A near-ambient pressure flow reactor coupled with polarization-modulation infrared reflection absorption spectroscopy for operando studies of heterogeneous catalytic reactions over model catalysts.

The model catalyst approach is often used for fundamental investigations of complex heterogeneous catalysis, in which operando characterizations are critical. A flow reactor is usually adopted for gas-solid heterogeneous catalytic reactions. Herein, we report a home-designed near-ambient pressure (NAP) flow reactor coupled with polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) and an online quadrupole mass spectrometer for operando studies of heterogeneous catalytic reactions over model catalysts. A unique gas supply system is designed and manufactured to enable a stable gas inlet to the NAP flow reactor at pressures up to ∼100 mbar. An ultrahigh vacuum chamber equipped with the facilities for x-ray photoelectron spectroscopy, low-energy electron diffraction, thermal desorption spectroscopy, E-beam evaporation source, and ion sputtering gun is connected to the NAP flow reactor via a gate valve for preparations and routine characterizations of model catalysts. The functions of the system are demonstrated by in situ PM-IRAS characterization of CO adsorption on Pt(111) and operando characterizations of CO oxidation on Pt(111) under NAP conditions.

Oxidative Coupling of Methanol with Molecularly Adsorbed Oxygen on Au Surface to Methyl Formate.

Supported Au catalysts efficiently catalyze the oxidative coupling of methanol with O2 to methyl formate, in which the atomic O species (O(a)) formed via O2 dissociation on the Au surface has been considered as the active oxygen species. Herein we report for the first time that the oxidative coupling of methanol can occur facilely with molecularly adsorbed O2 species (O2(a)) on a Au(997) surface at temperatures as low as around 125 K, while that with O(a) occurs at around 175 K. Both experimental and theoretical calculation results demonstrate a novel reaction mechanism of oxidative coupling of CH3OH with O2(a) via a dioxymethylene (H2COO) intermediate, resulting in the production of both HCOOCH3 and HCOOCH3. These results reveal the unique reactivity of molecularly adsorbed O2 species on Au surfaces for low-temperature oxidation reactions.

Self-Anticoking of a Cobalt Surface by Subsurface Oxygen in the Fischer-Tropsch Synthesis.

Understanding the fundamental processes taking place on Co surfaces during the Fischer-Tropsch (FT) synthesis is of great interest and importance. We herein report a self-anticoking mechanism of a cobalt surface by subsurface oxygen. The active carbidic carbon species for FT synthesis tends to transform into the inactive graphitic carbon species on clean Co(0001) and poisons the Co surface. Subsurface atomic oxygen on Co(0001) can stabilize the active carbidic carbon species and quench the transformation process. These results reveal, to the best of our knowledge, for the first time the reactivity of various surface species on Co surfaces that dynamically maintain a delicate balance to enhance the long-term stability of Co catalysts during FT synthesis.

Surface reaction network of CO oxidation on CeO2/Au(110) inverse model catalysts.

CeO2/Au(110) inverse model catalysts were prepared and their activity toward the adsorption and co-adsorption of O2, CO, CO2 and water was studied by means of X-ray photoelectron spectroscopy, low energy electron diffraction, thermal desorption spectra and temperature-programmed reaction spectra. The Au surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs CO, CO2 and water, and the polycrystalline CeO2 surface of CeO2/Au(110) inverse model catalysts molecularly adsorbs O2, and molecularly and reactively adsorbs CO, CO2 and water. By controllably preparing co-adsorbed surface species on CeO2/Au(110) inverse model catalysts, we successfully identified various surface reaction pathways of CO oxidation to produce CO2 with different barriers both on the CeO2 surface and at the Au-CeO2 interface, including CO oxidation by various oxygen species, and water/hydroxyl group-involved CO oxidation. These results establish a surface reaction network of CO oxidation catalyzed by Au/CeO2 catalysts, greatly advancing the fundamental understandings of catalytic CO oxidation reactions.

Methanol Conversion into Dimethyl Ether on the Anatase TiO2(001) Surface.

Exploring reactions of methanol on TiO2 surfaces is of great importance in both C1 chemistry and photocatalysis. Reported herein is a combined experimental and theoretical calculation study of methanol adsorption and reaction on a mineral anatase TiO2(001)-(1×4) surface. The methanol-to-dimethyl ether (DME) reaction was unambiguously identified to occur by the dehydration coupling of methoxy species at the fourfold-coordinated Ti(4+) sites (Ti(4c)), and for the first time confirms the predicted higher reactivity of this facet compared to other reported TiO2 facets. Surface chemistry of methanol on the anatase TiO2(001)-(1×4) surface is seldom affected by co-chemisorbed water. These results not only greatly deepen the fundamental understanding of elementary surface reactions of methanol on TiO2 surfaces but also show that TiO2 with a high density of Ti(4c) sites is a potentially active and selective catalyst for the important methanol-to-DME reaction.

Hydrogen spillover enhanced hydroxyl formation and catalytic activity toward CO oxidation at the metal/oxide interface.

H2-promoted catalytic activity of oxide-supported metal catalysts in low-temperature CO oxidation is of great interest but its origin remains unknown. Employing an FeO(111)/Pt(111) inverse model catalyst, we herewith report direct experimental evidence for the spillover of H(a) adatoms on the Pt surface formed by H2 dissociation to the Pt-FeO interface to form hydroxyl groups that facilely oxidize CO(a) on the neighboring Pt surface to produce CO2. Hydroxyl groups and coadsorbed water play a crucial role in the occurrence of hydrogen spillover. These results unambiguously identify the occurrence of hydrogen spillover from the metal surface to the noble metal/metal oxide interface and the resultant enhanced catalytic activity of the metal/oxide interface in low-temperature CO oxidation, which provides a molecular-level understanding of both H2-promoted catalytic activity of metal/oxide ensembles in low-temperature CO oxidation and hydrogen spillover.

Active hydrogen species on TiO2 for photocatalytic H2 production.

Photocatalytic H2 production over TiO2 has attracted tremendous attention and achieved great progress, but the active hydrogen species is still unknown. Employing a rutile TiO2(110) surface as a model catalyst we report here for the first time the direct observation of photocatalytic H2 production under ultrahigh vacuum conditions during UV-light irradiation at 115 K and the identification of negatively-charged hydride-type H-Ti species as the corresponding photoactive surface species by means of thermal desorption spectroscopy, photon-stimulated desorption spectroscopy, X-ray photoelectron spectroscopy and DFT calculations. The formation and stability of H-Ti species are closely related to available surplus electrons on the rutile TiO2(110) surface that can be created by the formation of surface BBO vacancies or by the formation of surface hydroxyls via the adsorption of atomic H or molecular H2 on O sites. The photocatalytic H2 production from H-Ti species is hole-mediated and co-existing water exerts a negative effect on this process.

Reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts revealed by an FeO(111)/Pt(111) inverse model catalyst.

We have employed XPS and TDS to study the adsorption and surface reactions of H2O, CO and HCOOH on an FeO(111)/Pt(111) inverse model catalyst. The FeO(111)-Pt(111) interface of the FeO(111)/Pt(111) inverse model catalyst exposes coordination-unsaturated Fe(II) cations (Fe(II)CUS) and the Fe(II)CUS cations are capable of modifying the reactivity of neighbouring Pt sites. Water facilely dissociates on the Fe(II)CUS cations at the FeO(111)-Pt(111) interface to form hydroxyls that react to form both water and H2 upon heating. Hydroxyls on the Fe(II)CUS cations can react with CO(a) on the neighbouring Pt(111) sites to produce CO2 at low temperatures. Hydroxyls act as the co-catalyst in the CO oxidation by hydroxyls to CO2 (PROX reaction), while they act as one of the reactants in the CO oxidation by hydroxyls to CO2 and H2 (WGS reaction), and the recombinative reaction of hydroxyls to produce H2 is the rate-limiting step in the WGS reaction. A comparison of reaction behaviors between the interfacial CO(a) + OH reaction and the formate decomposition reaction suggest that formate is the likely surface intermediate of the CO(a) + OH reaction. These results provide some solid experimental evidence for the associative reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts.

Photocatalytic cross-coupling of methanol and formaldehyde on a rutile TiO2(110) surface.

The photocatalytic oxidation of methanol on a rutile TiO2(110) surface was studied by means of thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). The combined TDS and XPS results unambiguously identify methyl formate as the product in addition to formaldehyde. By monitoring the evolution of various surface species during the photocatalytic oxidation of methanol on TiO2(110), XPS results give direct spectroscopic evidence for the formation of methyl formate as the product of photocatalytic cross-coupling of chemisorbed formaldehyde with chemisorbed methoxy species and clearly demonstrate that the photocatalytic dissociation of chemisorbed methanol to methoxy species occurs and contributes to the photocatalytic oxidation of methanol. These results not only greatly broaden and deepen the fundamental understanding of photochemistry of methanol on the TiO2 surface but also demonstrate a novel green and benign photocatalytic route for the synthesis of esters directly from alcohols or from alcohols and aldehydes.