ABSTRACT
The efficient use of natural gas will require catalysts that can activate the first C-H bond of methane while suppressing complete dehydrogenation and avoiding overoxidation. We report that single iron sites embedded in a silica matrix enable direct, nonoxidative conversion of methane, exclusively to ethylene and aromatics. The reaction is initiated by catalytic generation of methyl radicals, followed by a series of gas-phase reactions. The absence of adjacent iron sites prevents catalytic C-C coupling, further oligomerization, and hence, coke deposition. At 1363 kelvin, methane conversion reached a maximum at 48.1% and ethylene selectivity peaked at 48.4%, whereas the total hydrocarbon selectivity exceeded 99%, representing an atom-economical transformation process of methane. The lattice-confined single iron sites delivered stable performance, with no deactivation observed during a 60-hour test.
ABSTRACT
An undercover agent: graphene has been used as an imaging agent to visualize interfacial reactions under its cover, and exhibits a strong confinement effect on the chemistry of molecules underneath. In a CO atmosphere, CO penetrates into the graphene/Pt(111) interface and reacts with O(2) therein, whereas intercalated CO desorbs from the Pt surface.
ABSTRACT
Intercalation of Pb at graphene/Ru(0001) interfaces has been dynamically observed using in situ low energy electron microscopy and photoemission electron microscopy. A comparative study of Pb intercalation on the submonolayer and complete monolayer graphene surfaces suggest that the Pb intercalation happens through the open edges of graphene islands, starting at around 150 °C. Spatially-resolved low energy electron diffraction measurements reveal that the Pb-intercalated graphene overlayers are quasi-free-standing. The intercalated graphene sheets show lower reactivity to oxidation in O(2).
ABSTRACT
Various well-defined Ni-Pt(111) model catalysts are constructed at atomic-level precision under ultra-high-vacuum conditions and characterized by X-ray photoelectron spectroscopy and scanning tunneling microscopy. Subsequent studies of CO oxidation over the surfaces show that a sandwich surface (NiO(1-x)/Pt/Ni/Pt(111)) consisting of both surface Ni oxide nanoislands and subsurface Ni atoms at a Pt(111) surface presents the highest reactivity. A similar sandwich structure has been obtained in supported Pt-Ni nanoparticles via activation in H(2) at an intermediate temperature and established by techniques including acid leaching, inductively coupled plasma, and X-ray adsorption near-edge structure. Among the supported Pt-Ni catalysts studied, the sandwich bimetallic catalysts demonstrate the highest activity to CO oxidation, where 100% CO conversion occurs near room temperature. Both surface science studies of model catalysts and catalytic reaction experiments on supported catalysts illustrate the synergetic effect of the surface and subsurface Ni species on the CO oxidation, in which the surface Ni oxide nanoislands activate O(2), producing atomic O species, while the subsurface Ni atoms further enhance the elementary reaction of CO oxidation with O.
ABSTRACT
The reactivity of a bulk Ag surface, an Ag monolayer film on Si(111)- 7 × 7 (denoted as the [Formula: see text]-Ag-Si surface), and Si(111)-7 × 7 to CCl(4) was investigated by x-ray photoelectron spectroscopy (XPS) and ultraviolet photoemission electron microscopy (UV-PEEM). In situ UV-PEEM was used to monitor simultaneously the CCl(4) dissociation on different surface domains, including the bulk Ag, [Formula: see text]-Ag-Si, and Si(111). The PEEM results combined with XPS data show that CCl(4) adsorbs dissociatively on bulk Ag(111) and Si(111) but adsorbs molecularly on the [Formula: see text]-Ag-Si surface, and the surface reactivity follows the order of [Formula: see text]-Ag-Si.
ABSTRACT
Various sizes of Ag particles were grown on highly oriented pyrolytic graphite (HOPG) surfaces, which had previously been modified with nanopits to act as anchoring sites. Surface reactions of O2, CHCl3, and CCl4 on the Ag particles and bulk Ag(111) surfaces were studied by X-ray photoelectron spectroscopy (XPS), and it has been shown that size dependence of O2 and CHCl3 reactions on Ag differs from that of CCl4. Weak reactions of O2 and CHCl3 were observed on the bulk Ag(111) surfaces, while strong reactions occur on Ag particles with medium Ag coverage, suggesting that the reactions are controlled by the number of surface defect sites. On the contrary, the dissociation of CCl4 is mainly determined by the exposed Ag facet area, mainly Ag(111) facet, and strong dissociation reaction happens on the bulk Ag(111) surface. The results suggest that the size effects, which are often discussed in heterogeneous catalysis, are strongly dependent on the reaction mechanism.
ABSTRACT
Pb quantum well films with atomic-scale uniformity in thickness over macroscopic areas were prepared on Si(111)-7x7 surfaces. As a probe molecule, O(2) was used to explore the effect of electron confinement in the metal films on the surface reactivity. X-ray photoelectron spectroscopy results showed clear oscillations of oxygen adsorption and Pb oxidation with the thickness of the Pb films. The higher reactivity to O(2) on the films with 23 and 25 ML Pb has been attributed to their highest occupied quantum well states being close to the Fermi level (E(F)) and the high density of the electron states at E(F) (DOS-E(F)), as evidenced by the corresponding ultraviolet photoelectron spectroscopy. A dominant role of DOS-E(F) was suggested to explain the quantum modulation of surface reactivity in metal quantum well films.
ABSTRACT
CO chemisorption on the metallic molybdenum nanoparticles supported on the thin alumina film was investigated by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). A binary compound of molybdenum and CO is found to be formed on the surface upon CO dose, accompanied with a positive binding energy shift of the Mo 3d doublet and a localized Mo 4d valence band. A loose packing of the metallic molybdenum favors the formation of this intermediate Mox(CO)y species. The formation of the Mox(CO)y species implies that the property of the metallic molybdenum nanoparticles on the thin alumina film is much different from that of the bulk molybdenum, indicating a significant nanometer size effect.
ABSTRACT
The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface.