Defect-Engineered LaFeO3 Stabilizing Oxidized Pt Single-Atom Sites 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.

Propane Dehydrogenation on Single-Site [PtZn4] Intermetallic Catalysts

Single atom catalysts (SACs) are highly desirable for the effort to maximize the efficiency of metal atom use. However, the synthesis of SACs is a major challenge that largely depends on finding an appropriate supporting substrate to achieve a well-defined and highly dispersed single atom. This work demonstrates that, based on the density functional theory (DFT) calculation, graphyne is a good substrate for single Fe atom catalysts. The Fe atom can be tightly embedded in a graphyne sheet with a high binding energy of ∼4.99 eV and a high diffusion energy barrier of ∼1.0 eV. The graphyne-supported Fe (Fe-graphyne) SAC shows high catalytic activity towards CO oxidation, which is often regarded as a prototype reaction for designing atomic-scale catalysts. We studied the adsorption characteristics of CO and O2 on Fe-graphyne SACs, and simulated the reaction mechanism of CO oxidation involving Fe-graphyne. The simulation results indicate that O2 binding on Fe-graphyne is much stronger than that of CO, and the adsorbed O2 prior to occupy the Fe atoms as the co-existence of O2 and CO. The reaction of CO oxidation by adsorbed O2 on Fe-graphyne SACs favors to proceed via the Eley-Rideal (ER) mechanism with the energy barrier of as low as ∼0.21 eV in the rate-limiting step. Calculation of the electronic density of states (DOS) of each reaction step demonstrates that the strong interaction of the O2 and Fe adatom promotes the CO oxidation on Fe-graphyne SACs. The results presented here suggest that graphyne could provide a unique platform to synthesize SACs, and the Fe-graphyne SACs could find potential use in solving the growing environmental problems caused by CO emission from automobiles and industrial processes, in removing CO contamination from vehicle exhaust and in fuel cells.

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.

Copper(II) oxide nanopowders exhibit a high catalytic activity in CO oxidation at low temperatures. The combination of in situ XPS, XRD, and HRTEM methods was applied to investigate initial steps of CuO nanoparticles reduction, to identify oxygen and copper species and to revealed structural features in the dependence on reducing power of reaction medium. At the oxygen deficient surface of CuO nanopowders the metastable Cu4O3 oxide was formed under the mild reducing conditions −10–5 mbar CO or CO + O2 mixture with oxygen excess. Destruction of Cu4O3 structures in strong reducing medium (P(CO) ≥ 10–2 mbar) or under UHV conditions resulted in the formation of Cu2O which was epitaxially bounded with initial CuO particle. The reversible bulk reduction of CuO nanopowder to Cu2O at temperatures ∼150 °C can be explained by effortless propagation of Cu2O∥CuO epitaxial front inside the nanoparticle. The model of the surface restructuring along the {−111}CuO → {202}Cu4O3 → {111}Cu2O planes under the reduction of CuO nanopowders is proposed. The initial surface of CuO nanopowders is probably distorted and resembles Cu4O3-like structures that facilitates the CuOx ↔ Cu4O3 transition in mild reducing conditions. Such restructuring results in a unique electronic Cu4O3 structure with high oxygen deficiency and low-valence Cu1+ sites stimulating the formation of highly reactive CO and O2 adsorbed species. It was shown that the most active oxygen species on the surface of CuOx is stabilized as O–, which was previously reported in papers by Roberts and Madix in their study of the copper–oxygen systems.

Synthesis of nanosized Ce0.85M0.1Ru0.05O2−δ (M = Si, Fe) solid solution exhibiting high CO oxidation and water gas shift activity

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.

Structure dependence and reaction mechanism of CO oxidation: A model study on macroporous CeO2 and CeO2-ZrO2 catalysts

Oxidation of CO over Ru containing perovskite type oxides

Facile synthesis of multi-shelled MnO2–Co3O4 hollow spheres with superior catalytic activity for CO oxidation

Ceria-terbia solid solution nanobelts were prepared by an electrochemical route and tested as catalysts of high activity for CO oxidation.

Origins of catalysis for CO oxidation on porous Ag fabricated by leaching of intermetallic compound Mg3Ag

Au/Ce1−xZrxO2 as effective catalysts for low-temperature CO oxidation

Three different CeO2 sphere nanomaterials (hollow sphere, flowerlike sphere, spherical cluster) were controllably synthesized by carbon sphere template method, hydrothermal and solvothermal method respectively. Then 2.5 wt% Au was doped on the supports by the deposition precipitation method and Au/CeO2 catalysts with three different morphologies were obtained. Composition, morphology and structure of these catalysts were characterized by the techniques of XRD, Raman, TPR, SEM and TEM, and the activity for CO oxidation of the catalysts was investigated. The catalytic test results indicated that the addition of Au could remarkably improve catalytic performance on CO oxidation. The activities of the three catalysts differ largely, the flowerlike Au/CeO2 catalyst had the highest activity for CO oxidation and its T100% was 29°C. The mechanism for the different activity of the catalysts was investigated. H2-TPR result indicated flowerlike had a more intensive peak at 125°C than others and it implied more reducible Au species in this case, that plays a vital role in the CO oxidation.

Pd supported on SnO2–MnOx–CeO2 catalysts for low temperature CO oxidation