt/α-MnO₂	170	[56]
Pt/β-MnO₂	185	[56]
Pt/MnO₂-r-WI	toluene	0.15	40000	224	[57]
Pd/MnO₂	toluene	0.1	60000	200	[58]
0.91Au_0.48Pd/α-MnO₂	toluene	0.1	40000	185	[59]
m-xylene	0.1	200	[59]
toluene in mixture	0.1	40000	212	[59]
m-xylene in mixture	0.1	210	[59]
Pt/Mn₃O₄-R	toluene	0.1	48000	183	[60]
Pt/Mn₃O₄-C	226	[60]
Pt/Mn₂O₃	toluene	0.1	120000	202	[61]
acetone	0.1	120000	169	[61]
H₂-Pt₁/MnO_x-200	toluene	0.1	40000	219	[62]
Ag/HMO	benzene	0.02	23000	200	[63]
0.0383Pt₁/OMS-2	benzene	0.1	20000	189	[64]

Catalyst

VOCs type

Volume fraction/%

Air velocity/(mL·g⁻¹·h⁻¹)

t₉₀/℃

Reference

Pt/H-MnO₂

toluene

0.1

60000

180

[56]