PEPICO analysis of catalytic reactor effluents towards quantitative isomer discrimination: DME conversion over a ZSM-5 zeolite.

The methanol-to-hydrocarbons (MTH) process involves the conversion of methanol, a C1 feedstock that can be produced from green sources, into hydrocarbons using shape-selective microporous acidic catalysts - zeolite and zeotypes. This reaction yields a complex mixture of species, some of which are highly reactive and/or present in several isomeric forms, posing significant challenges for effluent analysis. Conventional gas-phase chromatography (GC) is typically employed for the analysis of reaction products in laboratory flow reactors. However, GC is not suitable for the detection of highly reactive intermediates such as ketene or formaldehyde and is not suitable for kinetic studies under well defined low pressure conditions. Photoelectron-photoion coincidence (PEPICO) spectroscopy has emerged as a powerful analytical tool for unraveling complex compositions of catalytic effluents, but its availability is limited to a handful of facilities worldwide. Herein, PEPICO analysis of catalytic reactor effluents has been implemented at the FinEstBeAMS beamline of MAX IV Laboratory. The conversion of dimethyl ether (DME) on a zeolite catalyst (ZSM-5-MFI27) is used as a prototypical model reaction producing a wide distribution of hydrocarbon products. Since in zeolites methanol is quickly equilibrated with DME, this reaction can be used to probe vast sub-networks of the full MTH process, while eliminating or at least slowing down methanol-induced secondary reactions and catalyst deactivation. Quantitative discrimination of xylene isomers in the effluent stream is achieved by deconvoluting the coincidence photoelectron spectra.

Solar light driven atomic and electronic transformations in a plasmonic Ni@NiO/NiCO3 photocatalyst revealed by ambient pressure X-ray photoelectron spectroscopy.

This work employs ambient pressure X-ray photoelectron spectroscopy (APXPS) to delve into the atomic and electronic transformations of a core-shell Ni@NiO/NiCO3 photocatalyst - a model system for visible light active plasmonic photocatalysts used in water splitting for hydrogen production. This catalyst exhibits reversible structural and electronic changes in response to water vapor and solar simulator light. In this study, APXPS spectra were obtained under a 1 millibar water vapor pressure, employing a solar simulator with an AM 1.5 filter to measure spectral data under visible light illumination. The in situ APXPS spectra indicate that the metallic Ni core absorbs the light, exciting plasmons, and creates hot electrons that are subsequently utilized through hot electron injection in the hydrogen evolution reaction (HER) by NiCO3. Additionally, the data show that NiO undergoes reversible oxidation to NiOOH in the presence of water vapor and light. The present work also investigates the contribution of carbonate and its involvement in the photocatalytic reaction mechanism, shedding light on this seldom-explored aspect of photocatalysis. The APXPS results highlight the photochemical reduction of carbonates into -COOH, contributing to the deactivation of the photocatalyst. This work demonstrates the APXPS efficacy in examining photochemical reactions, charge transfer dynamics and intermediates in potential photocatalysts under near realistic conditions.

Special Issue "Advanced Spectroscopy Techniques in Food Analysis: Qualitative and Quantitative Chemometric Approaches".

The globalization of the food market has created a pressing need for food producers to meet the ever-increasing demands of consumers while ensuring adherence to stringent food safety and quality standards [...].

Photocatalytic setup for in situ and operando ambient-pressure X-ray photoelectron spectroscopy at MAX IV Laboratory.

The Ambient-Pressure X-ray Photoelectron Spectroscopy (APXPS) endstation at the SPECIES beamline at MAX IV Laboratory has been improved. The latest upgrades help in performing photo-assisted experiments under operando conditions in the mbar pressure range using gas and vapour mixtures whilst also reducing beam damage to the sample caused by X-ray irradiation. This article reports on endstation upgrades for APXPS and examples of scientific cases of in situ photocatalysis, photoreduction and photo-assisted atomic layer deposition (photo-ALD).

Performance and characterization of the FinEstBeAMS beamline at the MAX IV Laboratory.

FinEstBeAMS (Finnish-Estonian Beamline for Atmospheric and Materials Sciences) is a multidisciplinary beamline constructed at the 1.5 GeV storage ring of the MAX IV synchrotron facility in Lund, Sweden. The beamline covers an extremely wide photon energy range, 4.5-1300 eV, by utilizing a single elliptically polarizing undulator as a radiation source and a single grazing-incidence plane grating monochromator to disperse the radiation. At photon energies below 70 eV the beamline operation relies on the use of optical and thin-film filters to remove higher-order components from the monochromated radiation. This paper discusses the performance of the beamline, examining such characteristics as the quality of the gratings, photon energy calibration, photon energy resolution, available photon flux, polarization quality and focal spot size.

Synchronizing gas injections and time-resolved data acquisition for perturbation-enhanced APXPS experiments.

An experimental approach is described in which well-defined perturbations of the gas feed into an Ambient Pressure X-ray Photoelectron Spectroscopy (APXPS) cell are fully synchronized with the time-resolved x-ray photoelectron spectroscopy data acquisition. These experiments unlock new possibilities for investigating the properties of materials and chemical reactions mediated by their surfaces, such as those in heterogeneous catalysis, surface science, and coating/deposition applications. Implementation of this approach, which is termed perturbation-enhanced APXPS, at the SPECIES beamline of MAX IV Laboratory is discussed along with several experimental examples including individual pulses of N2 gas over a Au foil, a multi-pulse titration of oxygen vacancies in a pre-reduced TiO2 single crystal with O2 gas, and a sequence of alternating precursor pulses for atomic layer deposition of TiO2 on a silicon wafer substrate.

Upgrade of the SPECIES beamline at the MAX IV Laboratory.

The SPECIES beamline has been transferred to the new 1.5 GeV storage ring at the MAX IV Laboratory. Several improvements have been made to the beamline and its endstations during the transfer. Together the Ambient Pressure X-ray Photoelectron Spectroscopy and Resonant Inelastic X-ray Scattering endstations are capable of conducting photoelectron spectroscopy in elevated pressure regimes with enhanced time-resolution and flux and X-ray scattering experiments with improved resolution and flux. Both endstations offer a unique capability for experiments at low photon energies in the vacuum ultraviolet and soft X-ray range. In this paper, the upgrades on the endstations and current performance of the beamline are reported.

Understanding the mechanical limitations of the performance of soft X-ray monochromators at MAX IV laboratory.

MAX IV is a fourth-generation, or diffraction-limited, synchrotron light source with a number of state-of-the-art beamlines. The performance of a beamline is, to a high degree, set by the energy resolution it can achieve, which in turn is governed to a large extent by the monochromator. During the design phase of a monochromator, the mechanical requirements must be fully understood and met with margin. During commissioning, the performance must be verified and optimized. In this paper, six soft X-ray monochromators at MAX IV beamlines (Bloch, Veritas, HIPPIE, SPECIES, FinEstBeAMS and SoftiMAX) are examined with a focus on their resolving power, energy range and the time required to change measurement range, as those parameters are dependent on each other. The monochromators have a modern commercial design, planned and developed in close collaboration with the vendors. This paper aims to present the current status of the commissioning at MAX IV with emphasis on elucidating the mechanical limitations on the performance of the monochromators. It contains analysis of the outcome and our approach to achieve fast and high-resolution monochromators.

Probing a battery electrolyte drop with ambient pressure photoelectron spectroscopy.

Operando ambient pressure photoelectron spectroscopy in realistic battery environments is a key development towards probing the functionality of the electrode/electrolyte interface in lithium-ion batteries that is not possible with conventional photoelectron spectroscopy. Here, we present the ambient pressure photoelectron spectroscopy characterization of a model electrolyte based on 1M bis(trifluoromethane)sulfonimide lithium salt in propylene carbonate. For the first time, we show ambient pressure photoelectron spectroscopy data of propylene carbonate in the liquid phase by using solvent vapor as the stabilizing environment. This enables us to separate effects from salt and solvent, and to characterize changes in electrolyte composition as a function of probing depth. While the bulk electrolyte meets the expected composition, clear accumulation of ionic species is found at the electrolyte surface. Our results show that it is possible to measure directly complex liquids such as battery electrolytes, which is an important accomplishment towards true operando studies.

Self-cleaning and surface chemical reactions during hafnium dioxide atomic layer deposition on indium arsenide.

Atomic layer deposition (ALD) enables the ultrathin high-quality oxide layers that are central to all modern metal-oxide-semiconductor circuits. Crucial to achieving superior device performance are the chemical reactions during the first deposition cycle, which could ultimately result in atomic-scale perfection of the semiconductor-oxide interface. Here, we directly observe the chemical reactions at the surface during the first cycle of hafnium dioxide deposition on indium arsenide under realistic synthesis conditions using photoelectron spectroscopy. We find that the widely used ligand exchange model of the ALD process for the removal of native oxide on the semiconductor and the simultaneous formation of the first hafnium dioxide layer must be significantly revised. Our study provides substantial evidence that the efficiency of the self-cleaning process and the quality of the resulting semiconductor-oxide interface can be controlled by the molecular adsorption process of the ALD precursors, rather than the subsequent oxide formation.

Exciting H2 Molecules for Graphene Functionalization.

Hydrogen functionalization of graphene by exposure to vibrationally excited H2 molecules is investigated by combined scanning tunneling microscopy, high-resolution electron energy loss spectroscopy, X-ray photoelectron spectroscopy measurements, and density functional theory calculations. The measurements reveal that vibrationally excited H2 molecules dissociatively adsorb on graphene on Ir(111) resulting in nanopatterned hydrogen functionalization structures. Calculations demonstrate that the presence of the Ir surface below the graphene lowers the H2 dissociative adsorption barrier and allows for the adsorption reaction at energies well below the dissociation threshold of the H-H bond. The first reacting H2 molecule must contain considerable vibrational energy to overcome the dissociative adsorption barrier. However, this initial adsorption further activates the surface resulting in reduced barriers for dissociative adsorption of subsequent H2 molecules. This enables functionalization by H2 molecules with lower vibrational energy, yielding an avalanche effect for the hydrogenation reaction. These results provide an example of a catalytically active graphene-coated surface and additionally set the stage for a re-interpretation of previous experimental work involving elevated H2 background gas pressures in the presence of hot filaments.

The SPECIES beamline at the MAX IV Laboratory: a facility for soft X-ray RIXS and APXPS.

SPECIES is an undulator-based soft X-ray beamline that replaced the old I511 beamline at the MAX II storage ring. SPECIES is aimed at high-resolution ambient-pressure X-ray photoelectron spectroscopy (APXPS), near-edge X-ray absorption fine-structure (NEXAFS), X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS) experiments. The beamline has two branches that use a common elliptically polarizing undulator and monochromator. The beam is switched between the two branches by changing the focusing optics after the monochromator. Both branches have separate exit slits, refocusing optics and dedicated permanent endstations. This allows very fast switching between two types of experiments and offers a unique combination of the surface-sensitive XPS and bulk-sensitive RIXS techniques both in UHV and at elevated ambient-pressure conditions on a single beamline. Another unique property of the beamline is that it reaches energies down to approximately 27 eV, which is not obtainable on other current APXPS beamlines. This allows, for instance, valence band studies under ambient-pressure conditions. In this article the main properties and performance of the beamline are presented, together with selected showcase experiments performed on the new setup.