Robust Ru/Ce@Co Catalyst with an Optimized Support Structure for Propane Oxidation.

Short carbon chain alkanes, as typical volatile organic compounds (VOCs), have molecular structural stability and low molecular polarity, leading to an enormous challenge in the catalytic oxidation of propane. Although Ru-based catalysts exhibit a surprisingly high activity for the catalytic oxidation of propane to CO2 and H2O, active RuOx species are partially oxidized and sintered during the oxidation reaction, leading to a decrease in catalytic activity and significantly inhibiting their application in industrial processes. Herein, the Ru/Ce@Co catalyst is synthesized with a specific structure, in which cerium dioxide is dispersed in a thin layer on the surface of Co3O4, and Ru nanoparticles fall preferentially on cerium oxide with high dispersity. Compared with the Ru/CeO2 and Ru/Co3O4 catalysts, the Ru/Ce@Co catalyst demonstrates excellent catalytic activity and stability for the oxidation of propane, even under severe operating conditions, such as recycling reaction, high space velocity, a certain degree of moisture, and high temperature. Benefiting from this particular structure, the Ru/Ce@Co (5:95) catalyst with more Ce3+ species leads to the Ru species being anchored more firmly on the CeO2 surface with a low-valent state and has a strong potential for adsorption and activation of propane and oxygen, which is beneficial for RuOx species with high activity and stability. This work provides a novel strategy for designing high-efficiency Ru-based catalysts for the catalytic combustion of short carbon alkanes.

Crystal Engineering of TiO2 for Enhanced Catalytic Oxidation of 1,2-Dichloroethane on a Pt/TiO2 Catalyst.

Crystal engineering of metal oxide supports represents an emerging strategy to improve the catalytic performance of noble metal catalysts in catalytic oxidation of chlorinated volatile organic compounds (CVOCs). Herein, Pt catalysts on a TiO2 support with different crystal phases (rutile, anatase, and mixed phase (P25)) were prepared for catalytic oxidation of 1,2-dichloroethane (DCE). The Pt catalyst on P25-TiO2 (Pt/TiO2-P) showed optimal activity, selectivity, and stability, even under high-space velocity and humidity conditions. Due to the strong interaction between Pt and P25-TiO2 originating from the more lattice defects of TiO2, the Pt/TiO2-P catalyst possessed stable Pt0 and Pt2+ species during DCE oxidation and superior redox property, resulting in high activity and stability. Furthermore, the Pt/TiO2-P catalyst possessed abundant hydroxyl groups, which prompted the removal of chlorine species in the form of HCl and significantly decreased the selectivity of vinyl chloride (VC) as the main byproduct. On the other hand, the Pt/TiO2-P catalyst exhibited a different reaction path, in which the hydroxyl groups on its surface activated DCE to form VC and enolic species, besides the lattice oxygen of TiO2 for the Pt catalysts on rutile and anatase TiO2. This work provides guidance for the rational design of catalysts for CVOCs.

Total Oxidation of Light Alkane over Phosphate-Modified Pt/CeO2 Catalysts.

Developing efficient catalysts for the total oxidation of light alkane at low temperatures is challenging. In this study, superior catalytic performance in the total oxidation of light alkane was achieved by modulating the acidity and redox property of a Pt/CeO2 catalyst through phosphorus modification. Surface modification with phosphorus resulted in electron withdrawal from Pt, leading to platinum species with high valency and the generation of Brönsted acid sites, leading to increased acidity of the Pt/CeO2 catalyst. Consequently, the ability of the Pt/CeO2 catalyst to activate the C-H bond increased with increasing P content in the catalyst owing to the synergistic effect of Ptδ+-(CeO2-POx)δ- dipolar catalytic sites. In contrast, the redox property of the Pt/CeO2 catalyst weakened at first; subsequently, it was partially restored owing to the recovery of a part of the bare ceria surface with increasing P content. The turnover frequency in propane oxidation over the phosphate-modified Pt/CeO2 catalyst with a P/Ce atomic ratio of 0.06 was 10-fold higher than that over the unmodified Pt/CeO2 catalyst at 220 °C. This comprehensive study not only sheds light on the mechanism underlying the surface modification process but also offers a strategy for realizing higher catalytic activity in the total oxidation of light alkanes.

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.

Highly Efficient Oxidation of Propane at Low Temperature over a Pt-Based Catalyst by Optimization Support.

Pt-based catalysts have attracted widespread attention in environmental protection applications, especially in the catalytic destruction of light alkane pollutants. However, developing a satisfying platinum catalyst with high activity, excellent water-resistance, and practical suitability for hydrocarbon combustion at low temperature is challenging. In this study, the Pt catalyst supported on the selected Nb2O5 oxide exhibited an efficient catalytic activity in propane oxidation and exceeded that of most catalysts reported in the literature. More importantly, the Pt/Nb2O5 catalyst maintained excellent activity and durability even after high-temperature aging at 700 °C and under harsh working conditions, such as a certain degree of moisture, high space velocity, and composite pollutants. The excellent performance of the Pt/Nb2O5 catalyst was attributed to the abundant metallic Pt species stabilized on the surface of Nb2O5, which prompted the C-H bond dissociation ability as the rate-determining step. Furthermore, propane was initially activated via oxidehydrogenation and followed the acrylate species path as a more efficient propane oxidation path on the Pt/Nb2O5 surface. Overall, Pt/Nb2O5 can be considered a promising catalyst for the catalytic oxidation of alkanes from industrial sources and could provide inspiration for designing superb catalysts for the oxidation of light alkanes.

HCl-Tolerant HxPO4/RuOx-CeO2 Catalysts for Extremely Efficient Catalytic Elimination of Chlorinated VOCs.

Bulk metal doping and surface phosphate modification were synergically adopted in a rational design to upgrade the CeO2 catalyst, which is highly active but easily deactivated for the catalytic oxidation of chlorinated volatile organic compounds (Cl-VOCs). The metal doping increased the redox ability and defect sites of CeO2, which mostly promoted catalytic activity and inhibited the formation of dechlorinated byproducts but generated polychlorinated byproducts. The subsequent surface modification of the metal-doped CeO2 catalysts with nonmetallic phosphate completely suppressed the formation of polychlorinated byproducts and, more importantly, enhanced the stability of the surface structure by forming a chainmail layer. A highly active, durable, and selective catalyst of phosphate-functionalized RuOx-CeO2 was the most promising among all the metal-doped (Ru, Pd, Pt, Cr, Mn, Fe, Co, and Cu) CeO2 catalysts investigated owing to the prominent chemical stability of RuOx and its superior versatility in the catalytic oxidation of different kinds of Cl-VOCs and other typical pollutants, including dimethyl sulfide, CO, and C3H8. Moreover, the chemical stability of the catalyst, including its bulk and surface structural stability, was investigated by combining intensive treatment with HCl/H2O or HCl with subsequent ex situ ultraviolet-visible light Raman spectroscopy and confirmed the superior resistance to Cl poisoning of the phosphate-functionalized RuOx-CeO2. This work exemplifies a promising strategy for developing ideal catalysts for the removal of Cl-VOCs and provides a catalyst with the superior catalytic performance in Cl-VOC oxidation to date.

Significant Improvement of Catalytic Performance for Chlorinated Volatile Organic Compound Oxidation over RuOx Supported on Acid-Etched Co3O4.

Ru catalysts have attracted increasing attention in catalytic oxidation of chlorinated volatile organic compounds (CVOCs). However, the development of Ru catalysts with high activity and thermal stability for CVOC oxidation still poses significant challenges due to their restrictive relationship. Herein, a strategy for constructing surface defects on Co3O4 support by acid etching was utilized to strengthen the interaction between active RuOx species and the Co3O4 support. Consequently, both the dispersity and thermal stability of RuOx species were significantly improved, achieving both high activity and stability of Ru catalysts for CVOC oxidation. The optimized Ru catalyst on the HF-etched Co3O4 support (Ru/Co3O4-F) achieved complete oxidation of vinyl chloride at 260 °C under 30 000 mL·g-1·h-1, which was lower than 300 °C for the Ru catalyst on the original Co3O4 (Ru/Co3O4). More importantly, the Ru species on the Ru/Co3O4-F catalyst were hardly lost after calcination at 500-700 °C and even reacting at 650 °C for 120 h. On this basis, the polychlorinated byproducts over the Ru/Co3O4-F catalyst were almost completely effaced by phosphate modification on the catalyst surface. These findings show that the method combining acid etching of the support and phosphate modification provides a strategy for the advancement of catalyst design for CVOC oxidation.

Titania-Samarium-Manganese Composite Oxide for the Low-Temperature Selective Catalytic Reduction of NO with NH3.

A novel Ti-doped Sm-Mn mixed oxide (TiSmMnOx) was first designed for the selective catalytic reduction (SCR) of NOx with NH3 at a low temperature. The TiSmMnOx catalyst exhibited a superior catalytic performance, in which NOx conversion higher than 80% and N2 selectivity above 90% could be achieved in a wide-operating temperature window (60-225 °C). Specially, the catalyst also showed high durability against the large space velocity and excellent SO2/H2O resistance. Ti incorporation can efficiently inhibit MnOx crystallization and tune the MnOx phase during calcination at a high temperature. Subsequently, a high specific surface area as well as an increased amount of acid sites on the TiSmMnOx catalysts were produced. Further, the reducibility of the Sm-doped MnOx catalyst was modulated, facilitating NO oxidation and inhibiting NH3 nonselective oxidation. Consequently, a superior SCR activity was achieved at a low temperature and the operating temperature window of the TiSmMnOx catalyst was significantly widened. These findings may provide new insights into the reasonable design and development of the new non-vanadium catalysts with a high NH3-SCR activity for industrial application.

Mechanochemical Synthesis of Ruthenium Cluster@Ordered Mesoporous Carbon Catalysts by Synergetic Dual Templates.

Ruthenium (Ru)@Ordered mesoporous carbon (OMC) is a key catalyst in fine-chemical production. In general, the OMC support is prepared by a wet self-assembly requiring excessive solvent, toxic phenol-aldehyde precursors and a long reaction time, followed by post-immobilization to load Ru species. Herein, we wish to report a solid-state, rapid, and green strategy for the synthesis of Ru@OMC with biomass tannin as the precursor. The chemistry essence of this strategy lies in the mechanical-force-driven assembly, during which tannin-metal (Zn2+ and Ru3+ ) coordination polymerization and hydrogen-bonding interactions between tannin-block copolymer (PEO-PPO-PEO, F127) simultaneously occur. After thermal treatment, Ru@OMC catalysts with mesoporous channels, narrow pore-size distribution (≈7 nm), and high surface area (up to 779 m2 g-1 ) were directed by F127 micelles. Meanwhile, the Zn2+ ions dilute Ru3+ and avoid the sintering of Ru species, resulting in Ru clusters around 1.4-1.7 nm during carbonization (800 °C). Moreover, the Ru@OMC catalyst afforded a good activity (TOF: up to 4170 h-1 ) in the selective oxidation of benzyl alcohol to benzaldehyde by molecular oxygen.

Ru/CeO2 Catalyst with Optimized CeO2 Support Morphology and Surface Facets for Propane Combustion.

Tailoring the interfaces between active metal centers and supporting materials is an efficient strategy to obtain a superior catalyst for a certain reaction. Herein, an active interface between Ru and CeO2 was identified and constructed by adjusting the morphology of CeO2 support, such as rods (R), cubes (C), and octahedra (O), to optimize both the activity and the stability of Ru/CeO2 catalyst for propane combustion. We found that the morphology of CeO2 support does not significantly affect the chemical states of Ru species but controls the interaction between the Ru and CeO2, leading to the tuning of oxygen vacancy in the CeO2 surface around the Ru-CeO2 interface. The Ru/CeO2 catalyst possesses more oxygen vacancy when CeO2-R with predominantly exposed CeO2{110} surface facets is used, providing a higher ability to adsorb and activate oxygen and propane. As a result, the Ru/CeO2-R catalyst exhibits higher catalytic activity and stability for propane combustion compared with the Ru/CeO2-C and Ru/CeO2-O catalysts. This work highlights a new strategy for the design of efficient metal/CeO2 catalysts by engineering morphology and associated surface facet of CeO2 support for the elimination of light alkane pollutants and other volatile organic compounds.

Total Oxidation of Propane over a Ru/CeO2 Catalyst at Low Temperature.

Ruthenium (Ru) nanoparticles (∼3 nm) with mass loading ranging from 1.5 to 3.2 wt % are supported on a reducible substrate, cerium dioxide (CeO2, the resultant sample is called Ru/CeO2), for application in the catalytic combustion of propane. Because of the unique electronic configuration of CeO2, a strong metal-support interaction is generated between the Ru nanoparticles and CeO2 to stabilize Ru nanoparticles for oxidation reactions well. In addition, the CeO2 host with high oxygen storage capacity can provide an abundance of active oxygen for redox reactions and thus greatly increases the rates of oxidation reactions or even modifies the redox steps. As a result of such advantages, a remarkably high performance in the total oxidation of propane at low temperature is achieved on Ru/CeO2. This work exemplifies a promising strategy for developing robust supported catalysts for short-chain volatile organic compound removal.

Phosphate-Functionalized CeO2 Nanosheets for Efficient Catalytic Oxidation of Dichloromethane.

Tuning the nature and profile of acidic and basic sites on the surface of redox-active metal oxide nanostructures is a promising approach to constructing efficient catalysts for the oxidative removal of chlorinated volatile organic compounds (CVOCs). Herein, using dichloromethane (DCM) oxidation as a model reaction, we report that phosphate (PO x) Brønsted acid sites can be incorporated onto a CeO2 nanosheet (NS) surface via an organophosphate-mediated route, which can effectively enhance the CeO2's catalytic performance by promoting the removal of chlorine poisoning species. From the systematic study of the correlation between PO x composition, surface structure (acid and basic sites), and catalytic properties, we find that the incorporated Brønsted acid sites can also function to decrease the amount of medium-strong basic sites (O2-), reducing the formation of chlorinated organic byproduct monochloromethane (MCM) and leading to the desirable product, HCl. At the optimized P/Ce ratio (0.2), the PO x-CeO2 NSs can perform a stable DCM conversion of 65-70% for over 10 h at 250 °C and over 95% conversion at 300 °C, superior to both pristine and other phosphate-modified CeO2 NSs. Our work clearly identifies the critical role of acid and basic sites over functionalized CeO2 for efficient catalytic CVOCs oxidation, guiding future advanced catalyst design for environmental remediation.

Crystal Structural Effect of AuCu Alloy Nanoparticles on Catalytic CO Oxidation.

Controlling the physical and chemical properties of alloy nanoparticles (NPs) is an important approach to optimize NP catalysis. Unlike other tuning knobs, such as size, shape, and composition, crystal structure has received limited attention and not been well understood for its role in catalysis. This deficiency is mainly due to the difficulty in synthesis and fine-tuning of the NPs' crystal structure. Here, Exemplifying by AuCu alloy NPs with face centered cubic (fcc) and face centered tetragonal (fct) structure, we demonstrate a remarkable difference in phase segregation and catalytic performance depending on the crystal structure. During the thermal treatment in air, the Cu component in fcc-AuCu alloy NPs segregates more easily onto the alloy surface as compared to that in fct-AuCu alloy NPs. As a result, after annealing at 250 °C in air for 1 h, the fcc- and fct-AuCu alloy NPs are phase transferred into Au/CuO and AuCu/CuO core/shell structures, respectively. More importantly, this variation in heterostructures introduces a significant difference in CO adsorption on two catalysts, leading to a largely enhanced catalytic activity of AuCu/CuO NP catalyst for CO oxidation. The same concept can be extended to other alloy NPs, making it possible to fine-tune NP catalysis for many different chemical reactions.

Surfactant-Assisted Stabilization of Au Colloids on Solids for Heterogeneous Catalysis.

The stabilization of surfactant-assisted synthesized colloidal noble metal nanoparticles (NPs, such as Au NPs) on solids is a promising strategy for preparing supported nanocatalysts for heterogeneous catalysis because of their uniform particle sizes, controllable shapes, and tunable compositions. However, surfactant removal to obtain clean surfaces for catalysis through traditional approaches (such as solvent extraction and thermal decomposition) can easily induce the sintering of NPs, greatly hampering their use in synthesis of novel catalysts. Such unwanted surfactants have now been utilized to stabilize NPs on solids by a simple yet efficient thermal annealing strategy. After being annealed in N2 flow, the surface-bound surfactants are carbonized in situ as sacrificial architectures that form a conformal coating on NPs and assist in creating an enhanced metal-support interaction between NPs and substrate, thus slowing down the Ostwald ripening process during post-oxidative calcination to remove surface covers.

A Sacrificial Coating Strategy Toward Enhancement of Metal-Support Interaction for Ultrastable Au Nanocatalysts.

Supported gold (Au) nanocatalysts hold great promise for heterogeneous catalysis; however, their practical application is greatly hampered by poor thermodynamic stability. Herein, a general synthetic strategy is reported where discrete metal nanoparticles are made resistant to sintering, preserving their catalytic activities in high-temperature oxidation processes. Taking advantage of the unique coating chemistry of dopamine, sacrificial carbon layers are constructed on the material surface, stabilizing the supported catalyst. Upon annealing at high temperature under an inert atmosphere, the interactions between support and metal nanoparticle are dramatically enhanced, while the sacrificial carbon layers can be subsequently removed through oxidative calcination in air. Owing to the improved metal-support contact and strengthened electronic interactions, the resulting Au nanocatalysts are resistant to sintering and exhibit excellent durability for catalytic combustion of propylene at elevated temperatures. Moreover, the facile synthetic strategy can be extended to the stabilization of other supported catalysts on a broad range of supports, providing a general approach to enhancing the thermal stability and sintering resistance of supported nanocatalysts.

Enabling direct oxidation of ethane to acetaldehyde with oxygen using supported PdO nanoparticles.

Industrial-scale production of acetaldehyde relies heavily on homogeneous catalysts. Here, we used ethane as the feedstock and developed ZSM-5-supported PdO nanoparticles for the direct oxidation of ethane to acetaldehyde by utilizing O2 and CO. PdO nanoparticles clearly demonstrate effective activity and prevent the further deep oxidation of acetaldehyde.

Solvent-Free Synthesis Enables Encapsulation of Subnanometric FeOx Clusters in Pure Siliceous Zeolites for Efficient Catalytic Oxidation Reactions.

Metal/metal oxide clusters possess a higher count of unsaturated coordination sites than nanoparticles, providing multiatomic sites that single atoms do not. Encapsulating metal/metal oxide clusters within zeolites is a promising approach for synthesizing and stabilizing these clusters. The unique feature endows the metal clusters with an exceptional catalytic performance in a broad range of catalytic reactions. However, the encapsulation of stable FeOx clusters in zeolite is still challenging, which limits the application of zeolite-encapsulated FeOx clusters in catalysis. Herein, we design a modified solvent-free method to encapsulate FeOx clusters in pure siliceous MFI zeolites (Fe@MFI). It is revealed that the 0.3-0.4 nm subnanometric FeOx clusters are stably encapsulated in the 5/6-membered rings intersectional voids of the pure siliceous MFI zeolites. The encapsulated Fe@MFI catalyst with a Fe loading of 1.4 wt % demonstrates remarkable catalytic activity and recycle stability in the direct oxidation of methane, while also promoting the direct oxidation of cyclohexane, surpassing the performance of conventional zeolite-supported Fe catalysts.

Atomic Insights into the Cu Species Supported on Zeolite for Direct Oxidation of Methane to Methanol via Low-Damage HAADF-STEM.

Precise determination of the structure-property relationship of zeolite-based metal catalysts is critical for the development toward practical applications. However, the scarcity of real-space imaging of zeolite-based low-atomic-number (LAN) metal materials due to the electron-beam sensitivity of zeolites has led to continuous debates regarding the exact LAN metal configurations. Here, a low-damage high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging technique is employed for direct visualization and determination of LAN metal (Cu) species in ZSM-5 zeolite frameworks. The structures of the Cu species are revealed based on the microscopy evidence and also proved by the complementary spectroscopy results. The correlation between the characteristic Cu size in Cu/ZSM-5 catalysts and their direct oxidation of methane to methanol reaction properties is unveiled. As a result, the mono-Cu species stably anchored by Al pairs inside the zeolite channels are identified as the key structure for higher C1 oxygenates yield and methanol selectivity for direct oxidation of methane. Meanwhile, the local topological flexibility of the rigid zeolite frameworks induced by the Cu agglomeration in the channels is also revealed. This work exemplifies the combination of microscopy imaging and spectroscopy characterization serves as a complete arsenal for revealing structure-property relationships of the supported metal-zeolite catalysts.

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.

Si-doped Al2O3 nanosheet supported Pd for catalytic combustion of propane: effects of Si doping on morphology, thermal stability, and water resistance.

Catalytic combustion of propane as typical light alkanes was important for the purification of industrial VOCs and automobile hydrocarbon emissions. Si-doped Al2O3 nanosheet was synthesized by a hydrothermal method, and effects of Si content on the morphology and thermal stability of Al2O3 were investigated. The doping of SiO2 could tune the thickness of Al2O3 nanosheets and significantly improve its thermal stability, the θ phase was still maintained, and the specific surface area was as high as 56.3 m2 g-1 after calcination at 1200 °C. And then the Si-doped Al2O3 nanosheets were used as support of Pd catalysts (Pd/Si-Al2O3 nanosheets) for catalytic combustion of propane, especially Pd/3.6Si-Al2O3 nanosheets, which presented high activity, stability, and resistance to sintering and H2O due to the promotion of Si on the thermal stability of Al2O3 and the stabilization (dispersion, isolation, and strong interaction) of PdOx species.