High CO Oxidation Activity Research Articles

Синтез и каталитическая активность высокодисперсных твердых растворов Ce0,9Sn0,1O2 и Ce0,8Sn0,1Zr0,1O2 в реакции окисления СО

Fluorite-like solid solutions of Ce0.9Sn0.1O2 and Ce0.8Sn0.1Zr0.1O2 are synthesized by co-precipitation using ammonium carbonate as a precipitant. The samples were characterized by X-ray phase analysis, electron microscopy, energy dispersive analysis, low-temperature nitrogen adsorption, and gas chromatography. It is shown that the formation of solid solutions occurs even at an annealing temperature of 550°C. In this case, the formation of lamellar particles occurs, the size of which, according to SEM data, is 4 μm. The synthesized materials have a mesoporous structure. The specific surface area of Ce0.9Sn0.1O2 samples is 80.6 m2/g, Ce0.8Zr0.1Sn0.1O2 is 76.3 m2/g. Carrying out the calcination at a temperature of 800 °C leads to an increase in the particle size up to 8 – 10 µm. The highest specific surface area of 15.3 m2/g is typical for the Ce0.8Zr0.1Sn0.1O2 sample, which is due to the presence of zirconium ions in its composition. The synthesized compositions demonstrated high activity in CO oxidation. The maximum catalytic activity was observed for the bicomponent system Ce0.9Sn0.1O2: T50% — 180°C, T90% — 236 °C. For samples calcined at a temperature of 800 °C, the most active is Ce0.8Zr0.1Sn0.1O2, which is due to the formation of a more thermally stable system compared to cerium dioxide and Ce0.9Sn0.1O2. To increase the thermal stability, it is advisable to dope the bicomponent composition Ce0.9Sn0.1O2 with Zr+4 ions.

Ternary PdNiO nanocrystals-ornamented porous CeO2/onion-like carbon for electrooxidation of carbon monoxide: unveiling the effect of supports and electrolytes

Porous ternary Pd-based catalysts at low Pd mass exhibit inimitable surface area, accessible active sites, and tunable electronic structure advantageously utilized for high CO oxidation (COoxid) activity and stability in different electrolyte media.

Role of CeO2 in promoting the spillover in CO oxidation reaction over platinum nanoparticle-supported CeO2 catalyst

CeO2 has been extensively studied as a support material for platinum group metals because of the high catalytic activity of CeO2-supported catalysts in oxidation reactions. In particular, it has been reported that the Pt/CeO2 catalyst exhibits high CO oxidation activity after reductive treatment, thereby lowering the temperature of 50 % CO conversion to 150 ℃ or less. Such high activity of Pt/CeO2 has been attributed to the formation of active sites at the interface between the Pt nanoparticles (NP) and CeO2 surface. In this study, we attempt to deepen our understanding of the catalytic activity of Pt/CeO2 by studying the spillover of CO and O species at the interface. Combined kinetics and in situ CO-diffuse reflectance infrared Fourier transform spectroscopy studies reveal that CO spills over from Pt NPs to the CeO2 surface; this contributes to circumventing Pt poisoning by CO at low temperatures. Moreover, the CO oxidation activity of the Pt/CeO2 catalyst was considerably enhanced by simply mixing CeO2 particles with the Pt/CeO2 catalyst. This is explained by the formation of more reactive O atoms on the CeO2 surface after the reductive treatment. This study demonstrates that understanding the dynamic mobility of reactants is vital for discerning catalyst activity and designing more reactive catalysts.

Comparative Study of Pd-Mayenite Catalysts Prepared via Aerogel Approaches.

Pd-containing catalysts based on highly dispersed aerogel-derived mayenite were prepared via two approaches. The Pd@C12A7 sample was obtained through the addition of Pd nitrate solution to a fresh Ca(OH)2-Al(OH)3 gel. Pd/C12A7 was synthesized through conventional wet impregnation of the aerogel-derived mayenite. The evolution of the textural characteristics of the support (C12A7) depending on the calcination temperature was investigated. Pd-containing samples were explored using transmission electron microscopy and spin probe EPR spectroscopy. Using the latter method, the presence of active oxygen species capable of producing nitroxyl radicals from diphenylamine was observed. The activity of these species and the reproducibility of their redox behavior were studied in three cycles of temperature-programmed reduction in both hydrogen and CO atmospheres. A prompt thermal aging technique was used to access and compare the activity of the samples towards CO oxidation. The state of Pd species before and after the aging procedure was studied via UV-Vis spectroscopy. It was found that the dispersion of PdO was higher in the case of the Pd/C12A7 catalysts compared to the Pd@C12A7 sample. This is why the Pd/C12A7 catalyst demonstrated higher activity in CO oxidation and better reducibility in TPR cycles.

Effect of Pd precursors on the catalytic properties of Pd/CeO2 catalysts for CH4 and CO oxidation

Herein, Pd/CeO2 catalysts were prepared using different Pd precursors and applied to CH4 and CO oxidation. Significantly, the Pd/CeO2 catalyst prepared using palladium nitrate (Pd(2)/CeO2 (N)) was highly active toward CH4 oxidation, whereas the catalyst prepared using palladium acetate (Pd(2)/CeO2 (A)) exhibited high CO oxidation activity. The effects of the precursor on the catalytic activity and other properties were studied using various characterization techniques. The Pd(2)/CeO2 (N) catalyst contained surface PdO nanoparticles, which were active sites for CH4 oxidation. On the contrary, the Pd(2)/CeO2 (A) catalyst possessed Pd ions stabilized at CeO2 defect sites, which were not very reactive. However, the high Pd dispersion was beneficial for the CO oxidation reaction. Therefore, the Pd precursor clearly altered the Pd dispersion and state in the Pd/CeO2, which are critical for catalytic activity.

The Study of Thermal Stability of Mn-Zr-Ce, Mn-Ce and Mn-Zr Oxide Catalysts for CO Oxidation.

MnOx-CeO2, MnOx-ZrO2, MnOx-ZrO2-CeO2 oxides with the Mn/(Zr + Ce + Mn) molar ratio of 0.3 were synthesized by coprecipitation method followed by calcination in the temperature range of 400-800 °C and characterized by XRD, N2 adsorption, TPR, TEM, and EPR. The catalytic activity was tested in the CO oxidation reaction. It was found that MnOx-CeO2, MnOx-ZrO2-CeO2, MnOx-ZrO2 catalysts, calcined at 400-500 °C, 650-700 °C and 500-650 °C, respectively, show the highest catalytic activity in the reaction of CO oxidation. According to XRD and TEM results, thermal stability of catalysts is determined by the temperature of decomposition of the solid solution Mnx(Ce,Zr)1-xO2. The TPR-H2 and EPR methods showed that the high activity in CO oxidation correlates with the content of easily reduced fine MnOx particles in the samples and the presence of paramagnetic defects in the form of oxygen vacancies. The maximum activity for each series of catalysts is associated with the start of solid solution decomposition. Formation of active phase shifts to the high-temperature region with the addition of zirconium to the MnOx-CeO2 catalyst.

Pd-Ce-Ox/MWCNTs and Pt-Ce-Ox/MWCNTs Composite Materials: Morphology, Microstructure, and Catalytic Properties.

The composite nanomaterials based on noble metals, reducible oxides, and nanostructured carbon are considered to be perspective catalysts for many useful reactions. In the present work, multi-walled carbon nanotubes (MWCNTs) were used for the preparation of Pd-Ce-Ox/MWCNTs and Pt-Ce-Ox/MWCNTs catalysts comprising the active components (6 wt%Pd, 6 wt%Pt, 20 wt%CeO2) as highly dispersed nanoparticles, clusters, and single atoms. The application of X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) provided analysis of the samples' morphology and structure at the atomic level. For Pd-Ce-Ox/MWCNTs samples, the formation of PdO nanoparticles with an average crystallite size of ~8 nm was shown. Pt-Ce-Ox/MWCNTs catalysts comprised single Pt2+ ions and PtOx clusters less than 1 nm. A comparison of the catalytic properties of the samples showed higher activity of Pd-based catalysts in CO and CH4 oxidation reactions in a low-temperature range (T50 = 100 °C and T50 = 295 °C, respectively). However, oxidative pretreatment of the samples resulted in a remarkable enhancement of CO oxidation activity of Pt-Ce-Ox/MWCNTs catalyst at T < 20 °C (33% of CO conversion at T = 0 °C), while no changes were detected for the Pd-Ce-Ox/MWCNTs sample. The revealed catalytic effect was discussed in terms of the capability of the Pt-Ce-Ox/MWCNTs system to form unique PtOx clusters providing high catalytic activity in low-temperature CO oxidation.

A Tale of Two Sites: Neighboring Atomically Dispersed Pt Sites Cooperatively Remove Trace H2 in CO-Rich Stream.

Single-atom catalysts (SACs) exhibit distinct catalytic behavior compared with nano-catalysts because of their unique atomic coordination environment without the direct bonding between identical metal centers. How these single atom sites interact with each other and influence the catalytic performance remains unveiled as designing densely populated but stable SACs is still an enormous challenge to date. Here, a fabrication strategy for embedding high areal density single-atom Pt sites via a defect engineering approach is demonstrated. Similar to the synergistic mechanism in binuclear homogeneous catalysts, from both experimental and theoretical results, it is proved that electrons would redistribute between the two oxo-bridged paired Pt sites after hydrogen adsorption on one site, which enables the other Pt site to have high CO oxidation activity at mild-temperature. The dynamic electronic interaction between neighboring Pt sites is found to be distance dependent. These new SACs with abundant Pt-O-Pt paired structures can improve the efficiency of CO chemical purification.

Biomimetic Tremelliform Ultrathin MnO2/CuO Nanosheets on Kaolinite Driving Superior Catalytic Oxidation: An Example of CO.

Highly efficient three-dimensional (3D) kaolinite/MnO2-CuO (KM@CuO-NO3) catalysts were synthesized by a mild biomimetic strategy. Kaolinite flakes were uniformly wrapped by ultrathin tremelliform MnO2 nanosheets with thicknesses of around 1.0-1.5 nm. Si-O and Al-O groups in kaolinite hosted MnO2 nanosheets to generate a robust composite structure. The ultrathin MnO2 lamellar structure exhibited excellent stability even after calcination above 350 °C. Kaolinite/MnO2 exhibited abundant edges, sharp corners, and interconnected diffusion channels, which are superior to the common stacked structure. Open channels guaranteed fast transportation and migration of CO and O2 during CO oxidation. The synthesized KM@CuO-NO3 achieved a 90% CO conversion efficiency at a relatively low temperature (110 °C). Furthermore, the abundant oxygen vacancies on KM@CuO-NO3 assisted the adsorption and activation of oxygen species and thus enhanced the oxygen mobility and reactivity in the catalytic process. The mechanism results suggest that CuO introduced to the catalyst not only acted as CO active sites but also weakened the Mn-O bond, subsequently improved the mobilities of the oxygen species, which was found to contribute to its high activity for CO oxidation. This study provides new conceptual insights into rationally regulating structural assembly between transition metal oxides and natural minerals for high-performance catalysis reactions.

Investigation into support effects for Pt and Pd on LaMnO3

The catalytic properties of Pt and Pd supported on thin-film LaMnO3 were investigated. The LaMnO3 film consisted of an ALD-grown 0.5-nm-thick film supported on a high-surface-area MgAl2O4. Pt and Pd were added to the LaMnO3 films by Atomic Layer Deposition (ALD) and then aged by repeated oxidation and reduction cycles at 1073 K. X-Ray Diffraction (XRD), together with Scanning Transmission Electron Microscopy (STEM)/Energy Dispersive Spectroscopy (EDS) showed that Pt underwent extensive sintering during these redox treatments and formed a Pt-Mn alloy following reduction at 1073 K. Consistent with this, the activity of the supported Pt catalysts for CO oxidation decreased progressively with the number of redox cycles. In contrast to the results for Pt, STEM/EDS results indicated that Pd remained well dispersed on LaMnO3, even after five redox cycles. The Pd catalyst showed high activity for CO oxidation at lower temperatures due to a low activation energy and positive reaction order in CO. XRD results with Rietveld analysis for the Pd catalyst indicated the presence of very large crystallites for PdO on the oxidized catalyst and metallic Pd on the reduced catalyst, inconsistent with the high dispersions measured by STEM and the high CO-oxidation rates. Possible explanations for these observations are discussed.

Dual-template synthesis of defect-rich mesoporous Co3O4 for low temperature CO oxidation

CO oxidation is a benchmark in heterogeneous catalysis for evaluation of redox catalysts due to its practical relevance in many applications and the fundamental problems associated with its very high activity at low temperatures. Among which, Co3O4 is one of the most active non-precious metal catalysts. Exposed crystal planes and cobalt sites are considered to be important for its high catalytic activity. Herein, we demonstrate an enhanced CO oxidation activity by a defect-rich mesoporous Co3O4 that prepared by a designed dual-template method. Two different kinds of silicas are used as hard-templates at the same time, resulting in a defect-rich mesoporous Co3O4 with a surface area as high as 169 m2/g. This catalyst exhibited a very high catalytic activity for low temperature CO oxidation with a light-off temperature at −73 oC under the space velocity of 80,000 mL h-1 gcat-1. Further studies reveal that the high surface area promotes the lattice oxygen mobility, surface rich of Co2+ species and active oxygen species are crucial for the high catalytic activity. Moreover, the dual-template approach paves a way towards the design and construction of high-surface-area mesoporous metal oxides for various applications.

NaCl-Templated Ultrathin 2D-Yttria Nanosheets Supported Pt Nanoparticles for Enhancing CO Oxidation Reaction.

Morphology of support is of fundamental significance to the fabrication of highly efficient catalysts for CO oxidation reaction. Many methods for the construction of supports with specific morphology and structures greatly rely on controlling general physical and chemical synthesis conditions such as temperature or pH. In this paper, we report a facile route to prepare yttria nanosheet using NaCl as template to support platinum nanoparticles exhibiting higher CO oxidation activity than that of the normally prepared Pt/Y2O3. With the help of TEM and SEM, we found that Pt NPs evenly distributed on the surface of NaCl modified 2D-nanosheets with smaller size. The combination of XAFS and TEM characterizations demonstrated that the nano-size Pt species with PtxOy structure played an essential role in the conversion of CO and kept steady during the CO oxidation process. Moreover, the Pt nanoparticles supported on the NaCl templated Y2O3 nanosheets could be more easily reduced and thus exposed more Pt sites to adsorb CO molecules for CO oxidation according to XPS and DRIFTS results. This work offers a unique and general method for the preparation of potential non-cerium oxide rare earth element oxide supported nanocatalysts.

Catalytic properties of LaNiO3 and Mn-modified LaNiO3 catalysts for oxidation of CO and benzene

ABO3-type perovskite oxides containing transition metals at the B site are effective catalysts for oxidation reactions. In this study, LaNiO3 was prepared by the hydrolysis-precipitation method, and LaNiO3 was modified with Mn by the impregnation method. LaNiO3 showed higher CO oxidation activity than LaCoO3, LaMnO3, and LaFeO3. The high activity of LaNiO3 was attributed to the reactivity of the lattice oxygen in LaNiO3, as confirmed by temperature-programmed reduction by H2 (H2-TPR) and CO-TPR studies. The Mn-modified LaNiO3 exhibited higher activity for benzene oxidation than LaNiO3. The CO oxidation properties of the Mn-modified LaNiO3 catalysts correlated with their H2-reduction properties, whereas benzene oxidation properties were improved by the increasing amount of Mn on the catalyst surface.

Quality or Quantity? How Structural Parameters Affect Catalytic Activity of Iron Oxides for CO Oxidation

The replacement of noble metal catalysts by abundant iron as an active compound in CO oxidation is of ecologic and economic interest. However, improvement of their catalytic performance to the same level as state-of-the-art noble metal catalysts requires an in depth understanding of their working principle on an atomic level. As a contribution to this aim, a series of iron oxide catalysts with varying Fe loadings from 1 to 20 wt% immobilized on a γ-Al2O3 support is presented here, and a multidimensional structure–activity correlation is established. The CO oxidation activity is correlated to structural details obtained by various spectroscopic, diffraction, and microscopic methods, such as PXRD, PDF analysis, DRUVS, Mössbauer spectroscopy, STEM-EDX, and XAS. Low Fe loadings lead to less agglomerated but high percentual amounts of isolated, tetrahedrally coordinated iron oxide species, while the absolute amount of isolated species reaches its maximum at high Fe loadings. Consequently, the highest CO oxidation activity in terms of turnover frequencies can be correlated to small, finely dispersed iron oxide species with a large amount of tetrahedrally oxygen coordinated iron sites, while the overall amount of isolated iron oxide species correlates with a lower light-off temperature.

Neighboring sp-Hybridized Carbon Participated Molecular Oxygen Activation on the Interface of Sub-nanocluster CuO/Graphdiyne.

Activation of O2 is a crucial step in oxidation processes. Here, the concept of sp-hybridized C≡C triple bonds as an electron donor is adopted to develop highly active and stable catalysts for molecular oxygen activation. We demonstrate that the neighboring sp-hybridized C and Cu sites on the interface of the sub-nanocluster CuO/graphdiyne are the key structures to effectively modulate the O2 activation process in the bridging adsorption mode. The as-prepared sub-nanocluster CuO/graphdiyne catalyst exhibited the highest CO oxidation activity and readily converted 50% CO at around 133 °C, which is 34 and 94 °C lower than that for CuO/graphene and CuO/active carbon catalysts, respectively. In situ diffused reflectance infrared Fourier transform spectroscopy and density functional theory calculation results proved that the neighboring sp-hybridized C is more favorable to promote the rapid dissociation of carbonate than sp2-hybridized C without overcoming any energy barrier. The gaseous CO directly reacts with the active molecular oxygen and tends to proceed through the E-R mechanism with a relatively low energy barrier (0.20 eV). This work revealed that sp-hybridized C of graphdiyne-based materials could effectively improve the O2 activation efficiency, which could facilitate the low-temperature oxidation processes.

Promotion effect of Au single-atom support graphene for CO oxidation

CO oxidation is a vital catalytic reaction for environmental purification, facing challenges due to the catalysts applied to oxidize CO are mainly rare and expensive noble catalysts. Since the high atomic availability, catalytic efficiency, and selectivity of single-atom catalysis, it has been widely studied and proven to be brilliant in CO oxidation. Au single-atom catalysts are regarded as excellent single-atom catalysts in oxidizing CO, whose progress is limited by the indistinct understanding of the reaction mechanism and role of the active atom. Hence, DFT calculation was used to investigate CO oxidation processes, active mechanisms, and the role of Au single-atom. Graphene involving prominent physical and chemical properties was selected as a model supporter. The single-atom support graphene materials exhibit better CO oxidation activities than pristine graphene, among which CO oxidation property on Au/GP is the highest with a 0.38 eV rate-determining barrier following ER mechanism. The outstanding performances including excellent electronic structures, adsorption properties, and strong activation of intermediate products contribute to the high CO oxidation activity of Au/GP, and the Au single-atom is the active center. Our work provides a novel guide for single-atom catalytic CO oxidation, accelerating the development of single-atom catalysis.

CeO2/CuO/3DOM SiO2 catalysts with very high efficiency and stability for CO oxidation

0.5CeO2/0.25CuO/3DOM SiO2 show very high CO oxidation activity up to 100% at 160 °C and excellent stability up to 12 h in the range 160 °C–240 °C, thanks to the increased active oxygen sites created by the synergistic effect between Cu2+ and Ce3+.

Pd/Ni-metal-organic framework-derived porous carbon nanosheets for efficient CO oxidation over a wide pH range.

Metal nanocrystal ornamented metal-organic frameworks (MOFs) are of particular interest in multidisciplinary applications; however, their electrocatalytic CO oxidation performance over wide pH ranges is not yet reported. Herein, Ni-MOF-derived hierarchical porous carbon nanosheets (Ni-MOF/PC) with abundant Ni-N x sites decorated with Pd nanocrystals (Pd/Ni-MOF/PC) were synthesized by microwave-irradiation (MW-I) followed by annealing at 900 °C and subsequent etching of Ni-MOF/C prior to Pd deposition. The fabrication mechanism comprises the generation of self-reduced reducing gases from triethylamine during the annealing and selective chemical etching of Ni, thereby facilitating the reduction of Ni-anchored MOF and Pd nanocrystal deposition with the aid of ethylene glycol and MW-I to yield Pd/Ni-N x enriched MOF/PC. The synthetic strategies endear the Pd/Ni-MOF/PC with unique physicochemical merits: abundant defects, interconnected pores, high electrical conductivity, high surface area, Ni-deficient but more active sites for Pd/Ni-N x in porous carbon nanosheets, and synergism. These merits endowed the CO oxidation activity and stability on Pd/Ni-MOF/PC substantially than those of Pd/Ni-MOF/C and Pd/C catalysts in wide pH conditions (i.e., KOH, HClO4, and NaHCO3). The CO oxidation activity study reveals the utilization of MOF/PC with metal nanocrystals (Pd/Ni) in CO oxidation catalysis.

Preparation of catalyst as Au doped Mn1Co9Ox/ceramic system for total oxidation of CO

In this paper, the Au doped Mn1Co9Ox was investigated for total oxidation of CO. The sol-gel method was applied to prepare this catalyst and some modern analysis methods as XRD, EPR, TPx, SEM were utilized to characterize its properties. The XRD patterns showed only Co3O4 phase without any peaks belonging to Mn or Au. However, the presence of Au and Mn was confirmed by EPR and O2-TPD results. With the aim to further apply catalyst in reality, the Au doped Mn1Co9Ox was deposited on ceramic by sol-gel, wet impregnation. The SEM images displayed the successful coating of active phase on substrate. However, the complete catalyst system didn’t have the high activity in total CO oxidation like the catalyst powder because of large agglomerations on coatings.

Theoretical studies of MXene-supported single-atom catalysts: Os1/Ti2CS2 for low-temperature CO oxidation

We report herein a new sulfur-functionalized MXene Ti2C (Ti2CS2)-supported osmium-metal single-atom catalyst (SAC) Os1/Ti2CS2 with high low-temperature catalytic activity for CO oxidation. Using periodic density functional theory calculations, the most stable SAC, Os1/Ti2CS2, has been screened from a series of group 8–11 transition metal SACs M1/Ti2CS2 (M = Fe, Co, Ni, Cu; Ru, Rh, Pd, Ag; Os, Ir, Pt, Au). The calculations show that it is favorable for O2 and CO to be coadsorbed on the Os1 single atom (SA) of Os1/Ti2CS2 and the adsorption energy of the first O2 molecule is slightly higher than that of CO. Moreover, the termolecular co-adsorption of O2 + 2CO on Os1 SA is also possible, which is favorable for CO oxidation on Os1 SA through a novel three-molecule reaction mechanism. Accordingly, four different catalytic mechanisms, the Langmuir-Hinshelwood (L-H), Eley-Rideal (E-R), termolecular Langmuir-Hinshelwood-A (TLH-A) and termolecular Langmuir-Hinshelwood-B (TLH-B), are systematically studied for CO oxidation by O2 on Os1/Ti2CS2. The theoretical studies indicate that the TLH-B mechanism is the most feasible for CO oxidation with the reaction barrier energy of only 0.74 eV, which is far lower than for L-H, E-R and TLH-A with barrier energies of 1.06, 1.09 and 1.47 eV, respectively. The results provide fundamental understanding to the surface chemistry of MXene and designing new sulfur-functionalized two-dimensional MXene catalytic nanomaterials.