Activity For CO Oxidation Research Articles

Synergistic effect as a function of preparation method in CeO2-ZrO2-SnO2 catalysts for CO oxidation and soot combustion

The development of catalysts based on environmentally desirable components is a topical challenge. In the present work, we consider the effects of preparation method on phase composition, porous structure, nature and distribution of active sites as well as synergistic behavior of components in two series of CeO2-ZrO2-SnO2 catalysts for soot combustion and CO oxidation. The catalysts prepared by the citrate method feature rather large SnO2 aggregates distributed on CeO2 and/or ZrO2 oxides. On the contrary, the catalysts prepared by the CTAB-templated approach feature a uniform distribution of oxide species and usually show higher activity in both CO oxidation and soot combustion. In both series, the activity and characteristics of catalysts are enhanced due to the synergistic effects arising when two or more oxide components coexist in their composition, and the degree of synergy is a function of the preparation method. The features of the most active catalysts combine (1) high specific surface area and pore volume, (2) high microstrain values, (3) coexisting oxygen vacancies of different nature, (4) high H2 consumption at low temperatures, and (5) high fraction of adsorbed active oxygen species.

Revealing Dynamics and Competitive Mechanism of Gas-Induced Surface Segregation of PdFe0.08 Dilute Alloy by Multi-Dimensional Imaging.

The restructuring of dilute alloys under gas environments has shown a great impact on their catalytic performance due to intriguing structural sensitivity, but the structural dynamics and underlying mechanism remains elusive. Herein, we directly resolved the distinct dynamic behaviors of PdFe0.08 dilute alloys under CO or O2 environment by multidimensional imaging. The stronger binding of gaseous CO with Fe atoms stimulates Fe segregation out of the PdFe0.08, resulting in 3D growth of Fe islands, whereas the dissociative adsorption of O2 results in 2D layer-by-layer growth of segregated FeO as encapsulation overlayers that bind strongly with the Pd surface underneath. Such varied structures remarkably tune the catalytic activity for CO oxidation, showing a considerably high activity for a CO-treated sample. Our results reveal the competitive mechanism between adsorbate-metal and metal-metal interaction for gas-induced surface segregation, which should be highly considered for the rational design of dilute alloys with dynamically tuned structure and reactivity.

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.

Asymmetric coordinative modulation boosting the activity and thermal stability of Pt1/CeO2 for CO oxidation under harsh condition

Supported metal catalysts play a central role in chemical industry, but it remains a formidable challenge to realize high activity while maintaining atomically dispersed status to maximize atom efficiency under harsh conditions. Herein, a novel strategy of constructing asymmetric coordination Pt active sites via coating N-doped carbon onto ceria supported Pt single atoms (Pt1/CeO2@CN) is proposed, through which superior low-temperature CO oxidation activity and satisfactory thermal stability are achieved simultaneously. Experimental and density functional theory results confirm that the unique asymmetric N2-Pt1-O2 coordinative configuration on Pt1/CeO2@CN tailors the electronic properties of Pt 5d states, increasing the turnover frequency by 15 times for CO oxidation at 120 °C compared with that on Pt1/CeO2 and sustaining the atomically dispersed status of Pt at as high as 400 °C under H2-containing atmosphere. This strategy suggests a promising avenue to fabricating highly active and stable supported metal catalysts for practical applications under harsh conditions.

Effect of flame temperature on structure and CO oxidation properties of Pt/CeO2 catalyst by flame-assisted spray pyrolysis

Flame synthesis offers the potential for the synthesis of structure-controlled catalysts. In this study, Pt/CeO2 nanoparticles were synthesized via flame-assisted spray pyrolysis (FASP) and used as CO oxidation catalysts. The catalysts were synthesized using a burner diffusion flame at three different flame temperatures (maximum flame temperatures, Tf = 1556, 1785, and 2026 K), and their particle structure and CO oxidation activity were evaluated. The synthesized Pt/CeO2 catalysts had a bimodal structure containing 100 nm-scale CeO2 loaded with 10 nm-scale Pt and fine CeO2 less than 10 nm loaded with highly dispersed Pt (less than 1 nm). As the flame temperature increases from 1556 to 2026 K, the formation of fine CeO2 particles dominates, resulting in an increase in BET specific surface area from 7.97 to 112 m2/g and Pt dispersion from 4.67 to 20.6%. Insight into the particle formation routes that determine the catalyst structure is provided by numerical simulation of droplet evaporation in a burner flame. CO oxidation experiments showed that the temperature at which CO conversion reached 100% (T100) decreased from 513 to 378 K with increasing flame temperature in FASP. In addition, the thermal stability test showed that the Pt dispersion after thermal degradation was higher for Pt/CeO2 catalyst made by FASP at Tf = 2026 K than that prepared by the impregnation method, and the T100 for CO oxidation was lower by 20 K.

Facet-Dependent Diversity of Pt-O Coordination for Pt1/CeO2 Catalysts Achieved by Oriented Atomic Deposition.

The surface chemistry of CeO2 is dictated by the well-defined facets, which exert great influence on the supported metal species and the catalytic performance. Here we report Pt1/CeO2 catalysts exhibiting specific structures of Pt-O coordination on different facets by using adequate preparation methods. The simple impregnation method results in Pt-O3 coordination on the predominantly exposed {111} facets, while the photo-deposition method achieves oriented atomic deposition for Pt-O4 coordination into the "nano-pocket" structure of {100} facets at the top. Compared to the impregnated Pt1/CeO2 catalyst showing normal redox properties and low-temperature activity for CO oxidation, the photo-deposited Pt1/CeO2 exhibits uncustomary strong metal-support interaction and extraordinary high-temperature stability. The preparation methods dictate the facet-dependent diversity of Pt-O coordination, resulting in the further activity-selectivity trade-off. By applying specific preparation routes, our work provides an example of disentangling the effects of support facets and coordination environments for nano-catalysts.

Facet‐Dependent Diversity of Pt−O Coordination for Pt1/CeO2 Catalysts Achieved by Oriented Atomic Deposition

AbstractThe surface chemistry of CeO2 is dictated by the well‐defined facets, which exert great influence on the supported metal species and the catalytic performance. Here we report Pt1/CeO2 catalysts exhibiting specific structures of Pt−O coordination on different facets by using adequate preparation methods. The simple impregnation method results in Pt−O3 coordination on the predominantly exposed {111} facets, while the photo‐deposition method achieves oriented atomic deposition for Pt−O4 coordination into the “nano‐pocket” structure of {100} facets at the top. Compared to the impregnated Pt1/CeO2 catalyst showing normal redox properties and low‐temperature activity for CO oxidation, the photo‐deposited Pt1/CeO2 exhibits uncustomary strong metal‐support interaction and extraordinary high‐temperature stability. The preparation methods dictate the facet‐dependent diversity of Pt−O coordination, resulting in the further activity‐selectivity trade‐off. By applying specific preparation routes, our work provides an example of disentangling the effects of support facets and coordination environments for nano‐catalysts.

Supported Binuclear Gold Phosphine Complexes as CO Oxidation Catalysts: Insights into the Formation of Surface‐Stabilized Au Particles

Atomically precise gold phosphine complexes as precursors for supported Au catalysts tested in CO oxidation are presented. Using a variety of analytical techniques, including in situ and operando X‐ray absorption spectroscopy, it is discovered that minor changes in the ligand of the molecular complexes result in significantly different activation behaviors of supported Au catalysts under reaction conditions. When using [Au2(μ2‐POP)2]OTf2 (POP = tetraphenylphosphoxane) as single‐source precursor, an active supported oxidation catalyst in second light‐off is obtained, outperforming a commercial Au/TiO2 and a P‐free Au/Al2O3 reference catalyst. Conversely, using [Au2(μ2‐dppe)2]OTf2 (dppe = diphenylphosphinoethane) on alumina leads to a significant decrease in CO oxidation activity. This difference is attributed to the formation of P‐containing ligand residues on the support in the case of [Au2(μ2‐POP)2]OTf2/Al2O3, which enhances the thermal stability of the Au particles and affects the particle's electronic properties through charge transfer processes. This work provides insights into the dynamic ligand decomposition of molecular gold complexes under reaction conditions and demonstrates the delicate balance between the stabilization of Au particles, clusters, and complexes using ligands and the blocking of active sites. This knowledge will pave the way for the targeted use of molecular transition metal complexes as precursors in synthesizing surface‐stabilized nanoparticles.

Deciphering the structural origin for the remarkable CO oxidation activities of the CuO-based catalysts with diverse morphological CeO2 supports

In this work, octahedral, cubic, particle-like, spherical and rod-shaped nano-CeO2 supports were synthesized by hydrothermal method. CuO/CeO2 catalysts were then prepared via an ultrasonic-assisted impregnation method, employing these differently shaped CeO2 supports. The resulting catalysts were tested for their performance in CO oxidation. The findings revealed that the CuO active sites significantly influenced the oxygen storage and release capacity of CeO2, thereby improving its catalytic activity for low-temperature CO oxidation. The key factors affecting the CO oxidation performance of CuO/CeO2 catalysts with different CeO2 morphologies were investigated through various characterizations. It was found that the specific surface area was not the primary factor in determining catalytic activity. Instead, the exposed crystal planes played a crucial role. By adjusting the crystal plane exposure of CeO2, the supported 1CuO/CeO2 catalysts exhibited different crystal surface configurations. Notably, the 1CuO/CeO2-S catalyst, with exposed (100) and (110) crystal planes, and the 1CuO/CeO2-P catalyst, with exposed (111), (100), and (110) planes, exhibited higher surface defect concentrations. This increased defect concentration facilitated the formation of Cu+ species, enhancing the redox properties and further improving the overall catalytic performance of CO oxidation.

Enhancing Activity and Stability of Pd-on-TiO2 Single-Atom Catalyst for Low-Temperature CO Oxidation through in Situ Local Environment Tailoring.

The development of efficient Pd single-atom catalysts for CO oxidation, crucial for environmental protection and fundamental studies, has been hindered by their limited reactivity and thermal stability. Here, we report a thermally stable TiO2-supported Pd single-atom catalyst that exhibits enhanced intrinsic CO oxidation activity by tunning the local coordination of Pd atoms via H2 treatment. Our comprehensive characterization reveals that H2-treated Pd single atoms have reduced nearest Pd-O coordination and form short-distanced Pd-Ti coordination, effectively stabilizing Pd as isolated atoms even at high temperatures. During CO oxidation, partial replacement of the Pd-Ti coordination by O or CO occurs. This unique Pd local environment facilitates CO adsorption and promotes the activity of the surrounding oxygen species, leading to superior catalytic performance. Remarkably, the turnover frequency of the H2-treated Pd single-atom catalyst at 120 °C surpasses that of the O2-treated Pd single-atom catalyst and the most effective Pd/Pt single-atom catalysts by an order of magnitude. These findings open up new possibilities for the design of high-performance single-atom catalysts for crucial industrial and environmental applications.

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.

In-situ formed stable Pt nanoclusters on ceria-zirconia solid solutions induced by hydrothermal aging for efficient low-temperature CO oxidation

Pt nanoclusters (PtC) on the surface of ceria-zirconia solid solutions exhibit superior low-temperature CO oxidation activity compared to Pt single atoms (Pt1). However, the redispersion behavior of the PtC to Pt1 lowers the efficiency of CO Oxidation. In this work, the stable surface hydroxyl groups were constructed by high-temperature hydrothermal aging treatment. Specifically, the Pt1 catalyst (Pt/CZOe-SA) prepared by atom trapping was subjected to high-temperature hydrothermal treatment to obtain the stable PtC catalyst (Pt/CZOe-HT) with in-situ formed PtC. The experimental results showed that PtC with 2–3 nm size could achieve excellent low-temperature activity and thermal stability. In addition, the ab initio molecular dynamics and density functional theory calculations revealed the specific evolution process of dynamic dispersion for PtC with or without hydroxyl groups from the femtosecond scale, suggesting that the hydroxyl groups limited the dispersion of PtC in the form of “energy fence”. The hydrothermal treatment not only introduced high-temperature stable hydroxyl groups to improve the stability of the in-situ formed PtC, but also optimized the ratio of Pt1 and PtC, and then enhanced the low-temperature activity by the synergistic effect between Pt1 and PtC. The present work can provide theoretical guidance for developing high-performance and high-stability Pt-based catalysts.

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.

Mutual effects of CO and benzene oxidation over Cu catalysts: The role of surface oxygen species and reaction pathways

CuMn, CuMnCe, and CuCe metal oxide catalysts were prepared and applied in oxidizing CO and benzene as representative volatile organic compounds (VOCs). Various characterization methods and in situ diffuse reflectance infrared Fourier transform spectra (DRIFTS) were used to explore mutual effects between CO and benzene oxidation and the role of reactive oxygen species. CuMn shows the highest activity in independent and simultaneous oxidation of CO and benzene due to its spinel Cu1.5Mn1.5O4 structure, which gives abundant Cu+ sites, acidic sites, Oα, and Oβ. Cu+ sites and Oα benefit CO oxidation, while acidic sites, Oα, and Oβ contribute to benzene oxidation, producing intermediates decomposable at low temperatures. Mechanism study reveals that benzene inhibits CO oxidation by competing for Oα at low temperatures to retard carbonate intermediates formation. CO enhances benzene oxidation by promoting benzene preliminary oxidation and intermediates deep degradation. On CuMn, the formation and degradation of maleate and acetate are facilitated, while maleate and formate degradation are promoted on CuMnCe and CuCe, respectively.

Nature of CuxCe1-xO2 solid solution catalysts

Identifying the local environments of active sites of CuxCe1-xO2 solid solution for low-temperature CO oxidation remains significant challenges. In this study, we coupled density functional theory and microkinetic modeling to thoroughly investigate local structures of CuxCe1-xO2 solid solution catalysts, as well as its catalytic performance for low-temperature CO oxidation. Combined with the infrared spectra simulations, we propose that the substitution of Cu3 or Cu4 clusters for one Ce atom accounts for the experimentally observed vibrational peaks of the adsorbed CO, rather than the Cu single atom or dimer. Cu single-atom and Cun clusters (n = 2–4) doped into CeO2 all exhibit an excellent stability against ripening and a promising catalytic activity for low-temperature CO oxidation. This research for the first time elucidates the nature of CuxCe1-xO2 solid solution catalysts and paves the way for the rational design of Cu/CeO2 catalysts for CO oxidation.

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.

Enhancing the Carbon Monoxide Oxidation Performance through Surface Defect Enrichment of Ceria-Based Supports for Platinum Catalyst.

Effective synthesis and application of single-atom catalysts on supports lacking enough defects remain a significant challenge in environmental catalysis. Herein, we present a universal defect-enrichment strategy to increase the surface defects of CeO2-based supports through H2 reduction pretreatment. The Pt catalysts supported by defective CeO2-based supports, including CeO2, CeZrOx, and CeO2/Al2O3 (CA), exhibit much higher Pt dispersion and CO oxidation activity upon reduction activation compared to their counterpart catalysts without defect enrichment. Specifically, Pt is present as embedded single atoms on the CA support with enriched surface defects (CA-HD) based on which the highly active catalyst showing embedded Pt clusters (PtC) with the bottom layer of Pt atoms substituting the Ce cations in the CeO2 surface lattice can be obtained through reduction activation. Embedded PtC can better facilitate CO adsorption and promote O2 activation at PtC-CeO2 interfaces, thereby contributing to the superior low-temperature CO oxidation activity of the Pt/CA-HD catalyst after activation.

Unraveling distinct effects between CuOx and PtCu alloy sites in Pt−Cu bimetallic catalysts for CO oxidation at different temperatures

In situ exploration of the dynamic structure evolution of catalysts plays a key role in revealing reaction mechanisms and designing efficient catalysts. In this work, PtCu/MgO catalysts, synthesized via the co-impregnation method, outperforms monometallic Pt/MgO and Cu/MgO. Utilizing quasi/in-situ characterization techniques, it is discovered that there is an obvious structural evolution over PtCu/MgO from PtxCuyOz oxide cluster to PtCu alloy with surface CuOx species under different redox and CO oxidation reaction conditions. The synergistic effect between PtCu alloy and CuOx species enables good CO oxidation activity through the regulation of CO adsorption and O2 dissociation. At low temperatures, CO oxidation is predominantly catalyzed by surface CuOx species via the Mars-van Krevelen mechanism, in which CuOx can provide abundant active oxygen species. As the reaction temperature increases, both surface CuOx species and PtCu alloy collaborate to activate gaseous oxygen, facilitating CO oxidation mainly through the Langmuir-Hinshelwood mechanism.