Bifunctionality of Re Supported on TiO2 in Driving Methanol Formation in Low-Temperature CO2 Hydrogenation.

Low temperature and high pressure are thermodynamically more favorable conditions to achieve high conversion and high methanol selectivity in CO2 hydrogenation. However, low-temperature activity is generally very poor due to the sluggish kinetics, and thus, designing highly selective catalysts active below 200 °C is a great challenge in CO2-to-methanol conversion. Recently, Re/TiO2 has been reported as a promising catalyst. We show that Re/TiO2 is indeed more active in continuous and high-pressure (56 and 331 bar) operations at 125-200 °C compared to an industrial Cu/ZnO/Al2O3 catalyst, which suffers from the formation of methyl formate and its decomposition to carbon monoxide. At lower temperatures, precise understanding and control over the active surface intermediates are crucial to boosting conversion kinetics. This work aims at elucidating the nature of active sites and active species by means of in situ/operando X-ray absorption spectroscopy, Raman spectroscopy, ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Transient operando DRIFTS studies uncover the activation of CO2 to form active formate intermediates leading to methanol formation and also active rhenium carbonyl intermediates leading to methane over cationic Re single atoms characterized by rhenium tricarbonyl complexes. The transient techniques enable us to differentiate the active species from the spectator one on TiO2 support, such as less reactive formate originating from spillover and methoxy from methanol adsorption. The AP-XPS supports the fact that metallic Re species act as H2 activators, leading to H-spillover and importantly to hydrogenation of the active formate intermediate present over cationic Re species. The origin of the unique reactivity of Re/TiO2 was suggested as the coexistence of cationic highly dispersed Re including single atoms, driving the formation of monodentate formate, and metallic Re clusters in the vicinity, activating the hydrogenation of the formate to methanol.

Origin of the High Selectivity of the Pt-Rh Thin-Film H2 Gas Sensor Studied by Operando Ambient-Pressure X-ray Photoelectron Spectroscopy at Working Conditions.

The Pt-Rh thin-film sensors exhibit excellent sensitivity and selectivity for H2 gas detection. Here, we studied the mechanism of highly selective detection of H2 by the Pt-Rh thin-film sensors with ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) measurements at working conditions, which were paralleled with electric resistivity measurements. The elemental composition and chemical state of surface Pt and Rh drastically change depending on the background gas environments, which directly link to the sensor response. It is revealed that surface segregated Pt atoms accelerate dissociative adsorption of H2, resulting in a reduction of the sensor surface and then a decrease of electric resistivity of the film, whereas a thin oxidized Rh layer blocks dissociation of the other reducing agent, that is, NH3. This is supported from the adsorption energetics obtained by the density functional theory (DFT) calculations.

A newly designed compact CEY-XAFS cell in the soft X-ray region and its application to surface XAFS measurements under ambient-pressure conditions without photoinduced side effects.

We report a newly designed compact cell to measure XAFS spectra with the conversion electron yield (CEY) method in the soft X-ray region under ambient-pressure gas conditions. Secondary electrons generated from the gas and sample by collision of X-ray-absorption-induced Auger electrons are collected by a positively biased collector electrode to obtain XAFS spectra. It was confirmed that this cell is applicable to soft X-ray surface XAFS measurements for different types of materials such as insulating organic materials and metal oxides under 1 bar gas conditions. During the measurements, photoinduced side effects were observed; i.e. photoinduced degradation of organic materials and photoinduced reduction/oxidation of metal oxides. We found that these photoinduced side effects can be sufficiently suppressed by controlling the measuring conditions. The presented measuring approach will enable surface XAFS spectra to be obtained in the soft X-ray region for various types of functional materials under ambient-pressure working conditions.

Initial oxidation of GaAs(100) under near-realistic environments revealed by in situ AP-XPS.

In situ monitoring of initial oxidation of GaAs surfaces was performed under (near-) realistic oxidizing environments, using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). The surface chemical states drastically change with time. The oxidation process at the sub-nano-meter-scale exhibits a significantly small activation energy, which can be regarded as a quasi-barrier-less oxidation.

Orientation-Dependent Hindrance to the Oxidation of Pd-Au Alloy Surfaces.

Oxidation of monometallic Pd and bimetallic Pd3Au alloy surfaces are observed by in situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at an elevated pressure (100 mTorr O2 ambient). It is directly evidenced that the alloying with Au hinders the surface oxidation of Pd3Au surfaces compared with monometallic Pd surfaces. Remarkably, the oxidation behavior is clearly different between Pd3Au(111) and (100) surfaces. The (100) surface has a relatively Pd-rich surface composition, and the surface oxide layer is formed, whereas the (111) surface has a Au-rich composition, and the surface oxidation is quite limited. A combined approach of experimental and theoretical techniques reveals that Pd/Au surface composition and atomic arrangement are key factors determining the oxidation behavior.

In situ AP-XPS analysis of a Pt thin-film sensor for highly sensitive H2 detection.

In situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) combined with resistivity measurement was performed for a Pt thin-film H2 gas sensor. We experimentally demonstrate that the chemical state of the Pt surface changes under working conditions, and it directly links to the sensing performance. Moreover, the operating principle is discussed at the atomic scale.

Element selective oxidation on Rh-Pd bimetallic alloy surfaces.

The interactions between oxygen and Rh-Pd bimetallic alloy surfaces were investigated using surface sensitive experimental techniques and density functional theory calculations. The alloy surfaces were oxidized under 10-5 Torr and 100 mTorr oxygen upon heating above 250 °C. A thin Rh oxide layer was preferentially formed on a Rh1Pd9(100) surface, while a thin Pd oxide layer was formed on a Rh1Pd9(111) surface, though the Rh oxide is thermodynamically more stable irrespective of the surface orientation. Chemical analyses revealed that the initial Rh fraction for the (111) surface was significantly lower than that for the (100) surface, which suggests that the oxidized element on the surface is kinetically selected depending on the near surface initial composition.

Catalytic CO oxidation over Pd70Au30(111) alloy surfaces: spectroscopic evidence for Pd ensemble dependent activity.

Catalytic CO oxidation over Pd(111) and Pd70Au30(111) surfaces was investigated by in situ spectroscopic observations to understand the alloying effect. The reaction behaviour on Pd70Au30(111) is greatly different from that on Pd(111). Pd monomer and dimer ensembles can act as active centers, whereas triangular-shaped trimers and larger ensembles are inactive.

In-situ observations of catalytic surface reactions with soft x-rays under working conditions.

Catalytic chemical reactions proceeding on solid surfaces are an important topic in fundamental science and industrial technologies such as energy conversion, pollution control and chemical synthesis. Complete understanding of the heterogeneous catalysis and improving its efficiency to an ultimate level are the eventual goals for many surface scientists. Soft x-ray is one of the prime probes to observe electronic and structural information of the target materials. Most studies in surface science using soft x-rays have been performed under ultra-high vacuum conditions due to the technical limitation, though the practical catalytic reactions proceed under ambient pressure conditions. However, recent developments of soft x-ray based techniques operating under ambient pressure conditions have opened a door to the in-situ observation of materials under realistic environments. The near-ambient-pressure x-ray photoelectron spectroscopy (NAP-XPS) using synchrotron radiation enables us to observe the chemical states of surfaces of condensed matters under the presence of gas(es) at elevated pressures, which has been hardly conducted with the conventional XPS technique. Furthermore, not only the NAP-XPS but also ambient-pressure compatible soft x-ray core-level spectroscopies, such as near-edge absorption fine structure (NEXAFS) and x-ray emission spectroscopy (XES), have been significantly contributing to the in-situ observations. In this review, first we introduce recent developments of in-situ observations using soft x-ray techniques and current status. Then we present recent new findings on catalytically active surfaces using soft x-ray techniques, particularly focusing on the NAP-XPS technique. Finally we give a perspective on the future direction of this emerging technique.

A high-pressure-induced dense CO overlayer on a Pt(111) surface: a chemical analysis using in situ near ambient pressure XPS.

We investigated the high-density CO adsorption phase formed on a Pt(111) surface when exposed to CO gas of pressure ranging from UHV to 100 mTorr using near-ambient-pressure (NAP)-XPS. Combined results from the NAP-XPS measurements and DFT calculations reveal the adsorption structure of CO molecules in the dense CO overlayer, which is stable under realistic conditions.

Active Surface Oxygen for Catalytic CO Oxidation on Pd(100) Proceeding under Near Ambient Pressure Conditions.

Catalytic CO oxidation reaction on a Pd(100) single-crystal surface under several hundred mTorr pressure conditions has been studied by ambient pressure X-ray photoelectron spectroscopy and mass spectroscopy. In-situ observation of the reaction reveals that two reaction pathways switch over alternatively depending on the surface temperature. At lower temperatures, the Pd(100) surface is covered by CO molecules and the CO2 formation rate is low, indicating CO poisoning. At higher temperatures above 190 °C, an O-Pd-O trilayer surface oxide phase is formed on the surface and the CO2 formation rate drastically increases. It is likely that the enhanced rate of CO2 formation is associated with an active oxygen species that is located at the surface of the trilayer oxide.