Catalytic Oxidation Of Toluene Research Articles

Promotion of toluene catalytic oxidation by M−La/CoOx catalysts directly prepared from Co-MOFs precursors

Volatile organic compounds (VOCs) are identified as volatility and toxicity, and have become major pollutants in the atmosphere. The development of low-energy and high-efficiency environmentally friendly VOCs purification technologies is urgent. Therefore, in this paper, a series of M−La/CoOx (M = La addition) catalysts with different La additions were synthesized by a combination of impregnation and calcination using Co-MOFs as precursors. It was shown that the catalytic activity of the constructed 0.012-La/CoOx catalyst was unexpectedly improved (T90% = 227 °C) under optimal reaction conditions (catalyst mass-air velocity = 60000 mL/(g•h)), initial toluene concentration = 1000 ppm) when employing gaseous toluene (C7H8) as typical target VOCs. Among the La-doping catalysts, the catalysts containing La on the surface have smaller grain sizes as well as more homogeneous grain distributions than the pure Co3O4-MOF catalysts. 0.012-La/CoOx displayed the highest activity, which is attributed to its smaller particle size, larger specific surface area (SSA), richer content of Co3+ and surface Oads, which could enhance the oxygen mobility and the redox performance. The possible degradation mechanism of toluene on 0.012-La/CoOx was revealed using in-situ DRIFTS. This work might provide guidance for the development of efficient and environmentally friendly catalytic oxidation of toluene.

Tuning the crystallinity of the MnOx catalysts to promote toluene catalytic oxidation

ABSTRACT In this paper, the MnOx catalysts with excellent toluene oxidation performance were prepared by a simple precipitation method. The physicochemical properties of the prepared MnOx catalysts were investigated by XRD, BET, H2-TPR, O2-TPD and XPS. The obtained results revealed that the crystallinity of the prepared MnOx catalysts could be effectively regulated by changing the (NH4)2CO3/Mn(NO3)2 molar ratio, and thus affecting the oxygen vacancy concentration of the prepared MnOx catalysts. The prepared MnOx-4 catalyst with the (NH4)2CO3/Mn(NO3)2 molar ratio of 4.0 had the poor crystallinity and small grain size, which effectively promoted the oxygen defects in the MnOx catalyst to be formed. At the same time, the MnOx-4 catalyst had a large specific surface area, the highest low temperature reducibility and the largest number of oxygen vacancies and surface adsorbed oxygen species, which allowed more surface oxygen species to participate in the redox reaction, and promoted the toluene deep oxidation. Therefore, when the (NH4)2CO3/Mn(NO3)2 molar ratio was 4.0, the prepared MnOx-4 catalyst exhibited an excellent toluene catalytic oxidation performance and robust catalytic stability. What’s more, the toluene oxidation conversion on the MnOx-4 catalyst reached 99% at 230°C, and the MnOx-4 catalyst showed excellent resistance to water vapour.

Construction of core–shell structured CrOx/NiCoxO4 catalyst for low temperature catalytic oxidation of toluene: Understanding the reactivity promotion mechanism of the core–shell interactions

Bimetallic-based spinels are potential materials for toluene oxidation ascribing to their remarkable stability and oxidation activity. However, the insufficient toluene adsorption capacity and limited reactive oxygen species severely restrict their low-temperature catalytic reactivity. This study reports a facile two-step solvothermal strategy for the synthesis of core–shell structured CrOx/NiCoxO4 catalyst, which exhibits excellent toluene oxidation performance with T50 and T90 values of 187 and 218 °C, respectively, and the toluene conversion remains above 90 % at 218 °C for 20 h. The in-situ DRIFTs indicate that the oxidation of toluene to CO2 and H2O follows Mars-van Krevelen (MvK) mechanism, and the rate limiting step is the oxidation of maleic anhydride. The strong interaction between core NiCo2O4 and shell Cr2O3 regulates the morphology of Cr2O3 from particles to porous flocculent structure, which increases the porosity of catalyst and promotes the adsorption of toluene for further oxidation. Moreover, the interaction promotes the charge transfer from NiCo2O4 to Cr2O3, which increases the adsorbed oxygen species contents and the redox capability of the catalyst. A further density functional theory (DFT) calculation confirms that the core NiCo2O4 is the main active component, where the oxygen vacancy formation energy of NiCo2O4 and Cr2O3 decrease from 2.43 and 3.85 eV to 0.31 and 1.52 eV, while the toluene adsorption energy decrease from −0.04 and −0.94 eV to −5.29, and −4.48 eV, respectively, which evidently demonstrates that the formation of core–shell structured CrOx/NiCoxO4 would significantly promote the adsorption and oxidation of toluene, thereby exhibiting excellent low temperature toluene oxidation reactivity.

Comparative study of Mn oxide catalysts on toluene oxidation: The effect of Mn valence electronic structures

Understanding the structure-activity relationship of Mn-based oxide catalysts is of great importance for the rational development of highly performance catalysts for VOCs catalytic oxidation. However, the knowledge of the electronic structure-catalytic oxidation activity relationship over Mn-based oxide catalysts is still limited. Herein, we investigated the typical MnxOy (Mn3O4, MnO2, and Mn2O3) with different valence electronic structures by using various characterizations and DFT calculations. The MnO2 exhibits superior intrinsic activities (RS, 1.14×10−9 mol·m−2·s−1) when compared with Mn3O4 (0.54×10−9 mol·m−2·s−1) and Mn2O3 (0.45×10−9 mol·m−2·s−1) for toluene catalytic oxidation. The solid experimental and DFT calculation results show that the d-band center of Mn determines the intrinsic activity. The superior catalytic oxidation activity of MnO2 can be attributed to its higher d-band center (-1.03 eV) in comparison with that of Mn3O4 (-1.25 eV) and Mn2O3 (-1.59 eV). The higher d-band center can weaken the surface Mn-O bonds strength (k = 290.9 N/m) and strengthen the gaseous O2 adsorption simultaneously, then enhancing the mobility of surface lattice oxygen and the amount of adsorbed oxygen species. This work firstly reveals the intrinsic relationship between catalytic oxidation activity and d electronic structure over Mn-based oxide catalysts and provides knowledge that will advance the design of high-performance catalysts for catalytic oxidation.

Highly efficient catalytic oxidation of toluene by amorphous/microcrystalline mixed-phase MnO2

Amorphous transition metal oxides exhibit considerable potential in the catalytic oxidation of volatile organic compounds (VOCs) owing to their distinctive surface properties. In this study, we achieved the modulation of the crystalline structure of manganese oxides by employing various C3 alcohols (alcohols with three carbons) with distinct hydroxyl types during the reduction process with potassium permanganate. Subsequently, a series of characterization techniques were employed to assess the catalytic performance of the prepared MnO2 in the oxidation of toluene. Notably, the MnO2-G obtained from glycerol presented excellent catalytic activity (T90 = 219 °C), stability, and water resistance. The unique amorphous/microcrystalline state of MnO2-G exposed more phase boundaries, and the unsaturated coordination structure facilitated the generation of additional defective sites, favoring the adsorption and activation of oxygen. Furthermore, the mixed-crystalline state induced the elevated Mn3+ content on the surface of MnO2-G, leading to elongation of the Mn-O bond due to the pronounced Jahn-Teller effect of Mn3+. Consequently, the synergistic effects of the mixed crystalline state contributed to the efficient catalytic oxidation of toluene at relatively low temperatures. Additionally, the conversion pathway of toluene on MnO2-G was further revealed by in situ DRIFTS.

Solar photothermo-catalytic conversion of CO2 on phyllosilicates modified with Ni and CeO2

One of the strategies to mitigate the greenhouse effect is converting the CO2 into high-added value products. In this work, a photothermo-catalytic approach, using peculiar Ni-phyllosilicates samples, was applied for the CO2 conversion into solar fuels. In particular, the Ni-phyllosilicates were modified with the introduction of the Ce ions in their structure and successively they were covered with the CeO2 semiconductor. The structural, morphological, textural, optical and reducibility properties as well as the interaction with CO2 were investigated. The Ni/Ce-phyllosilicate covered with CeO2 achieved a CO2 conversion of 87% after 5 hours of photothermo-catalytic test using simulated solar irradiation at 120°C, producing 15.8 μmol/gcat∙h of CO and 5.6 μmol/gcat∙h of CH4. The same sample was tested in an integrated approach where the CO2 was evolved by the catalytic oxidation of toluene and then was converted into CO and CH4, obtaining a CO2 conversion of 50% and 8.8 μmolCO/gcat∙h and 3.3 μmolCH4/gcat∙h. The presence of Ni in the phyllosilicates structure guaranteed a good catalytic stability whereas the deposition of CeO2 allowed to exploit the improved thermal (redox) properties of cerium oxide and favoured the CO2 adsorption on its basic sites and oxygen vacancies. Furthermore, the high surface area of the as-synthetized Ni-phyllosilicates permitted to efficiently expose the CeO2 surface-active sites to the solar radiation. The here investigated catalysts showed versatile properties ideal for hybrid catalytic approaches as the photothermo-catalysis, allowing to propose new solutions for the CO2 valorization.

Modification of red mud catalyst using oxalic acid-assisted UV treatment for toluene removal

An innovative simplified modification method for red mud had been proposed, which enabled its utilization as an active Fe2O3-rich component for catalytic oxidation of toluene. The Box-Behnken design, based on Response Surface Methodology (RSM), was employed to optimize the modification of bauxite residue using oxalic acid combined with UV irradiation. Based on the experimental conditions, the optimal conditions for three independent parameters were determined: acid leaching time (2 hours), UV irradiation time (1 hour), and acid dosage (150 ml),which was in order to enhance the maximum catalytic efficiency of toluene at 300 °C. Under the optimal preparation conditions provided by the Box-Behnken design, the catalytic efficiency of toluene at 300°C could reach 99.2%. In comparison to the acid-modified mud (MRM) and untreated bauxite residue (RM), the aluminum refinery residue modified with oxalic acid-assisted UV irradiation (MRM-UV) exhibited the formation of oxalate sub-iron precipitates, resulting in significantly lower catalytic temperatures (238°C). Furthermore, through XRF, XRD, XPS, O2-TPD, and H2-TPD analysis, it was discovered that a large amount of iron oxide and calcium oxide formed CaO+Fe2O3→Ca2Fe2O5, strengthening the interaction between iron and calcium, augmenting the migration rate of lattice oxygen from the bulk phase to the surface. Consequently, T50 were reduced by 20.9% and 31.8% when compared to MRM and RM. Moreover, the CO2 selectivity of MRM-UV increased from 8.6% to 70.5% compared to RM at 300°C. Using in situ DRIFTS, the reaction pathway of toluene on MRM-UV was identified as benzyl alcohol → benzaldehyde or benzoyl → benzoate→maleic anhydride→CO2 and H2O. The process refinement reduced VOCs emissions and promoted sustainable waste management by combining oxalic acid with catalytically active red mud.

Synergistic oxidation of toluene through bimetal/cordierite monolithic catalysts with ozone

Toluene treatment has received extensive attention, and ozone synergistic catalytic oxidation was thought to be a potential method to degrade VOCs (violate organic compounds) due to its low reaction temperature and high catalytic efficiency. A series of bimetal/Cord monolithic catalysts were prepared by impregnation with cordierite, including MnxCu5−x/Cord, MnxCo5−x/Cord and CuxCo5−x/Cord (x = 1, 2, 3, 4). Analysis of textural properties, structures and morphology characteristics on the prepared catalysts were conducted to evaluate their performance on toluene conversion. Effects of active component ratio, ozone addition and space velocity on the catalytic oxidation of toluene were investigated. Results showed that MnxCo5−x/Cord was the best among the three bimetal catalysts, and toluene conversion and mineralization rates reached 100 and 96% under the condition of Mn2Co3/Cord with 3.0 g/m3 O3 at the space velocity of 12,000 h−1. Ozone addition in the catalytic oxidation of toluene by MnxCo5−x/Cord could efficiently avoid the 40% reduction of the specific surface area of catalysts, because it could lower the optimal temperature from 300 to 100 °C. (Co/Mn)(Co/Mn)2O4 diffraction peaks in XRD spectra indicated all the four MnxCo1−x/Cord catalysts had a spinel structure, and diffraction peak intensity of spinel reached the largest at the ratio of Mn:Co = 2:3. Toluene conversion rate increased with rising ozone concentration because intermediate products generated by toluene degradation might react with excess ozone to generate free radicals like ·OH, which would improve the toluene mineralization rate of Mn2Co3/Cord catalyst. This study would provide a theoretical support for its industrial application.

Application insights of environmental catalysts: Synergistic effects of cellulose-based porogens and catalytic metal sites in toluene catalytic oxidation

Utilizing environmentally-friendly bacterial cellulose as a scaffold, a highly porous, layered OA-BC catalyst was synthesized through an enhanced sol-gel process. This catalyst demonstrated exceptional performance in the oxidation of toluene, outperforming conventional alternatives that utilize chemical porogens. The OA-BC catalyst efficiently degrades toluene at 220℃ with high stability and hydrophobicity, indicating resistance to deactivation. Its superior activity is due to increased oxygen vacancies, enhanced metal oxide cooperation, and a layered porous structure, which together enhance active oxygen species and oxygen diffusion. Calcination of the OA-BC catalyst results in molecular cleavage and formation of small aggregates, increasing hydroxyl groups that stabilize Cu and Ce centers, enhancing toluene-oxygen reactions. In-situ infrared and X-ray photoelectron spectroscopy confirm stable monodentate Cu+ ligands, contributing to its high catalytic activity. This study introduces a novel approach by employing bacterial cellulose as a template for synthesizing a porous stratified OA-BC catalyst, demonstrating superior performance in toluene oxidation. The efficacy of catalyst results from a tripartite synergy involving the stratified porous architecture, the stabilizing effect of Cu+-coordinating ligands and hydroxyl groups, and the interplay of hydroxyl electron donors and acceptors, shedding light on environmentally benign catalyst development.

Unveiling the confinement and interface effect on low temperature degradation of toluene over mesoporous zeolite encapsulated Pt-CeO2 catalyst

The efficient degradation of volatile organic compounds (VOCs) at low temperatures is urgently needed due to the serious environmental and health hazards they pose. While precious metal-based catalysts offer excellent performance, their application is limited by high-temperature sintering and aggregation. Therefore, inhibiting the migration and aggregation of precious metals during the reaction process can effectively improve their utilization and alleviate catalyst deactivation. In this study, a novel encapsulated catalyst (Pt-CeO@meso-S1) containing Pt-CeO2 interfaces was constructed using mesoporous-rich zeolite as a shell layer and applied to the catalytic oxidation of toluene. The introduction of CeO2 constructed a Pt-CeO2 active interface that promoted the low-temperature degradation of toluene, achieving complete oxidation of toluene at 160 ℃. The crystalline phase transition strategy enhanced the specific surface area, improving the dispersion of platinum and facilitating the construction of the Pt-CeO2 interface. The zeolite shell and mesoporous pores effectively confined/stabilized the Pt-CeO2 active components and inhibited platinum sintering, resulting in outstanding water resistance and high-temperature stability. DFT calculations demonstrated that the presence of the Pt-CeO2 active interfaces reduced oxygen vacancy formation energy and facilitated gas-phase oxygen activation. DFT calculations demonstrated that the presence of the Pt-CeO2 active interfaces reduces the oxygen vacancy formation energy and boosts the activation of gas-phase oxygen. The Mars-van-Krevelen (MvK) mechanism governing toluene degradation over Pt-CeO2@meso-S1 was revealed by in situ DRIFTS. This work provides a promising candidate for industrial high-performance catalytic removal of VOCs at low temperatures.

Mechanism of the generation of benzaldehyde and benzoic acid on Pd (1 1 1) surface during the destruction of toluene: Verification of experiments and models

Catalytic oxidation technology is still the mainstream technology of VOCs treatment at present, and it is of great significance to study the main active components of catalysts and clarify the evolution and transformation process of intermediate products in the catalytic process for clarifying the reaction mechanism and guiding the catalyst design. Pd was identified as the main active component in catalytic oxidation of toluene, and the important intermediate products in the degradation of toluene, i.e., benzaldehyde and benzoic acid, were obtained through experiment and In-situ DRIFT spectra. However, the specific evolution process of intermediates is difficult to observe experimentally. The conversion of toluene on Pd (111) surface was studied by DFT calculation. Benzaldehyde was the most stable intermediate and benzoic acid was the most stable energy state of the reaction products. Then the activation energies and reaction energies of all possible reaction paths from toluene to benzaldehyde or benzoic acid were calculated, and the only transition state was obtained. Two pathways for the formation of benzaldehyde and benzoic acid were identified, in which the oxidation reaction after dehydrogenation may be the common rate-determining step of the two pathways, with a maximum energy barrier of 0.80 eV.

Synergistic photothermal catalytic oxidation of methanol and toluene mixture over Co-MOFs-derived catalyst: Interfacial and promotion effects

Herein, a series of Co/CoOx@CN nanocomposites with tunable synergistic interfacial structure were successfully obtained by a facile pyrolysis treatment. Among these nanocomposites, the nanocomposite pyrolyzed at 500 °C (denoted as Co/CoOx@CN-500) exhibited the best methanol photothermal catalytic activity (97% methanol conversion and 96% CO2 yield) under simulated solar irradiation. Compared with Co nanoparticles and Co@CN, Co/CoOx@CN-500 showed higher methanol photothermal catalytic activity. Moreover, the Co/CoOx@CN-500 also displayed a good ability to degrade methanol under outdoor natural solar. Such excellent photothermal activity mainly benefited from the strong interaction between the metals Co, CoOx and graphitic-carbon, which enhanced the photothermal effect by inducing the high work temperature, and the surface adsorb oxygen species of Co/CoOx@CN-500. Besides, the promotion effect of methanol on toluene oxidation was observed over Co/CoOx@CN-500 for the photothermal catalytic oxidation of the methanol and toluene mixture relative to their individual component. Water molecules did not affect the promotion effect of methanol on the photothermal catalytic oxidation of toluene. Reaction mechanism studies showed that 2-methylbenzaldehyde, the key intermediate formed by the reaction of formaldehyde generated by methanol oxidation and toluene, is the main reason for the improvement of the oxidation activity of toluene.

Enhanced oxygen mobility of Mn-Ce solid solution catalysts for polysaccharide-assisted catalytic oxidation of toluene

This paper discusses the modification of (MnCe)Ox by incorporating various metallic and non-metallic auxiliaries. The findings reveal that the introduction of dextran as a modifier has a positive impact on the catalyst's performance for oxidation of toluene. Complexation reactions between dextran molecules and metal ions lead to a weakening of the M(Mn/Ce)-O bond energy, resulting in increased lattice distortions and oxygen vacancies. Moreover, the mobility of lattice oxygen species was enhanced. The hydroxyl species within the dextran molecule not only promoted the generation of reactive oxygen species but also created acidic sites that reduced the accumulation of intermediates and enhanced selectivity. Optimization of the dextran ratio was conducted, and the results indicated that the MC-2 %-D catalyst exhibited T50 and T90 values of 190 °C and 219 °C. Dextran demonstrated valence regulation function as it contributes to constructing a porous structure and enriching active substances such as Mn3+/Ce3+. The excellent redox properties were maintained based on the formation of some lattice defects. O2-TPD and O 1 s spectroscopic analyses demonstrated that highly migratory and reproducible reactive oxygen species on the catalyst's surface synergistically interact with lattice oxygen, ensuring a continuous and efficient toluene-catalysed oxidation reaction.

Study on the Catalytic Oxidation of Toluene Using CeO2@S-AZMB Prepared from Spent Zn-Mn Batteries

The recycling and utilization of waste alkaline zinc manganese batteries (S-AZMB) has always been a focus of attention in the fields of environment and energy. However, current research mostly focuses on the recycling of purified materials, while neglecting the direct reuse of waste batteries. Here, we propose a new concept of preparing thermal catalysts by combining unpurified S-AZMB with CeO2 by means of ball milling. A series of characterizations and experiments have confirmed that the combination with S-AZMB not only enhances the thermal catalytic activity of CeO2 but also significantly enhances the concentration of surface oxygen vacancies. In the toluene removal experiment, the temperature (T90) at 90% toluene conversions of CeO2@S-AZMB was 180 °C, lower than the 220 °C for CeO2. More noteworthy is that this S-AZMB-based thermal catalyst can maintain a good structure and thermal catalytic stability in cyclic catalysis.

Effect of Fe/Mn Ratio on the Catalytic Oxidation of Toluene over Porous γ-Al2O3 Supported Fe and Mn Bimetal Catalysts

Effect of Fe/Mn Ratio on the Catalytic Oxidation of Toluene over Porous γ-Al2O3 Supported Fe and Mn Bimetal Catalysts

MOF-derived FeOx with highly dispersed active sites as an efficient catalyst for enchaning catalytic oxidation of VOCs

Highly efficient and stable catalysts serve as the crucial factor in VOCs catalytic oxidation technology. Iron-based materials are recognized as potential VOCs catalysts due to their cost-effectiveness and non-toxic nature. However, the limited catalytic performance of traditional iron oxide catalysts hinders their further industrial applications. A series of FeOx catalysts were synthesized via pyrolysis of Fe-based MOFs with diverse morphologies for toluene catalytic oxidation. Characterization results demonstrated that the FeOx-100 catalyst performed optimal characteristics, including the abundant specific surface area and smaller crystallite size, which offered highly dispersed active sites and defects for toluene oxidation. The catalytic activity of FeOx-100 was improved by adjusting the precursors and pyrolysis conditions, achieving a 50% toluene conversion at 223 °C and 90% conversion at 249 °C. The redox abilities of FeOx catalysts were carefully evaluated to assess their impact on catalytic activity. The results confirmed that FeOx-100 exhibited superior low-temperature reducibility, remarkable presence of surface active oxygen and lattice oxygen species, jointly facilitating the toluene oxidation performance at lower temperatures. The results of in situ DRIFTS provided evidence supporting a degradation pathway for toluene, likely proceeding as follows: toluene→ benzaldehyde→ benzoate→ anhydride → …→ CO2 and H2O.

Simultaneous catalytic oxidation of toluene and CO over Cu-V/Al-Ce catalysts: Physicochemical properties-activity relationship and simultaneous oxidation mechanism

Cu-V/Al-Ce with varying ratios of Al2O3/CeO2 were prepared to study the simultaneous catalytic oxidation of toluene and CO. Experimental results show that Cu-V/20Al-80Ce exhibits optimal simultaneous oxidation activity and good durability. This superior performance is related to Cu-Ce, V-Ce, and Al-Ce interactions, which facilitate the exposure of active centers, the creation of oxygen vacanicies, and efficient electron transfer. The mutual influence between toluene and CO during the simultaneous oxidation is then demonstrated. Toluene hinders CO oxidation through the competitive adsorption and the consumption of reactive oxygen species. CO enhances toluene oxidation, which is comprehensively explained by affecting the competition between the desorption and oxidation of benzaldehyde. Despite the mutual influence between toluene and CO, the pathways of CO and toluene oxidation are mutually independent. Toluene oxidation proceeds sequentially from toluene to benzyl alcohol, benzaldehyde, benzoate, and finally to CO2. Before being completely oxidized to CO2, CO is initially converted to carboxylic acid, hydrogen carbonate, free carbonate ion, bidentate formate, and monodentate carbonate.

Regulating electronic metal-support interaction (EMSI) via pore-confinement to enhance non-thermal plasma catalytic oxidation of toluene

The non-thermal plasma catalysis holds great promise for VOCs removal, and the development of catalysts with electronic metal-support interaction (EMSI) effect is beneficial for VOCs removal. In this study, we prepared three Mn@M catalysts with EMSI coordination structures by encapsulating MnOx particles within the mesoporous molecular sieve (MCM-41) with different pore size (2.9 nm, 4.4 nm, and 7.9 nm), and investigated the effect of pore size on EMSI and non-thermal plasma catalytic performance of Mn@M for toluene. Among three catalysts, Mn@M2 with an average pore size of 4.38 nm exhibited the strongest EMSI and superior redox capabilities, thus demonstrating the highest mineralization rate, carbon balance, and CO2 selectivity for plasma catalytic oxidation of toluene. The EMSI effect leads to the formation of electron-rich and electron-poor centers on the Si-O-Mn-O bond, facilitating the generation of reactive oxygen species and enhancing the oxygen cycle. In addition, the reaction degradation pathway was investigated using in situ DRIFTS and GC–MS. This study provides valuable insights for designing highly effective supported catalysts by pore confinement to degrade VOCs in adsorption-plasma catalysis system.

Enhanced catalytic oxidation of toluene over amorphous cubic structured manganese oxide-based catalysts promoted by functionally designed Co–Fe nanowires

Manganese oxide with a special cubic structure grown on Co–Fe nanowire (NW)-coated nickel foam (Mn/Co–Fe/NF) was successfully fabricated by a facile hydrothermal method and applied as an efficient catalyst for the oxidation of toluene.

Engineering Co3O4@3DOM LaCoO3 multistage-pore nanoreactor with superior SO2 resistance for toluene catalytic combustion.

Sulfur dioxide poisoning is a significant factor in catalyst deactivation during the catalytic combustion of volatile organic compounds. In this study, we prepared the LaCoO3 and Co3O4 composite catalysts using both the Ship-in-Bottle and Building-Bottle-Around-Ship approaches. Three-dimensionally ordered macropores (3DOM LaCoO3) were utilized as nanoreactors to protect the active sites during the catalytic combustion of toluene, preventing SO2 poisoning. Additionally, we grew ZIF-67 confined in the nanoreactor to create a multistage-pore structure. The Co3O4@3DOM LaCoO3 catalysts exhibited excellent activity in the complete catalytic oxidation of toluene. Various characterization studies confirmed the presence of a significant number of Co3+ species and an abundance of surface weak acid sites in the Co3O4@3DOM LaCoO3 catalysts, which synergistically enhanced the conversion of VOCs at low temperatures. Notably, the multistage pore structure provided a favorable reaction environment, accelerating the adsorption and diffusion of toluene and intermediates, resulting in excellent sulfur resistance of the catalysts. Moreover, XPS analysis confirmed a strong interaction between Co3O4 and LaCoO3, promoting rapid electron transfer and increasing the activation of O2-. In situ DRIFTS experiments verified that toluene mainly follows the MvK mechanism over Co3O4@3DOM LaCoO3 catalysts, indicating the following reaction pathway: toluene adsorption → benzyl alcohol → benzaldehyde → benzoate → anhydride → CO2 and H2O.