Pt on Atomic-Layered WO3 Islands: Electronic Tuning of Platinum-Tungsten Heterostructures for Highly Efficient Low-Temperature VOC Combustion.

Adjusting the electronic state of noble metal catalysts on a nanoscale is crucial for optimizing the performance of nanocatalysts in many important environmental catalytic reactions, particularly in volatile organic compound (VOC) combustion. This study reports a novel strategy for optimizing Pt catalysts by modifying their electronic structure to enhance the electron density of Pt. The research illustrates the optimal 0.2Pt-0.3W/Fe2O3 heterostructure with atomic-thick WO3 layers as a bulking block to electronically modify supported Pt nanoparticles. Methods such as electron microscopy, X-ray photoelectron spectroscopy, and in situ Fourier transform infrared spectroscopy confirm Pt's electron-enriched state resulting from electron transfer from atomic-thick WO3. Testing for benzene oxidation revealed enhanced low-temperature activity with moderate tungsten incorporation. Kinetic and mechanistic analyses provide insights into how the enriched electron density benefits the activation of oxygen and the adsorption of benzene on Pt sites, thereby facilitating the oxidation reaction. This pioneering work on modifying the electronic structure of supported Pt nanocatalysts establishes an innovative catalyst design approach. The electronic structure-performance-dependent relationships presented in this study assist in the rational design of efficient VOC abatement catalysts, contributing to clean energy and environmental solutions.

Nanocrystalline FeMnO3 Powder as Catalyst for Combustion of Volatile Organic Compounds.

The paper shows the obtaining of nanocrystalline iron manganite (FeMnO3) powders and their investigation in terms of catalytic properties for a series of volatile organic compounds. The catalyst properties were tested in the catalytic combustion of air-diluted vapors of ethanol, methanol, toluene and xylene at moderate temperatures (50-550 °C). Catalytic combustion of the alcohols starts at temperatures between 180 °C and 230 °C. In the case of ethanol vapors, the conversion starts at 230 °C and increases rapidly reaching a value of around 97% at 300 °C. For temperatures higher than 300 °C, the degree of conversion is kept at the same value. In the case of methanol vapors, the conversion starts at a slightly lower temperature (180 °C), and the degree of conversion reaches the value of 97% at a higher temperature (440 °C) than in the case of ethanol, and it also remains constant as the temperature increases. Catalytic combustion of the hydrocarbons starts at lower temperatures (around 50 °C), the degree of conversion is generally lower, and it increases proportionally with the temperature, with the exception of toluene, which shows an intermediate behavior, reaching values of over 97% at 430 °C. The studied iron manganite can be recommended to achieve catalysts that operate at moderate temperatures for the combustion of some alcohols and, especially, ethanol. The performance of this catalyst with regard to ethanol is close to that of a catalyst that uses noble metals in its composition.

Catalytic combustion of lean methane over different Co3O4 nanoparticle catalysts.

Three types of Co3O4 catalyst, namely Co3O4 nanoparticles (denoted as Co3O4-NPs, ∼12 nm in diameter), Co3O4 nanoparticles encapsulated in mesoporou s SiO2 (denoted as Co3O4@SiO2), and Co3O4 nanoparticles inside microporous SiO2 hollow sub-microspheres (denoted as Co3O4-in-SiO2), were explored to catalyze the combustion of lean methane. It was found that the methane conversion over the three catalysts has the order of Co3O4-NPs ≈ Co3O4@SiO2 > Co3O4-in-SiO2 due to the different catalyst structure. The comparison experiments at high temperatures indicate the Co3O4@SiO2 has a significantly improved anti-sintering performance. Combined with the TEM and BET measurements, the results prove that the presence of the mesoporous SiO2 layer can maintain the catalytical activity and significantly improve the anti-sintering performance of Co3O4@SiO2. In contrast, the microporous SiO2 layer reduces the catalytical activity of Co3O4-in-SiO2 possibly due to its less effective diffusion path of combustion product. Thus, the paper demonstrates the pore size of SiO2 layer and catalyst structure are both crucial for the catalytical activity and stability.

Insights into the Electronic Structure Effect of SnMnOx Nanorod Catalysts for Low-Temperature Catalytic Combustion of o-Dichlorobenzene.

For the catalytic combustion reaction of chlorinated volatile organic compounds (CVOCs), the redox properties and acid sites of the catalyst surface are key factors in determining the activity, selectivity, and chlorine-resistance stability. Herein, a series of SnMnOx catalysts for the catalytic combustion of CVOCs were prepared by the changing of Sn-doping way to regulate the electron valance state of Mn element, including reflux (R-SnMnOx ), co-precipitation (C-SnMnOx ) and impregnation (I-SnMnOx ). It was discovered that the R-SnMnOx catalyst had better activity and chlorine resistance than the R-MnOx , C-SnMnOx and I-SnMnOx catalyst, and we discovered that the doping ways of Sn in MnOx catalyst could regulate greatly the surface acidity, active oxygen species, the chemical state of Mnn+ species, and redox ability. Especially, the R-SnMnOx catalysts exhibit excellent water resistance, and the reasons were related to the strong interaction of Snn+ and Mnn+ , which could promote obviously the dispersion of active Mn species, form a large number of acid sites, provide the abundant lattice oxygen species, and own the excellent redox ability, which accelerate the rate of charge transfer between Snn+ and Mnn+ (Sn4+ +Mn2+ →Sn2+ +Mn4+ ) to produce the abundant active species and accelerate the rapid conversion of benzene and intermediates conversion.

Modelling of Catalytic Combustion in a Deformable Porous Burner Using a Fluid-Solid Interaction (FSI) Framework.

The various concepts involved in the mathematical modeling of the fluid-solid interactions (FSIs) of catalytic combustion processes occurring within a porous burner are presented and discussed in this paper. The following aspects of them are addressed: (a) the relevant physical and chemical phenomena appearing at the interface between the gas and the catalytic surface; (b) a comparison of mathematical models; (c) a proposal of a hybrid two/three-field model, (d) an estimation of the interphase transfer coefficients; (e) a discussion of the proper constitutive equations and the closure relations; and (f) a generalization of the Terzaghi concept of stresses. Selected examples of application of the models are then presented and described. Finally, a numerical verification example is presented and discussed to demonstrate the application of the proposed model.

Mechanistic Insight into Catalytic Combustion of Ethyl Acetate on Modified CeO2 Nanobelts: Hydrolysis-Oxidation Process and Shielding Effect of Acetates/Alcoholates.

In this study, based on the comparison of two counterparts [Mn- and Cr-modified CeO2 nanobelts (NBs)] with the opposite effects, some novel mechanistic insights into the ethyl acetate (EA) catalytic combustion over CeO2-based catalysts were proposed. The results demonstrated that EA catalytic combustion consisted of three primary processes: EA hydrolysis (C-O bond breakage), the oxidation of intermediate products, and the removal of surface acetates/alcoholates. Rapid EA hydrolysis typically occurs on surface acid/base sites or hydroxyl groups, and the removal of surface acetates/alcoholates resulting from EA hydrolysis is considered the rate-determining step. The deposited acetates/alcoholates like a shield covered the active sites (such as surface oxygen vacancies), and the enhanced mobility of the surface lattice oxygen as an oxidizing agent played a vital role in breaking through the shield and promoting the further hydrolysis-oxidation process. The Cr modification impeded the release of surface-activated lattice oxygen from the CeO2 NBs and induced the accumulation of acetates/alcoholates at a higher temperature due to the increased surface acidity/basicity. Conversely, the Mn-substituted CeO2 NBs with the higher lattice oxygen mobility effectively accelerated the in situ decomposition of acetates/alcoholates and facilitated the re-exposure of surface active sites. This study may contribute to a further mechanistic understanding into the catalytic oxidation of esters or other oxygenated volatile organic compounds over CeO2-based catalysts.

Synthesis of Cu2O micro/nanocrystals for catalytic combustion of high-concentration CO: The crucial role of glucose.

Cubic Cu2O micro/nanocrystals were successfully synthesized by liquid-phase reduction using copper salt of CuSO4 or CuCl2·2H2O, and glucose or ascorbic acid as reducing agent, respectively. The activity of the catalysts was evaluated by light-off curves of CO self-sustained catalytic combustion via temperature-programmed oxidation of CO (CO-TPO), with the results showing the activity of catalysts following the order of Cu2O-Cl-GLU > Cu2O-S-GLU > Cu2O-S-AA > Cu2O-Cl-AA, (Cl denotes CuCl2·2H2O, GLU denotes glucose, S denotes CuSO4 and AA denotes ascorbic acid, respectively), corresponding to the ignition temperature of 109 °C, 122 °C, 137 °C and 186 °C, respectively. The crystal structure, elemental valence, morphology and redox property of the prepared catalysts were analyzed by using various characterization techniques. Combined with in situ infrared spectrum, the CO self-sustained catalytic combustion over Cu2O catalysts mainly follows the Mars-van-Krevelen (M-v-K) mechanism: the adsorbed and activated CO reacts with lattice oxygen to yield CO2 and oxygen vacancy, and then the oxygen vacancy can be replenished by gaseous oxygen. Combined with catalytic performance of high-concentration CO, it is found that the catalysts prepared using glucose as reducing agent are more angular compared with ascorbic acid. The Cu2O-Cl-GLU synthesized with glucose and CuCl2·2H2O exhibits the best catalytic activity among all the catalysts tested, attributing to its more obvious edge and rough crystal surface. The unique structure of Cu2O-Cl-GLU leads to the high exposure rate and coordination unsaturation of atoms on the cubic Cu2O micro/nanocrystals that can improve the ability of activating gaseous O2 and low temperature reducibility, and consequently facilitating the catalytic activity.

Expediting Toluene Combustion by Harmonizing the Ce-O Strength over Co-Doped CeZr Oxide Catalysts.

Low-temperature catalytic degradation of volatile organic compounds (VOCs) by enhancing the activity of non-precious metal catalysts has always been the focus of attention. The mineralization of aromatic VOCs requires the participation of a large number of oxygen atoms, so the activation of oxygen species is crucial in the degradation reaction. Herein, we originally adjust the Ce-O bond strength in CeZr oxide catalysts by cobalt doping to promote the activation of oxygen species, thus improving the toluene degradation performance while maintaining high stability. Subsequent characterizations and theoretical calculations demonstrate that the weakening of the Ce-O bond strength increases the oxygen vacancy content, promotes the activation of oxygen species, and enhances the redox ability of the catalysts. This strategy also promotes the activation of toluene and accelerates the depletion of intermediate species. This study will contribute a strategy to enhance the activation ability of oxygen species in non-noble metal oxide catalysts, thereby enhancing the degradation performance of VOCs.

Nanosheet-state cobalt-manganese oxide with multifarious active regions derived from oxidation-etching of metal organic framework precursor for catalytic combustion of toluene.

For the first time, a nanosheet-state CoMnx mixed oxide with multifarious active regions was synthesized by oxidation-etching assembly of metal organic framework (MOF) precursor and applied for catalytic combustion of toluene at low temperatures. The obtained optimum catalyst denoted as CoMn6 showed excellent performance, which achieved 90% conversion of 1,000 ppm toluene under a weight hourly space velocity (WHSV) of 60,000 mL/(g·h) at 219 °C. While, it also exhibited long-term stability with strong water resistance property. The characterizations of physicochemical properties indicated that the oxidation-etching assembly process built an abundant mesoporous structure in the CoMnx catalyst, which greatly increased the specific surface area (SSA). Especially, potassium permanganate as oxidant and manganese source led to uniform dispersion and assembling of cobalt atoms, which caused the generation of low-crystallinity CoMnx mixed oxide with abundant dislocations, vacancies, phase interfaces and amorphous structures, resulting in excellent low-temperature reducibility, outstanding lattice oxygen mobility and abundant active species such as Mn3+, Co3+ and adsorbed oxygen species. Density functional theory (DFT) calculations demonstrated that gaseous oxygen with the longer bond length (1.406 Å) and stronger adsorption energy (-4.443 eV) could be adsorbed and activated well on the MnCo2O4.5 (311) plane, which is beneficial for the toluene oxidation. In situ diffuse reflectance infrared spectroscopy (DRIFTS) technique was applied to track the intermediates of toluene combustion under different atmospheres, which further deduced the contributions of different active regions and oxidation mechanism over the CoMnx catalyst. The present facile strategy of oxidation-etching assembly of the MOF precursor for the creating of novel catalyst with high performance could be applied in a wide variety of materials besides VOC combustion catalysts.

Core-shell CoCuOx@MOx (MNb, Ti and Ce) catalysts with outstanding durability and resistance to H2O for the catalytic combustion of o-dichlorobenzene.

Configuring Co-based catalysts with excellent activity, durability, anti-H2O capability and superior chlorine resistance is an effective strategy for catalytic combustion of CVOCs. In this work, we elaborated a CoCuOx catalysts with the same core but different shell. The CoCuOx dodecahedron surface was successfully coated with shells of Nb2O5, TiO2, and CeO2 using a range of conventional synthesis methods. The prepared core-shell catalysts (CoCuOx@TiO2 and CoCuOx@Nb2O5) were found to generate plentiful acid sites and abundant lattice oxygen species, indicating a strong interaction between the core and shell layers that resulted in a significant enhancement of catalytic activity. Additionally, by-products generation was successfully controlled by acid sites and lattice oxygen species. More importantly, the core-shell structure design significantly improved the thermal stability and anti-H2O capability of the catalysts. Furthermore, the possible formation pathways and reaction mechanisms were proposed based on in-situ FTIR and selectivity analysis.

Efficient Catalytic Combustion of Cyclohexane over PdAg/Fe2O3 Catalysts under Low-Temperature Conditions: Establishing the Degradation Mechanism Using PTR-TOF-MS and in Situ DRIFTS.

Cyclohexane, a typical volatile organic compound (VOC), poses high risks to the environment and humans. Herein, synthesized PdAg/Fe2O3 catalysts exhibited exceptional catalytic performance for cyclohexane combustion at lower temperatures (50% mineralization temperature (T50) of 199 °C, 90% mineralization temperature (T90) of 315 °C) than Pd/Fe2O3 (T50 of 262 °C, T90 of 335 °C) and Fe2O3 (T50 of 305 °C, T90 of 360 °C). In addition, PdAg/Fe2O3 displayed enhanced stability by alloying Ag with Pd. The redox and acidity of the PdAg/Fe2O3 were studied by XPS, H2-TPR, and NH3-TPD. In situ diffuse reflectance infrared Fourier transform spectroscopy and proton-transfer-reaction time-of-flight mass spectrometry were applied to identify the intermediates formed on the catalyst surface and in the tail gas during oxidation, respectively. Results suggested that loading PdAg onto Fe2O3 significantly enhanced the adsorption and activation of oxygen and cyclohexane, oxidative dehydrogenation of cyclohexane to benzene, and catalytic cracking of cyclohexane to olefins at low temperatures. This in-depth study will benefit the design and application of efficient catalysts for the effective combustion of VOCs at low temperatures.

Pd/δ-MnO2 nanoflower arrays cordierite monolithic catalyst toward toluene and o-xylene combustion.

Exploring high-efficiency and stable monolithic structured catalysts is vital for catalytic combustion of volatile organic compounds. Herein, we prepared a series of Pd/δ-MnO2 nanoflower arrays monolithic integrated catalysts (0.01-0.07 wt% theoretical Pd loading) via the hydrothermal growth of δ-MnO2 nanoflowers onto the honeycomb cordierite, which subsequently served as the carrier for loading the Pd nanoparticles (NPs) through the electroless plating route. Moreover, we characterized the resulting monolithic integrated catalysts in detail and evaluated their catalytic activities for toluene combustion, in comparison to the controlled samples including only Pd NPs loading and the δ-MnO2 nanoflower arrays. Amongst all the monolithic samples, the Pd/δ-MnO2 nanoflower arrays monolithic catalyst with 0.05 wt% theoretical Pd loading delivered the best catalytic performance, reaching 90% toluene conversion at 221°C at a gas hourly space velocity (GHSV) of 10,000 h-1. Moreover, this sample displayed superior catalytic activity for o-xylene combustion under a GHSV of 10,000 h-1. The monolithic sample with optimal catalytic activity also displayed excellent catalytic stability after 30 h constant reaction at 210 and 221°C.

Defect Engineering on CuMn2O4 Spinel Surface: A New Path to High-Performance Oxidation Catalysts.

Catalytic combustion is an efficient method to eliminate CO and volatile organic compound (VOC) pollutants. CuMn2O4 spinel is a high-performance non-noble metal oxide catalyst for catalytic combustion and has the potential to replace noble metal catalysts. In order to further improve the catalytic activity of CuMn2O4 spinel, we propose a simple and low-cost approach to introduce numerous oxygen and metal vacancies simultaneously in situ on the CuMn2O4 spinel surface for the catalytic combustion of CO and VOCs. Alkali treatment was used to generate oxygen vacancies (VO), copper vacancies (VCu), and novel active sites (VO combines with Mn2O3 at the interface between Mn2O3(222) and CuMn2O4(311)) on the CuMn2O4 spinel surface. In the catalytic combustion of CO and VOCs, the vacancies and new active sites showed high activity and stability. The oxidation rate of CO increased by 4.13 times at 160 °C, and that of toluene increased by 11.63 times at 250 °C. Oxygen is easier to adsorb and dissociate on VO and novel sites, and the dissociated oxygen also more easily participates in the oxidation reaction. Furthermore, the lattice oxygen at VCu more readily participates in the oxidation reaction. This strategy is beneficial for the development of defect engineering on spinel surfaces and provides a new idea for improving the catalytic combustion activity of CuMn2O4 spinel.

Insights into Chlorobenzene Catalytic Oxidation over Noble Metal Loading {001}-TiO2: The Role of NaBH4 and Subnanometer Ru Undergoing Stable Ru0↔Ru4+ Circulation.

Catalytic combustion of ubiquitous chlorinated volatile organic compounds (CVOCs) encounters bottlenecks regarding catalyst deactivation by chlorine poisoning and generation of toxic polychlorinated byproducts. Herein, Ru, Pd, and Rh were loaded on {001}-TiO2 for thermal catalytic oxidation of chlorobenzene (CB), with Ru/{001}-TiO2 representing superior reactivity, CO2 selectivity, and stability in the 1000 min on-stream test. Interestingly, both acid sites and reactive active oxygen species (ROS) were remarkably promoted via adding NaBH4. But merely enhancing these active sites of the catalyst in CVOC treatment is insufficient. Continuous deep oxidation of CB with effective Cl desorption is also a core issue successfully tackled through the steady Ru0↔Ru4+ circulation. This circulation was facilitated by the observed higher subnanometer Ru dispersion on {001}-TiO2 than the other two noble metals that was supported by single atom stability DFT calculation. Nearly 88 degradation products in off-gas were detected, with Ru/{001}-TiO2 producing the lowest polychlorinated benzene byproducts. An effective and sustainable CB degradation mechanism boosted by the cooperation of NaBH4 enhanced active sites and Ru circulation was proposed accordingly. Insights gained from this study open a new avenue to the rational design of promising catalysts for the treatment of CVOCs.

Vinyl chloride catalytic combustion on Pt/CeO2: Tuning Pt chemical state to promote Cl removing.

Supported Pt catalysts usually produce chlorinated byproducts during chlorinated volatile organic compounds (CVOCs) combustion, the removal of formed surface chlorine species is the key to improve the activity, selectivity and stability. In this paper, the Pt chemical state is adjusted by the interaction between Pt and CeO2 through controlling the morphology of CeO2, which further affects the catalytic performance of VC combustion. For Pt/CeO2-octahedron, the weak interaction between Pt and CeO2 results in the formation of PtO2, facilities VC adsorption and C-Cl bonds cleavage and becomes a key active site to accommodate the dissociated Cl species. While the strong interaction leads to the formation of PtxCe1-xO2-σ solid solution on Pt/CeO2-rod has relative lower ability in Cl species removal compared with PtO2. Density functional theory (DFT) calculations also confirms that the introduced Pt species reduces the concentration of Cl species on the surface as well as the chlorinated-byproducts. Hence, Pt/CeO2-octahedron outperformed Pt/CeO2-rod and Pt/CeO2-cube with 90% VC conversion at 280 °C. Furthermore, under the same VC conversion (90%), the concentration of chlorinated byproducts on Pt/CeO2-octahedron was only 4% than that of Pt/CeO2-rod.

Recent progress of catalytic methane combustion over transition metal oxide catalysts.

Methane (CH4) is one of the cleanest fossil fuel resources and is playing an increasingly indispensable role in our way to carbon neutrality, by providing less carbon-intensive heat and electricity worldwide. On the other hand, the atmospheric concentration of CH4 has raced past 1,900 ppb in 2021, almost triple its pre-industrial levels. As a greenhouse gas at least 86 times as potent as carbon dioxide (CO2) over 20 years, CH4 is becoming a major threat to the global goal of deviating Earth temperature from the +2°C scenario. Consequently, all CH4-powered facilities must be strictly coupled with remediation plans for unburned CH4 in the exhaust to avoid further exacerbating the environmental stress, among which catalytic CH4 combustion (CMC) is one of the most effective strategies to solve this issue. Most current CMC catalysts are noble-metal-based owing to their outstanding C-H bond activation capability, while their high cost and poor thermal stability have driven the search for alternative options, among which transition metal oxide (TMO) catalysts have attracted extensive attention due to their Earth abundance, high thermal stability, variable oxidation states, rich acidic and basic sites, etc. To date, many TMO catalysts have shown comparable catalytic performance with that of noble metals, while their fundamental reaction mechanisms are explored to a much less extent and remain to be controversial, which hinders the further optimization of the TMO catalytic systems. Therefore, in this review, we provide a systematic compilation of the recent research advances in TMO-based CMC reactions, together with their detailed reaction mechanisms. We start with introducing the scientific fundamentals of the CMC reaction itself as well as the unique and desirable features of TMOs applied in CMC, followed by a detailed introduction of four different kinetic reaction models proposed for the reactions. Next, we categorize the TMOs of interests into single and hybrid systems, summarizing their specific morphology characterization, catalytic performance, kinetic properties, with special emphasis on the reaction mechanisms and interfacial properties. Finally, we conclude the review with a summary and outlook on the TMOs for practical CMC applications. In addition, we also further prospect the enormous potentials of TMOs in producing value-added chemicals beyond combustion, such as direct partial oxidation to methanol.

Effect of different coatings on the structure and performance of three-dimensional ordered macropores La0.7Ce0.3CoO3 catalysts.

In this work, monolithic catalysts with single coating Ce0.75Zr0.25O2, Al2O3 and composite coating Ce0.75Zr0.25O2-Al2O3 were prepared by PMMA hard template-excessive impregnation method with 3DOM La0.7Ce0.3CoO3 as the active component and cordierite as the carrier, and characterized by SEM, XRD, BET, H2-TPR, and XPS, and the catalytic performance for toluene was tested. The results showed that the active components of 3DOM La0.7Ce0.3CoO3/Ce0.75Zr0.25O2-Al2O3/cordierite catalyst were highly dispersed, forming a complete macroporous structure with the largest specific surface area (10.57 m2·g-1), high surface adsorbed oxygen concentration, and good low-temperature reducibility. Its catalytic activity (T50% = 103℃, T90% = 218℃) for toluene was obviously better than the others. According to the comprehensive analysis, the improvement of the performance of the catalyst may benefit from the excellent physicochemical properties and the synergistic effect between Ce0.75Zr0.25O2-Al2O3 composite coating and active components.

Low-Temperature Combustion of Toluene over Cu-Doped SmMn2O5 Mullite Catalysts via Creating Highly Active Cu2+-O-Mn4+ Sites.

Catalytic combustion of volatile organic compounds (VOCs) at low temperatures is still an urgent issue to be solved. Herein, low-temperature combustion of toluene over Cu-doped SmMn2O5 mullite catalysts via creating highly active Cu2+-O-Mn4+ sites has been originally demonstrated. Cu-doped SmMn2O5 mullite catalysts exhibited 90% conversion of toluene at 206 °C and displayed robust stability even in the presence of water. It has been demonstrated that Cu doping created Cu2+-O-Mn4+ active composite sites that were more exposed after removing surface Sm species via acid-etching. Benefiting from this, the redox and oxygen activation ability of catalysts was significantly enhanced. The consumption of benzaldehyde and benzoic acid as intermediate species and the CO2 generation ability were apparently promoted, which were the direct reasons for the enhanced low-temperature combustion of toluene. This work provides novel ideas for the development of high-performance catalysts for low-temperature VOC combustion, which has great industrial application prospects.

Oxy-Anionic Doping: A New Strategy for Improving Selectivity of Ru/CeO2 with Synergetic Versatility and Thermal Stability for Catalytic Oxidation of Chlorinated Volatile Organic Compounds.

Understanding the formation and inhibition of more toxic polychlorinated byproducts from the catalytic oxidation elimination of chlorinated volatile organic compounds (Cl-VOCs) and unveiling efficient strategies have been essential and challenging. Here, RuOx supported on CePO4-doped CeO2 nanosheets (Ru/Pi-CeO2) is designed for boosting catalytic oxidation for the removal of dichloromethane (DCM) as a representative Cl-VOC. The promoted acid strength/number and sintering resistance due to the doping of electron-rich and thermally stable CePO4 are observed along with the undescended redox ability and the exposed multi-active sites, which demonstrates a high activity and durability of DCM oxidation (4000 mg/m3 and 15,000 mL/g·h, stable complete-oxidation at 300 °C), exceptional versatility for different Cl-VOCs, alkanes, aromatics, N-containing VOCs, CO and their multicomponent VOCs, and enhanced thermal stability. The suppression of polychlorinated byproducts is determined over Ru/Pi-CeO2 and oxy-anionic S, V, Mo, Nb, or W doping CeO2, thus the oxy-anionic doping strategy is proposed based on the quenching of the electron-rich oxy-anions on chlorine radicals. Moreover, the simple mechanical mixing with these oxy-anionic salts is also workable even for other catalysts such as Co, Sn, Mn, and noble metal-based catalysts. This work offers further insights into the inhibition of polychlorinated byproducts and contributes to the convenient manufacture of monolithic catalysts with superior chlorine-poisoning resistance for the catalytic oxidation of Cl-VOCs.

Effects of sulfur poisoning on physicochemical properties and performance of MnO2/AlNi-PILC for toluene catalytic combustion.

AlNi pillared clay (AlNi-PILC) was synthesized firstly, and then MnO2 was supported via wetness impregnation from nitrate precursors. Sulphation was performed by in-situ decomposing ammonium sulfate with different concentrations over MnO2/AlNi-PILC. Catalysts before and after sulfur poisoning were characterized by XRD, N2 adsorption/desorption, HRTEM, XPS, H2-TPR and NH3-TPD. MnO2/AlNi-PILC exhibited high catalytic activity, allowing the complete toluene combustion. Structure of the catalyst was obviously damaged after sulfur poisoning. (001) crystal plane strength of AlNi-PILC was decreased significantly. Meanwhile, the specific surface area and pore volume reduced with increase of sulfate concentration. Sulfur species were readily formed on the surface of poisoned catalyst and deposited in the pore structure of AlNi-PILC, which resulted in significant impacts on the structural stability, acidity and the number of active species. These changes were responsible for the decreased catalytic performance.