Low-temperature Catalytic Oxidation Research Articles

Enhanced low-temperature CO oxidation activity through crystal facet engineering of Pd/CeO2 catalysts

Cerium dioxide (CeO2) supported palladium (Pd) catalysts have found widespread application in CO oxidation reaction owing to their exceptional catalytic performance. The morphology of the CeO2 support dictates the exposed crystal plane, exerting a profound influence on surface structure and redox properties. This is crucial as the atomic arrangement at the surface directly impacts catalytic activity. In this study, a range of CeO2 supports with diverse morphologies (e.g. nano-octahedra, nano-cubes, nano-particles, nano-spheres, and nano-rods) were successfully synthesized through hydrothermal methods and subsequently supported with Pd for CO oxidation. The spherical 1Pd/CeO2–S catalyst, revealing exposed (111) + (100) crystal planes, exhibited significantly higher CO catalytic oxidation activity compared to the catalysts with other morphological CeO2 supports. The results indicated a positive correlation between the content of PdxCe1-xO2-y species and catalytic activity. Notably, this species was most abundantly formed in the spherical 1Pd/CeO2–S catalyst with exposed (111) + (100) crystal planes. The presence of this active species facilitated the formation of surface defects, increased oxygen vacancy concentration, and enhanced metal-support interaction, consequently greatly improving the CO low-temperature catalytic oxidation activity. Consequently, the oxidation state of Pd in the Pd/CeO2 catalyst could be effectively regulated by controlling the exposure of (111) + (100) crystalline surfaces of the CeO2 support, further optimizing the catalytic performance of the Pd/CeO2 catalytic system.

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.

Density functional theory-based screening of Ti4C3O2-loaded single atoms for efficient selective catalytic oxidation of formaldehyde

Indoor formaldehyde (HCHO) pollution poses a major risk to human health. Low-temperature catalytic oxidation is an effective method for HCHO removal. The high activity and selectivity of single atomic catalysts provide a possibility for the development of efficient non-precious metal catalysts. In this study, the most stable single-atom catalyst Ti–Ti4C3O2 was screened by density functional theory among many single atomic catalysts with two-dimensional (2D) monolayer Ti4C3O2 as the support. The computational results show that Ti–Ti4C3O2 is highly selective to HCHO and O2 in complex environments. The HCHO oxidation reaction pathways are proposed based on the Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) mechanisms. According to the reaction energy and energy span models, the E-R mechanism has a lower maximum energy barrier and higher catalytic efficiency than the L-H mechanism. In addition, the stability of the Ti–Ti4C3O2 structure and active center was verified by diffusion energy barrier and ab initio molecular dynamics simulations. The above results indicate that Ti–Ti4C3O2 is a promising non-precious metal catalyst. The present study provides detailed theoretical insights into the catalytic oxidation of HCHO by Ti–Ti4C3O2, as well as an idea for the development of efficient non-precious metal catalysts based on 2D materials.

Enhancement Effect Induced by the Second Metal to Promote Ozone Catalytic Oxidation of VOCs.

It is a promising research direction to develop catalysts with high stability and ozone utilization for low-temperature ozone catalytic oxidation of VOCs. While bimetallic catalysts exhibit excellent catalytic activity compared with conventional single noble metal catalysts, limited success has been achieved in the influence of the bimetallic effect on the stability and ozone utilization of metal catalysts. Herein, it is necessary to systematically study the enhancement effect in the ozone catalytic reaction induced by the second metal. With a simple continuous impregnation method, a platinum-cerium bimetallic catalyst is prepared. Also highlighted are studies from several aspects of the contribution of the second metal (Ce) to the stability and ozone utilization of the catalysts, including the "electronic effect" and "geometric effect". The synergistic removal rate of toluene and ozone is nearly 100% at 30 °C, and it still shows positive stability after high humidity and a long reaction time. More importantly, the instructive significance, which is the in-depth knowledge of enhanced catalytic mechanism of bimetallic catalysts resulting from a second metal, is provided by this work.

Optimizing Pt/Pd Ratios for Enhanced Low-Temperature Catalytic Oxidation of CO and C3H6 on Al2O3 Support

Optimizing Pt/Pd Ratios for Enhanced Low-Temperature Catalytic Oxidation of CO and C3H6 on Al2O3 Support

Probing Catalytic Sites and Adsorbate Spillover on Ultrathin FeO2-x Film on Ir(111) during CO Oxidation.

The spatially resolved identification of active sites on the heterogeneous catalyst surface is an essential step toward directly visualizing a catalytic reaction with atomic scale. To date, ferrous centers on platinum group metals have shown promising potential for low-temperature CO catalytic oxidation, but the temporal and spatial distribution of active sites during the reaction and how molecular-scale structures develop at the interface are not fully understood. Here, we studied the catalytic CO oxidation and the effect of co-adsorbed hydrogen on the FeO2-x/Ir(111) surface. Combining scanning tunneling microscopy (STM), isotope-labeled pulse reaction measurements, and DFT calculations, we identified both FeO2/Ir and FeO2/FeO sites as active sites with different reactivity. The trilayer O-Fe-O structure with its Moiré pattern can be fully recovered after O2 exposure, where molecular O2 dissociates at the FeO/Ir interface. Additionally, as a competitor, dissociated hydrogen migrates onto the oxide film with the formation of surface hydroxyl and water clusters down to 150 K.

Study on the Catalytic Oxidation Modification Effect of Heavy Oil at Low Temperature under the Action of Different Ligand Ferric-Based Systems

This work explores the low-temperature catalytic oxidation of heavy oil (140 °C), resulting in structural changes with reduced heavy components and increased light components. The catalytic oxidation system consists of a catalyst, an oxidant, and a proton donor. Four different complexes of iron-based catalysts were utilized: ferric oleate, iron naphthenate, EDTA–FeNa, and EDDHA–FeNa. Catalytic oxidation processes with these catalysts produced four types of oxygenated oil, which were then analyzed using group composition analysis and a viscosity test. The results show that EDDHA–FeNa is more favorable for the catalytic oxidation of heavy oil in a low-temperature environment, achieving a viscosity reduction rate of 78.57%. Furthermore, the catalytic performance of heavy oil oxidation was investigated using EDDHA–FeNa as catalyst under three conditions: the amount of catalyst, oxidant and reaction temperature. These findings may provide researchers valuable guidance and principles for the investigation and development of advanced catalytic viscosity reduction of heavy oil.

Low-temperature catalytic oxidation of glycerol into glyceric acid over Zr@MCM-41-supported Pt catalyst

Abstract A series of mesoporous Zr@MCM-41 zeolites with different Si/Zr molar ratios were prepared using cetyltrimethylammonium bromide as a template. Pt nanoparticles were then successfully loaded onto the Zr@MCM-41 using a colloid-deposition method. These catalysts were evaluated for the catalytic oxidation of glycerol into glyceric acid at low temperature. The results showed that the molar ratios of the Si/Zr affected the oxidization of the primary OH group, in turn affecting the catalytic activity and selectivity. The Pt/Zr@MCM-41-100 catalyst showed the best catalytic activity, with the conversion of glycerol and selectivity for glyceric acid reaching 50.7% and 65.0%, respectively. The characterization result confirmed that the catalytic activity of Pt/Zr@MCM-41-100 was related to the support structure, the dispersion of the Pt nanoparticles, and the interaction between the Pt nanoparticles and the support. Meanwhile, we investigated the stability of the Pt/Zr@MCM-41-100 catalyst and analyzed the deactivation reasons using characterization.

Low-temperature oxidative removal of benzene from the air using titanium carbide (MXene)-Supported platinum catalysts

MXenes are an emerging class of two-dimensional (2D) inorganic materials with great potential for versatile applications such as adsorption and catalysis. Here, we describe the synthesis of a platinized titanium carbide MXene (Pt@Ti3C2) catalyst with varying amounts of platinum (0.1%–2 wt.%) for the low-temperature oxidation of benzene, an aromatic volatile organic compound often found in industrial flue gas. A 1% formulation of Pt@Ti3C2–R allowed near-complete (97%) oxidation of benzene to CO2 at 225 °C with a steady-state reaction rate (r) of 0.119 mol g−1·h−1. This low-temperature catalytic oxidation reaction was promoted by an increase in the lattice oxygen (O*)/Pt2+ species (active sites) of 1%Pt@Ti3C2–R from 45.3/34.6% to 71.0/61.1% through pre-thermal reduction under H2 flow, as revealed by X-ray photoelectron spectroscopy, temperature-programmed reduction, and in situ diffuse reflectance infrared Fourier transform spectroscopy analyses. The cataltyic activity of 1% Pt@Ti3C2–R against benzene was assessed under the control of the key process variables (e.g., catalyst mass, flow rate, benzene concentration, relative humidity, and time-on-stream) to help optimize the oxidation reaction process. The results provide new insights into the use of platinum-based 2D MXene catalysts for low-temperature oxidative removal of benzene from the air.

Hydrogen Spillover Induced PtCo/CoOx Interfaces with Enhanced Catalytic Activity for CO Oxidation at Low Temperatures in Humid Conditions.

The development of catalysts with abundant active interfaces for superior low-temperature catalytic CO oxidation is critical to meet increasingly rigorous emission requirements, yet still challenging. Herein, this work reports a PtCo/CoOx/Al2O3 catalyst with PtCo clusters and enriched Pt─O─Co interfaces induced by hydrogen spillover from the Pt sites and self-oxidation process in air, exhibiting excellent performance for CO oxidation at low temperatures and humid conditions. The combination of structural characterizations and in situ Fourier transform infrared spectroscopy reveals that the PtCo cluster effectively prevents CO saturation/poisoning on the Pt surface. Additionally, the presence of Pt─O─Co interfaces in the PtCo/CoOx/Al2O3 catalyst provides a significant number of active sites for oxygen activation and ─OH formation. This facilitates efficient generation of CO2 at ambient temperature by coupling with nearby adsorbed CO molecules, resulting in superior low-temperature activity and long-term stability for CO oxidation under humid conditions. This work provides a facile route toward rationalizing the design of catalysts with more active interfaces for superior low-temperature CO oxidation under humid conditions for practical applications.

Study on the mechanism of acid treatment La0.8Sr0.2Mn0.8Cu0.2O3 to improve the catalytic activity of formaldehyde at low temperature.

To address the issue of surface enrichment of A-site ions in perovskite and the resulting suppression of catalytic activity, the La0.8Sr0.2Mn0.8Cu0.2O3 was modified by treatment with dilute nitric acid (2mol/L) and dilute acetic acid (2mol/L). The results show that the effect of dilute nitric acid treatment on the morphology and catalytic activity of the catalyst is more significant. The specific surface area of the catalyst after dilute nitric acid treatment (268.78 m2/g) is seven times higher than before treatment (37.55 m2/g). The low-temperature catalytic oxidation activity of HCHO of the catalyst after dilute nitric acid treatment is significantly improved, achieving a 50% HCHO oxidation efficiency at 80 °C, while the original sample requires 127 °C to achieve a 50% HCHO conversion. The excellent catalytic activity of the catalyst after dilute nitric acid treatment is related to its large specific surface area, high surface-active site density, and abundant Mn4+ ions. Stability and water resistance experiments show that the catalyst after dilute nitric acid treatment has excellent reaction stability and good water resistance ability. The mechanism of the formaldehyde oxidation reaction is that formaldehyde is first oxidized to a dioxymethylene (DOM) intermediate and DOM dehydrogenation reaction is responsible for the formation of formate species (HCOO-).

Promoted low-temperature CO oxidation activity of CeO2 by Cu doping: The important role of oxygen vacancies

Oxygen vacancies play key roles in improving the activities of catalysts. In this paper, the concentration of oxygen vacancies in a CeO2 catalyst was regulated by a series of Cu doping amounts to promote low-temperature CO catalytic oxidation. Characterizations and DFT calculations show that introduction of an appropriate amount of Cu generates oxygen vacancies and benefits their chemical stabilization, which activates the lattice oxygen and eventually improves the performance of the catalyst. The catalyst exhibits the best CO oxidation activity (T95 = 90.5 °C) when Cu/Ce = 0.2/0.8. This study establishes a theoretical foundation for enhancing CO oxidation by CeO2 at low temperatures by manipulating the oxygen vacancies.

Thermally Inducing Viscous Fluids to Generate Co-Based Perovskites Enriched with Active Species for the Removal of VOCs.

Various Co-based perovskites are synthesized through thermally driving viscous fluids. In this process, rare earth salts, cobalt salts, and citric acid do not require homogeneous mixing but only need to be heated until they melt into a molten viscous slurry. The physicochemical properties of cobalt-based perovskites were examined using techniques such as X-ray diffraction (XRD), electron paramagnetic resonance (EPR), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-Mapping-EDS), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR), oxygen temperature-programmed desorption (O2-TPD), and N2 adsorption-desorption. The results indicate that the surface-active species can be controlled by altering the A-site elements of cobalt-based perovskites. All catalysts synthesized through the thermal treatment of viscous mixtures exhibited a low activation temperature and a low apparent activation energy for the catalytic oxidation of toluene. Among all cobalt-based perovskites, LaCoO3 demonstrated the most outstanding catalytic activity, primarily attributed to its capacity to expose a larger number of surface-active sites and oxygen species, as well as its superior reducibility. Furthermore, the formation process of optimal LaCoO3 was monitored using thermogravimetric analysis-differential scanning calorimetry (TGA-DSC), and the byproducts of the low-temperature catalytic oxidation of toluene by the catalyst were identified using gas chromatography-mass spectrometry (GC-MS). The possible mechanism of toluene oxidation was inferred by in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS). Moreover, LaCoO3 exhibits a predominant resistance to high-temperature hydrothermal conditions. This work provides a scalable and innovative approach to fabricating exceptionally effective catalysts for the efficient purification of VOCs.

Low-temperature catalytic oxidation of PCDD/Fs over MnCeCoOx/PPS catalytic filter.

Catalytic destruction of nitrogen oxides (NOx) combined with dust removal technique has attracted much attention, yet the application in the solid waste incineration air pollution control process is still lacking due to the complex flue gas atmosphere. In this work, the Mn-Ce-Co-Ox catalyst-coated polyphenylene sulfide (PPS) filter fiber with efficient dust removal and low-temperature polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) destruction has been prepared with a redox-precipitation method. The catalyst was uniformly grown around the PPS fiber with appropriate catalyst loading. The effects of several key operating parameters (e.g., reaction temperature, catalyst loading amount, and filtration velocity) on the catalytic efficiency were comprehensively investigated. The results show that the Mn-Ce-Co-Ox/PPS has a decomposition yield of 78.0% in PCDD/Fs and 96% in nitric oxide (NO) conversion at 200 °C. The poisoned catalytic filter exhibits a removal efficiency of 88.6% for PCDD/Fs. In addition, the catalytic filter can completely reject particles smaller than 1.0 μm with a low filtration resistance. Therefore, this efficient and energy-conserving catalytic filter shows promising applications in flue gas pollution treatments.

Electron Donation from Boron Suboxides via Strong p-d Orbital Hybridization Boosts Molecular O2 Activation on Ru/TiO2 for Low-Temperature Dibromomethane Oxidation.

Low-temperature catalytic oxidation is of significance to the degradation of halogenated volatile organic compounds (HVOCs) to avoid hazardous byproducts with low energy consumption. Efficient molecular oxygen (O2) activation is pivotal to it but usually limited by the insufficient electron cloud density at the metal center. Herein, Ru-B catalysts with enhanced electron density around Ru were designed to achieve efficient O2 activation, realizing dibromomethane (DBM) degradation T90 at 182 °C on RuB1/TiO2 (about 30 °C lower than pristine Ru/TiO2) with a TOFRu value of 0.055 s-1 (over 8 times that of Ru/TiO2). Compared to the limited electron transfer (0.02 e) on pristine Ru/TiO2, the Ru center gained sufficient negative charges (0.31 e) from BOx via strong p-d orbital hybridization. The Ru-B site then acted as the electron donor complexing with the 2π* antibonding orbital of O2 to realize the O2 dissociative activation. The reactive oxygen species formed thereby could initiate a fast conversion and oxidation of formate intermediates, thus eventually boosting the low-temperature catalytic activity. Furthermore, we found that the Ru-B sites for O2 activation have adaptation for pollutant removal and multiple metal availability. Our study shed light on robust O2 activation catalyst design based on electron density adjustment by boron.

Styrene removal by low-temperature catalytic oxidation using Mn2O3/Al2SiO5

Highly efficient catalytic oxidation for the removal of volatile organic compounds (VOCs) is commonly accompanied by considerable energy demand to conduct the reaction at high temperature. Therefore, the development of low-temperature catalytic oxidation systems based on metal oxides has attracted widespread interest. In this study, we have assessed the performance of Mn2O3/Al2SiO5 in catalyzing the oxidation of styrene. Tests were conducted in a fixed-bed reactor with different loadings of the supported catalyst under different operating conditions (concentration of styrene, oxygen availability, space velocity, and temperature). The characteristics of the catalyst and the reaction kinetics have been studied in detail. The best catalytic activity was achieved with 38 wt% Mn2O3/Al2SiO5, which gave 95% styrene conversion (T95) at 298 °C. A space velocity of 5000 h−1 provided sufficient reaction time and favored the oxidation of styrene. The absence of O2 significantly suppressed styrene conversion to 25.4%, but the presence of just 1% O2 substantially enhanced its catalytic oxidation. A lower reaction temperature of 282 °C led to reduced performance of the catalyst, such that only 20% styrene conversion was achieved, which was due in part to extensive carbon deposition.

On the role of cationic defects over the surface reactivity of manganite-based perovskites for low temperature catalytic oxidation of formaldehyde

Defect engineering in catalytic materials is a versatile strategy to fine-tune their performance towards oxidation reactions, and break the related bottlenecks. Herein, a series of La1−xMnO3 perovskite-based materials was designedly synthesized to investigate the effect of cation defects on their physico-chemical properties. Based on extensive characterizations and density function theory (DFT) calculations, it is demonstrated that La-deficiency could orderly induce oxygen vacancies and electronic structure regulation on perovskite, which prominently promotes the catalytic activity towards formaldehyde oxidation. The leading material (La0.6MnO3) could retain high activity for 63 h, either under dry or humid air. In brief, this work unveils the feasibility of modulating the surface reactivity by modifying the electronic structure properties of lanthanum manganite perovskites following simple adjustment of the A-site cationic vacancies, and also highlights A-site deficient perovskite as a potentially efficient catalyst for environmental remediation.

Metal support interaction of defective-rich CuO and Au with enhanced CO low-temperature catalytic oxidation and moisture resistance

Metal support interaction of defective-rich CuO and Au with enhanced CO low-temperature catalytic oxidation and moisture resistance

Excellent low-temperature activity for oxidation of benzene serials VOCs over hollow Pt/CoMn2O4 sub-nanosphere: Synergistic effect between Pt and CoMn2O4 on improving oxygen activation

Constructing the interfacial active sites between noble metals and oxides is an effective way to enhancing the catalytic performance of noble metal-supported catalysts. Meanwhile, ultra-low dosage of the noble metal Pt but obtaining favorable catalytic activity is still major challenge to prepare noble metal-supported catalysts. Herein, the active Pt-CoMn2O4 interface with strong metal-support interaction (SMSI) is designed by loading ultra-low Pt content (0.12 wt%) on hollow structured CoMn2O4 sub-nanosphere (Pt/CoMn2O4). Compared with the reference MnOx, CoMn2O4 and Pt/MnOx, Pt/CoMn2O4 shows excellent catalytic activity even in presence of H2O, which is capable of completely converting toluene, ethylbenzene and o-xylene at 163, 207 and 218 °C, respectively. Various characterizations and density functional theory (DFT) calculations are performed to reveal the role of CoMn2O4 and specify the synergistic effect between Pt and CoMn2O4 on surface properties and catalytic performance. Intriguingly, in situ-designed temperature-programmed techniques and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy clarify the substitution of Co in CoMn2O4 enhances oxygen mobility, and the interface of Pt and support is the active sites for gaseous oxygen activation can also be confirmed by DFT calculation results. This SMSI is prone to promote the supplement of active oxygen species that is essential for excellent low-temperature catalytic oxidation performance. This study provides a new insight into the design of high-performance noble metal catalysts, and the understanding of textural structure, active species, synergistic effect, and mechanisms of catalytic systems.

Enhanced low-temperature catalytic combustion of toluene over Cu and Mn co-modified α-MnO2 with flower spheres

MnO2, MnO2-M and MnO2-CM were successfully obtained by one-pot hydrothermal method using different precursors, and were applied for the catalytic oxidation of toluene. A variety of characterization means were used to precisely define the physicochemical characteristics of these catalysts. The Cu and Mn co-modified MnO2-CM shows a nanosphere morphology which is made of worm-like particles. And it exhibits better low-temperature catalytic oxidation activity, long term activity stability and H2O resistance, in which the temperature of 90% toluene conversion is about 207 °C and the apparent activation energy of MnO2-CM is as low as 31.7 kJ∙mol−1. This is due to the strong interaction between Cu and Mn from the redox coupling reaction (Cu+ + Mn4+ ↔ Cu2+ + Mn3+) that contributes to produce more oxygen vacancies in MnO2-CM to enhance the gaseous oxygen activation and supplement of active oxygen species at low temperature, leading to stronger oxidation ability.