High CO Oxidation Activity Research Articles

Enhancing the CO Oxidation Performance of Copper by Alloying with Immiscible Tantalum.

Copper-tantalum (Cu-Ta) immiscible alloy nanoparticles (NPs) have been the subject of extensive research in the field of structural materials, due to their exceptional nanostructural stability and high-temperature creep properties. However, Cu is also a highly active oxidation catalyst due to its abundant valence changes. In this study, we have for the first time obtained homogeneous CuxTa1-x (x = 0.5, 0.7, 0.9, 1) nanoparticles by wet coreduction with an average particle size of approximately 30 nm. Testing verified all the CuxTa1-x/TiO2 (x = 0.5, 0.7, 0.9) showed higher CO oxidation activity than Cu/TiO2, with Cu0.7Ta0.3/TiO2 exhibiting the most promising performance. The temperature-programmed reduction with hydrogen demonstrated that Cu0.7Ta0.3/TiO2 exhibits enhanced redox properties. While kinetic studies indicated that the reaction of the Cu0.7Ta0.3/TiO2 catalyst followed the Langmuir-Hinshelwood mechanism, in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) verified the introduction of Ta induced the generation of bicarbonate as an intermediate product and increased the adsorption capacity of Cu+ on CO in the catalyst, which facilitated the reaction of surface adsorbed CO with oxygen and led to the enhanced CO oxidation activity.

A General Approach for Metal Nanoparticle Encapsulation Within Porous Oxides.

Encapsulation of metal nanoparticles within oxide materials has been shown as an effective strategy to improve activity, selectivity, and stability in several catalytic applications. Several approaches have been proposed to encapsulate nanoparticles, such as forming core-shell structures, growing ordered structures (zeolites or metal-organic frameworks) on nanoparticles, or directly depositing support materials on nanoparticles. Here, a general nanocasting method is demonstrated that can produce diverse encapsulated metal@oxide structures with different compositions (Pt, Pd, Rh) and multiple types of oxides (Al2O3, Al2O3-CeO2, ZrO2, ZnZrOx, In2O3, Mn2O3, TiO2) while controlling the size and dispersion of nanoparticles and the porous structure of the oxide. Metal@polymer structures are first prepared, and then the oxide precursor is infiltrated into such structures and the resulting material is calcined to form the metal@oxide structures. Most Pt@oxides catalysts show similar catalytic activity, demonstrating the availability of surface Pt sites in the encapsulated structures. However, the Pt@Mn2O3 sample showed much higher CO oxidation activity, while also being stable under aging conditions. This work demonstrated a robust nanocasting method to synthesize metal@oxide structures, which can be utilized in catalysis to finely tune metal-oxide interfaces.

CO Oxidation at Low Temperatures over the Au Cluster Supported on Crystalline Silicotitanate.

Crystalline silicotitanate (CST) with a sitinakite structure has attracted considerable attention as an ion exchanger because of its anionic surface owing to SiO4 tetrahedral and TiO6 octahedral linked structures. In particular, the anionic surface of CST is advantageous in immobilizing single Au atoms derived from a cationic precursor such as Au(en)2Cl3 (en = ethylenediamine). In this study, a Au/CST catalyst was prepared and evaluated for CO oxidation. The transmission electron microscopy and X-ray photoelectron spectroscopy results suggest that Au single atoms and clusters (Auδ+, 0 < δ < 1) were supported on Na+-CST particles. The 1.0 wt % Au/CST catalyst yielded high catalytic activity for CO oxidation, where 50% CO oxidation was achieved at a low temperature of -13 °C. In the low-temperature region (from -84 to 20 °C), CO oxidation over Au/CST may progress through the well-known Langmuir-Hinshelwood mechanism. Conversely, the experimental results of CO oxidation without O2 confirmed that the reaction proceeded according to the Au-assisted Mars-van Krevelen mechanism using the lattice oxygens of the CST particles at temperatures above 20 °C. Therefore, this work contributes to the design of highly dispersed single-atom or cluster catalysts using the anionic surface of the microporous CST.

Zinc oxide morphology-dependent CuOx-ZnO interactions and catalysis in CO oxidation and CO2 hydrogenation

CuO/ZnO catalysts with different ZnO morphologies, i.e. nanoplates (p-ZnO) and nanorods (r-ZnO), have been prepared to test for CO oxidation and CO2 hydrogenation. Strong morphology-dependent CuOx-ZnO interactions were observed, which are tightly associated with the ZnO morphology. p-ZnO predominantly exposing polar {002} facets greatly promote the CuOx-ZnO interactions, contributing to the stabilities of CuOx/ZnO catalysts in both reactions. Experimental evidences reveal that CuO-ZnO interfaces act as the active sites in CO oxidation. CuO/p-ZnO catalyst with stronger CuO-ZnO interactions can facilitate the generations of fine CuO and interfacial Cu(I) species, responsible for the adsorption and reactivity of CO and subsequently the high (intrinsic) activity in CO oxidation. However, CuO/ZnO catalysts undergo in situ restructuring to generate Cu/ZnO in CO2 hydrogenation, whose catalytic performance is determined by the key step of CO2 activation. Consequently, Cu/r-ZnO catalyst possessing more surface basic sites exhibits better catalytic performance. These results greatly deepen the fundamental understanding of Cu-based catalysts in both reactions and broaden the concept of morphology-dependent catalysis of oxide-based nanocrystal catalysts that varies with the reactions catalyzed.

Theoretical investigation of CO oxidation over polyoxometalate-supported Au cluster catalyst

A polyoxometalate-supported Au cluster catalyst (Au/POM) exhibited high catalytic activity for CO oxidation at room temperature; however, its activity decreased at the reaction temperature above 60 ℃. Density functional theory calculations were performed to elucidate the unique catalytic activities. Our calculations show that the interactions between water molecules accommodated within the defect site of the support and the O2 adsorbed on the Au cluster generate active OOH− species. This OOH− species reacts readily with CO, resulting in high CO oxidation catalytic activity between −40 and 40 degrees Celsius. The activation barrier of CO oxidation over Au/POM in the presence of H2O is much lower than that in the absence of H2O. This is in good agreement with the experimental results, indicating that surface-adsorbed water allows for high CO oxidation catalytic activity around room temperature, whereas the activity decreases at higher temperatures owing to the desorption of surface-adsorbed water molecules.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano‐Islands

AbstractCeO2‐supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2‐Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano-Islands.

CeO2-supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2-Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.

Effects of Synthesis Method on Catalytic Activities of Ag/TiO2 Catalyst in CO Oxidation Reaction

Supported silver catalysts on titanium dioxide have been synthesized by three different methods to compare catalytic activity in CO oxidation. The catalysts were prepared by the wet impregnation method with 10 mole% of silver. In the first method, the silver catalysts were impregnated on the titanium dioxide nanoparticles (Ag/TNP), while in the second method, the silver catalysts were impregnated on the titanium dioxide nanotubes (Ag/TNT). The third method, the silver catalysts were impregnated on the titanium dioxide nanoparticles before the nanotube process (Ag/TNP-TNT). The Ag/TNP and Ag/TNT catalysts showed highly dispersed silver nanoparticles with an average particle size of less than 5 nm on the surface of titanium dioxide, whereas the Ag/TNP-TNT catalyst exhibited much lower dispersion of silver nanoparticles. The highly dispersed silver on the titanium dioxide resulted in a large number of surface active sites (Ag0). The catalytic activity test found that the Ag/TNT catalysts with the highest number of active sites (2.20 × 1020 atom/g-catalyst) exhibited higher CO oxidation activity than the Ag/TNP and Ag/TNT catalysts with 100% CO conversion at 125°C.

Mining wastes as CO oxidation mesoporous catalysts from the Fe-skarns of Serifos Island, Cyclades, Greece

The Fe-skarns from the Greek Island of Serifos in Cyclades has been utilized only for the exploitation of magnetite ores, while significantly vast amounts of red and yellow hematite ores remained unexploited as mining wastes. This study explores the effective utilization of such mining wastes per se, as active mesoporous catalysts for energy applications, taking CO oxidation as a model reaction. The results of our multi-analytical study have illustrated that the physicochemical characteristics of the hematite materials can be positively influenced by the implementation of a simple calcination step, while the characteristics of magnetite remained unaffected. The calcined yellow and red mineral hematite from Serifos Fe-skarns mining wastes per se, act beneficial in the catalytic activity with respect to calcined magnetite catalyst. The calcinated counterparts of hematite, and especially yellow hematite, can efficiently be used as a support for depositing Au nanoparticles, and thus achieving even higher activity for CO oxidation (90% CO conversion), at much lower temperatures (T ∼62.0 °C). The mining wastes per se of Serifos, mainly of mesoporous hematite, are particularly active for CO oxidation, without any complex pretreatments or activation or functionalization in the context of circular economy.

Functionalisation of alkali-resistant nanoporous glass via Au nanoparticle decoration using alkaline impregnation: catalytic activity for CO removal.

The concerted use of nano-metal particles with catalytic functions and nanoporous materials holds promise for effective air purification and gas sensing; however, only a few studies have used porous glasses as supports for Au nanoparticles. Furthermore, Au/nanoporous glasses with activities comparable to that of Au/TiO2, which is a typical Au catalyst, have not been reported to date. This study demonstrates that a nanoporous glass, which is highly acid- and alkali-resistant and chemically stable, can be decorated with Au nanoparticles using an alkali impregnation method. The resulting composite exhibits high catalytic activity in CO oxidation. The catalysts reported herein are as active as Au/TiO2 catalysts per active site. Further optimisation of the pore properties of the glass and sizes of the Au nanoparticles is expected to result in excellent catalytic systems for CO removal and sensing.

Electrochemical Synthesis of Copper Mesh-Supported Thermo-Catalysts.

Metallic substrates, widely studied in the context of monolithic catalysts, offer inherent advantages in heterogeneous catalysis due to their exceptional thermal conductivity and mechanical properties. However, synthesizing stable monolithic catalysts with metallic substrates in a well-controlled manner remains a significant challenge. Here, this work introduces a simple, cost-efficient method to fabricate robust Cu mesh-supported thermo-catalysts using a modified cycling chronopotentiometry approach, where the Cu mesh serves as a donor of Cu ions. In this method, the Cu mesh surface generates two distinct layers of CuO and Cu2O. In this context, CuO acts as the active phase, accounting for the high CO oxidation activity of Cu mesh catalysts with T90 ≈ 120 °C. Additionally, these catalysts exhibit considerable potential in electrocatalysis, showcasing significant research and application value.

Highly Active and Water-Resistant Cu-Doped OMS-2 Catalysts for CO Oxidation: The Importance of the OMS-2 Synthesis Method and Cu Doping.

Porous cryptomelane-type Mn oxide (OMS-2) has an outstanding redox property, making it a highly desirable substitute for noble metal catalysts for CO oxidation, but its catalytic activity still needs to be improved, especially in the presence of water. Given the strong structure-performance correlation of OMS-2 for oxidation reactions, herein, OMS-2 is synthesized by solid state (OMS-2S), reflux (OMS-2R), and hydrothermal (OMS-2H) methods, aiming to improve its CO oxidation performance through manipulating synthesis parameters to tailor its particle size, morphology, and crystallinity. Characterization shows that OMS-2S has the highest CO oxidation activity in the absence of water due to its low crystallinity, high specific surface area, large oxygen vacancy content, and good redox property, but the presence of water can greatly reduce its CO oxidation activity. Doping Cu into an OMS-2 can not only improve its CO oxidation activity but also greatly improve its water tolerance. The Cu-doped OMS-2S catalyst with ∼4 wt % Cu can achieve a T90 of 49 °C (1% CO/10% O2/N2 and WHSV = 60,000 mL·g-1·h-1), ranking among the lowest reported T90 values for Mn oxide-based CO oxidation catalysts, and it can maintain nearly 100% CO conversion in the presence of 5 vol % water for over 50 h. In situ DRIFTs characterization indicates that the good water resistance of Cu-doped OMS-2S can be attributed to the significantly suppressed surface hydroxyl group generation because of Cu doping. This work demonstrates the importance of the synthesis method and Cu doping in determining the CO oxidation activity and water resistance of OMS-2 and will provide guidance for synthesizing highly active and water-resistant CO oxidation catalysts.

Evaluation of Pr2Zr2−xCexO7±δ pyrochlores as a potential Cu support catalysts for CO oxidation in simulated GDI conditions

This study evaluates the catalytic activity, both as bulk catalysts and as supports for copper catalysts for CO oxidation in a simulated Gasoline Direct Injection Engine (GDI) of two pyrochlores: Pr2Zr2O7 (PZ) and Pr2Zr1.9Ce0.1O7±δ (PZC). These pyrochlores were synthesized by the solvothermal method. XRD, FE-SEM, HR-TEM, XPS, H2-TPR, and O2-TPD characterization techniques were employed to determine the structural, microstructural, and redox properties of the samples. All materials exhibited high catalytic activity for CO oxidation, with Cu-PZC showing the best performance, which is comparable to that of a 1% Pt/Al2O3 commercial catalyst used as a reference. Thus, the synthesized solids could be a promising and cost-effective alternative to noble metal-based catalysts used to control GDI exhaust gas composition.

A-site cations tailoring the activity of LnMnO3 perovskites for CO and propane oxidation

To understand the role of A-site cations of perovskites on the reactivity, the LnMnO3 perovskites (Ln = La, Nd, Sm) with varied A-site cations were prepared by a facile glycine combustion method and evaluated for CO and propane oxidation. The activity for both reactions followed the trend: NdMnO3 > SmMnO3 > LaMnO3, demonstrating that lanthanide cations at A sites significantly affect the catalytic performance. Combined with Fourier transmission infrared spectra, temperature programmed reduction and desorption techniques, it was revealed that both the strength of Mn–O bonds and the adsorption of reactants played crucial roles on the activity for CO oxidation and C3H8 combustion on the LnMnO3. The adsorption of the reactants was responsible for the higher activity on the NdMnO3 than on the SmMnO3, while the strength of Mn–O bonds for the higher activity on the SmMnO3 than on the LaMnO3. The NdMnO3 possessed both weak Mn–O bonds and favorable adsorption of the reactants achieved the highest activity for CO oxidation and C3H8 combustion. The best NdMnO3 catalyst achieved CO and propane complete conversion at 160 and 360 °C, 90 and 60 °C lower than the LaMnO3, respectively.

CuGaO2 delafossite as a high-surface area model catalyst for Cu+-activated reactions

Copper is one of the goldilocks metals in catalysis. Deciphering the local atomic environment and oxidation state of active centers in supported copper catalysts, as well as the design of materials to control their stability under reaction conditions remains a great challenge today. We show here that a mixed-oxide of copper delafossite with gallium (CuGaO2, Cu1+ and Ga3+) in the form of porous nanoplates, mainly exposing (110) facets with Cu1+ and Ga3+ cations in well-defined surface positions is a promising material as a model catalyst to explore the activity and stability of Cu1+-activated reactions. It is shown that the delafossite structure is preserved after calcination or reduction pretreatments (in pure O2 or H2, respectively). Extensive reduction of the mixed-oxide leads to a stable catalyst with higher activity for CO oxidation, as a result of the formation of geminal dicarbonyl species on Cuδ+, with 0 < δ < 1, under reaction conditions.

Microwave-assisted CO oxidation over LaNiO3 and Ce-promoted LaNiO3

Microwave-assisted catalytic reactions have been investigated for energy-efficient chemical processes. However, catalysts with comparatively high heating properties, activities, and economics have been developed with limited success. In this study, we investigated the catalytic properties of Ce addition to LaNiO3 catalyst, which has high CO oxidation activity and high microwave heating properties. Ce-added catalysts exhibited high heating properties under microwave heating. Increasing the Ce content in the catalyst enhanced the dielectric loss factor, the ability to absorb microwaves and convert them to heat, and improved the microwave heating properties of the catalyst. The catalytic activity toward CO oxidation over Ce-added catalysts decreased in the order of La0.8Ce0.2NiO3 > La0.9Ce0.1NiO3 > LaNiO3 at all oxygen partial pressures when compared to the same microwave power. To clarify the role of Ce addition, temperature programmed reduction (TPR) by H2, CO, and XAFS measurements were performed. TPR results suggested that Ce promotes oxygen mobility and then affects both CO oxidation and microwave heating properties.

Understanding improved thermal stability of lanthanum-modified Cu/CeO2-ZrO2 for CO oxidation under lean-burn exhaust conditions

Rigorous emission regulations and the advancements in combustion engines have forced researchers to develop new strategies for removing CO at low temperatures. The Cu/CeO2-ZrO2 (Cu/CZ) catalyst has received an extensive attention due to its low cost and high CO oxidation activity at low temperatures. Nonetheless, the poor thermal stability of Cu/CZ remains as a major challenge for practical applications. In this study, we systematically investigated the effect of La doping on the hydrothermal stability of Cu/CZ. The La-doped catalyst, Cu/CZL, retained a high CO oxidation ability even after thermal aging at 800 °C for 20 h. La doping not only helped preserve the surface-active oxygen and oxygen storage capacity of Cu/CZ during thermal aging, but also enhanced its ability to efficiently convert intermediate surface carbonate species into CO2. These promoting effects of La resulted in the excellent CO oxidation activity over the aged-Cu/CZL under the simulated exhaust condition, significantly outperforming the conventional counterpart, PtPd/γ-Al2O3.

Submonolayer Cu/Pt film as bifunctional catalyst for CO oxidation: An STM study

Considering the high activity in CO oxidation as well as the related reactions, the surface structure of Cu/Pt bimetallic system and its interaction with CO and O2 molecules have been revisited with low-temperature scanning tunneling microscopy (STM) in combination with density-functional theory calculations (DFT). The extensively concerned Cu/Pt subsurface alloy (Cu-SSA) is clearly demonstrated with relative deactivation to CO and drastically weakened binding to O. In contrast, the submonolayer Cu film on Pt(111) manifests a significant enhancement in activating the O2 molecules while reserving the strong binding to CO at the uncovered Pt area. Detailed control experiments corroborated by DFT calculations revealed that the Cu/Pt interface serves as the critical sites for both O2 activation and the CO oxidation reaction. Therefore, the submonolayer Cu film may register a more promising catalyst structure than the Cu-SSA configuration for the Cu/Pt bimetallic system.

Origin of Higher CO Oxidation Activity of Pt/Rutile than That of Pt/Anatase

Herein, we show that the weak interaction of CO with Pt/TiO2 under the CO oxidation condition is the origin of higher CO oxidation activity of Pt/rutile than that of Pt/anatase. The results of CO temperature-programmed desorption (TPD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicate that the onset temperatures of CO desorption on freshly prepared Pt/rutile and Pt/anatase are the same. However, the CO-TPD curves of Pt/rutile after the reaction test show that the desorption temperature of CO shifts to a lower temperature, while that for Pt/anatase does not change. The in situ pulse reaction using DRIFTS reveals that CO on Pt/rutile reacted with oxygen faster than CO on Pt/anatase. IR spectra with peak deconvolution of adsorbed CO on Pt/rutile exhibit that CO adsorbed on the terrace sites of Pt clusters on rutile (2089 cm–1) reacts readily with O2. These results indicate that the higher low-temperature activity of Pt/rutile is related to its weaker interaction with CO compared with Pt/anatase under the reaction conditions. Our findings deepen the fundamental understanding of metal–support interaction and CO oxidation on Pt/TiO2 catalysts.

Regulating the surface Au sites of Au/TiO2 catalyst for achieving co-oxidation of HCHO and CO at room temperature

While supported Au catalyst is active for formaldehyde (HCHO) or CO oxidation alone at room temperature, it has not been reported hitherto to efficiently catalyze co-oxidation of HCHO and CO. In this work, we prepared the fresh Au/TiO2 (Au/Ti-F) and the Au/Ti-O by pretreating Au/Ti-F at 300 °C under O2 atmosphere. The Au/Ti-F is only active for HCHO oxidation during HCHO and CO co-oxidation, while the Au/Ti-O shows high efficiency for both HCHO and CO oxidation, achieving 100 % conversions at room temperature. Detailed characterization and DFT calculation indicate that only the Au-Ti interface sites were exposed on Au/Ti-F because other Au sites on Au NPs were covered by Au(OH)n (0 <n < 3). Over Au/Ti-O, besides the active sites at the Au-Ti interface, the metallic Au sites away from the interface were formed during the high-temperature treatment. HCHO oxidation occurs at the Au-Ti interface sites while CO oxidation occurs at the metallic top Au sites; hence high activity for HCHO and CO co-oxidation was achieved over Au/Ti-O. The obtained insight into the dual Au sites will benefit future design of supported Au catalysts.