Near-ambient Pressure Research Articles

Work function and electrochemistry of ZnO (wurtzite) single crystals (F-1:L07)

The work functions of two polar surfaces of ZnO (wurtzite), i.e., O-(000–1) and Zn-(0001) are determined by photoelectron spectroscopy in ultrahigh vacuum or in the presence of oxygen or water vapor at near-ambient pressures, and by Kelvin probe in air. The work functions were also determined by Mott-Schottky analysis in aqueous or aprotic (acetonitrile) electrolyte solutions. The values obtained by different techniques and in different environments are much less scattered compared to the fluctuations, reported for TiO2 (anatase or rutile). The Zn-(0001) surface has a smaller work function for all the solid/vacuum and solid/gas interfaces, and also in the acetonitrile electrolyte solution. Solely at the aqueous electrochemical interface, the difference is small or even opposite. We propose a hypothesis that the dissociative water adsorption on the O-(000–1) is responsible for this irregular downshift of the work function in aqueous medium.

Toward Water-Resistant, Tunable Perovskite Absorbers Using Peptide Hydrogel Additives.

In recent years, hydrogels have been demonstrated as simple and cheap additives to improve the optical properties and material stability of organometal halide perovskites (OHPs), with most research centered on the use of hydrophilic, petrochemical-derived polymers. Here, we investigate the role of a peptide hydrogel in passivating defect sites and improving the stability of methylammonium lead iodide (MAPI, CH3NH3PbI3) using closely controlled, in situ X-ray photoelectron spectroscopy (XPS) techniques under realistic pressures. Optical measurements reveal that a reduction in the density of defect sites is achieved by incorporating peptide into the precursor solution during the conventional one-step MAPI fabrication approach. Increasing the concentration of peptide is shown to reduce the MAPI crystallite size, attributed to a reduction in hydrogel pore size, and a concomitant increase in the optical bandgap is shown to be consistent with that expected due to quantum size effects. Encapsulation of MAPI crystallites is further evidenced by XPS quantification, which demonstrates that the surface stoichiometry differs little from the expected nominal values for a homogeneously mixed system. In situ XPS demonstrates that thermally induced degradation in a vacuum is reduced by the inclusion of peptide, and near-ambient pressure XPS (NAP-XPS) reveals that this enhancement is partially retained at 9 mbar water vapor pressure, with a reduced loss of methylammonium (MA+) from the surface following heating achieved using 3 wt % peptide loading. A maximum power conversion efficiency (PCE) of 16.6% was achieved with a peptide loading of 3 wt %, compared with 15.9% from a 0 wt % device, the former maintaining 81% of its best efficiency over 480 h storage at 35% relative humidity (RH), compared with 48% maintained by a 0 wt % device.

Atomic-Scale Friction and Adhesion at Ambient Pressure.

In this Perspective, we present the recent advancement and the prospects of atomic-scale friction and adhesion measurements across the pressure gap between ultrahigh vacuum and ambient pressure environments using variable-pressure atomic force microscopy (VP-AFM). We introduce the VP-AFM that enables nanotribological studies under various gas conditions with partial pressure ranging from UHV (1.0 × 10-10 mbar) to 1 bar. We highlight the frictional behaviors of ultrananocrystalline diamond surface in oxygen and water gas environments, as well as the chemical states probed with near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). The atomic scale degradation processes of MA(CH3NH3)PbBr3, which is an organic-inorganic hybrid perovskite (OHP) investigated with VP-AFM are introduced. Finally, we discuss the potential works on catalytic model systems including bimetallic Pt3Ni(111) and TiO2(110) and the future perspective of nanotribology under ambient conditions.

Electronic Structure Sensitivity to Hydration in Smectite Clays Unveiled by Near-Ambient Pressure X-ray Photoelectron Spectroscopy

Electronic Structure Sensitivity to Hydration in Smectite Clays Unveiled by Near-Ambient Pressure X-ray Photoelectron Spectroscopy

Exploring the dynamic evolution of lattice oxygen on exsolved-Mn2O3@SmMn2O5 interfaces for NO Oxidation

Lattice oxygen in metal oxides plays an important role in the reaction of diesel oxidation catalysts, but the atomic-level understanding of structural evolution during the catalytic process remains elusive. Here, we develop a Mn2O3/SmMn2O5 catalyst using a non-stoichiometric exsolution method to explore the roles of lattice oxygen in NO oxidation. The enhanced covalency of Mn–O bond and increased electron density at Mn3+ sites, induced by the interface between exsolved Mn2O3 and mullite, lead to the formation of highly active lattice oxygen adjacent to Mn3+ sites. Near-ambient pressure X-ray photoelectron and absorption spectroscopies show that the activated lattice oxygen enables reversible changes in Mn valence states and Mn-O bond covalency during redox cycles, reducing energy barriers for NO oxidation and promoting NO2 desorption via the cooperative Mars-van Krevelen mechanism. Therefore, the Mn2O3/SmMn2O5 exhibits higher NO oxidation activity and better resistance to hydrothermal aging compared to a commercial Pt/Al2O3 catalyst.

Near-Ambient Pressure Oxidation of Silver in the Presence of Steps: Electrophilic Oxygen and Sulfur Impurities.

The oxidation of Ag crystal surfaces has recently triggered strong controversies around the presence of sulfur impurities that may catalyze reactions, such as the alkene epoxidations, especially the ethylene epoxidation. A fundamental challenge to achieve a clear understanding is the variety of procedures and setups involved as well as the particular history of each sample. Especially, for the often-used X-ray photoemission technique, product detection, or photoemission peak position overlap are problematic. Here we investigate the oxidation of the Ag(111) surface and its vicinal crystal planes simultaneously, using a curved crystal sample and in situ X-ray photoelectron spectroscopy at 1 mbar O2 near-ambient pressure conditions to further investigate surface species. The curved geometry allows a straightforward comparative analysis of the surface oxidation kinetics at different crystal facets, so as to precisely correlate the evolution of different oxygen species, namely nucleophilic and electrophilic oxygen, and the buildup of sulfur as a function of the crystal orientation. We observed that emission from both surface and bulk oxide contributes to the characteristic nucleophilic oxygen core-level peak, which arises during oxygen dosing and rapidly saturates below temperatures of 180 °C. The electrophilic oxygen peak appears later, growing at a slower but constant rate, at the expenses of the surface oxide. Electrophilic oxygen and sulfur core-levels evolve in parallel in all crystal facets, although faster and stronger at vicinal surfaces featuring B-type steps with {111} microfacets. Our study confirms the intimate connection of the electrophilic species with the formation of adsorbed SO4, and points to a higher catalytic activity of B-type stepped silver surfaces for alkene epoxidation or methane to formaldehyde conversion.

Temperature Dependence of SEI Formation and Faradaic Efficiency in Electrochemical Lithium Mediated Nitrogen Reduction to Ammonia

Lithium-mediated nitrogen reduction (Li-N2R) is a promising electrochemical ammonia production alternative to the Haber Bosch process, a process responsible for 1.3% of CO2 emissions yearly.1 While Haber Bosch requires high temperatures and pressures in large centralized facilities, Li-N2R works at near-ambient temperatures and pressures allowing for decentralized production and can be powered by renewable electricity sources. In Li-N2R, Li ions are plated as Li metal on the working electrode, which then reacts with N2 gas to form lithium nitride (Li3N). Lithium nitride reacts with a proton source to form ammonia (NH3) (Figure left).Past research indicates that the solid electrolyte interface (SEI) formed in the electrochemical system has a large impact on the NH3 faradaic efficiency (FE) of the cell.2 Variations in the temperature during cell cycling can influence both the thickness and composition of the SEI. This, in turn, alters the kinetics of species transport to and from the electrode. Consequently, SEIs formed at different temperatures lead to varying proportions of products in the reaction, and are a helpful tool to tune the system towards NH3 selectivity. We elucidate temperature effects on SEI formation and FE for electrolytes with 1M LiBF4 in two common solvents, Tetrahydrofuran (THF) and diglyme (DG), with a 1v% ethanol (EtOH) proton source (Figure right). We also confirm the validity of our results with an Ar control. By dissolving SEI species in a D2O rinsate, we can quantify the composition of the SEI formed at different temperatures using a combination of nuclear magnetic resonance (NMR), inductively coupled plasma mass spectrometry (ICP-MS), and ion chromatography (IC). With our strategy, we correlate SEI composition trends with changes in FE, and provide pathways towards engineering the SEI for enhanced Li-N2R FE to NH3 and improved electrolyzer lifetime. 1J. W. Erisman et al., Nat. Geosci 2008, 1, 636–639 2K. Steinberg et al., Nat. Energy 2022, 8 (2), 138 Figure 1

Exploring the Gas-Sensing Mechanism of a WO3 Nanowires-Based Sensor for Ethanol Detection by Near-Ambient Pressure XPS

The WO3 nanowires (NWs), fabricated on a commercial Al2O3-based sensor platform, underwent near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) analysis during ethanol detection. Our findings revealed challenges that may appear in utilizing NAP-XPS studies for studying a real gas sensor in operando conditions. Through NAP-XPS analysis, we explored the gas-sensing mechanisms of pristine and Pt-decorated WO3 NWs for ethanol sensing at different temperatures, demonstrating a combination of several mechanisms commonly observed in metal-oxide chemiresistors. For ethanol sensing, the primary driving force for the sensor's macroscopic electrical response at low temperatures was the adsorption of ethanol molecules. Conversely, at high temperatures, it involved the adsorption of ethoxy groups along with the reducing effect of ethanol on the WO3 surface. It is shown that the surface oxygen vacancies play a crucial role in the ethanol sensing mechanism of WO3 NWs-based gas sensors. Figure 1

CeO2-Supported Single-Atom Cu Catalysts Modified with Fe for RWGS Reaction: Deciphering the Role of Fe in the Reaction Mechanism by In Situ/Operando Spectroscopic Techniques.

Reverse water-gas shift (RWGS) reaction has attracted much attention as a potential approach for CO2 valorization via the production of synthesis gas, especially over Fe-modified supported Cu catalysts on CeO2. However, most studies have focused solely on investigating the RWGS reaction over catalysts with high Cu and Fe loadings, thus leading to an increase in the complexity of the catalytic system and, hence, preventing the gain of any reliable information about the nature of the active sites and reaction mechanism. In this work, a CeO2-supported single-atom Cu catalyst modified with iron was synthesized and evaluated for the RWGS reaction. The catalytic results reveal a significant synergistic effect between CuCeO2 and Fe, demonstrating an activity up to three times higher than the combined catalytic activities of monometallic catalysts (Fe/CeO2 + CuCeO2) under identical conditions. Various ex situ and in situ/operando techniques are employed to unveil the concealed role of Fe in catalyst activity enhancement. The combined findings from hydrogen temperature-programmed reduction (H2-TPR) and operando electron paramagnetic resonance spectroscopy (EPR) reveal that the added Fe predominantly interacts with Cu-containing surface sites, resulting in the stabilization of higher proportions of Cu single sites. Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando EPR results unveil a synergistic interplay of Fe with Cu-containing sites and CeO x domains, efficiently enhancing both the reoxidation of Cu+ in Cu+-Ov-Ce3+ moieties and the reducibility of Ce4+ in CeO x domains under RWGS conditions. Detailed mechanistic studies reveal that the RWGS reaction predominantly proceeds via the redox mechanism.

Role of Cu Oxide and Cu Adatoms in the Reactivity of CO2 on Cu(110).

We investigate the interaction of CO2 with metallic and oxidized Cu(110) surfaces using a combination of near-ambient pressure scanning tunneling microscopy (NAP-STM) and theoretical calculations. While the Cu(110) and full CuO films are inert, the interface between bare Cu(110) and the CuO film is observed to react instantly with CO2 at a 10 mbar pressure. The reaction is observed to proceed from the interfacial sites of CuO/Cu(110). During reaction with CO2, the CuO/Cu(110) interface releases Cu adatoms which combine with CO3 to produce a variety of added Cu-CO3 structures, whose stability depends on the gas pressure of CO2. A main implication for the reactivity of Cu(110) is that Cu adatoms and highly undercoordinated CuO segments are created on the Cu(110) surface through the interaction with CO2, which may act as reaction-induced active sites. In the case of CO2 hydrogenation to methanol, our theoretical assessment of such sites indicates that their presence may significantly promote CH3OH formation. Our study thus implies that the CuO/Cu(110) interfacial system is highly dynamic in the presence of CO2, and it suggests a possible strong importance of reaction-induced Cu and CuO sites for the surface chemistry of Cu(110) in CO2-related catalysis.

Tuning the Size of TiO2-Supported Co Nanoparticle Fischer-Tropsch Catalysts Using Mn Additions.

Modifying traditional Co/TiO2-based Fischer-Tropsch (FT) catalysts with Mn promoters induces a selectivity shift from long-chain paraffins toward commercially desirable alcohols and olefins. In this work, we use in situ gas cell scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS) elemental mapping, and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) to demonstrate how the elemental dispersion and chemical structure of the as-calcined materials evolve during the H2 activation heat treatment required for industrial CoMn/TiO2 FT catalysts. We find that Mn additions reduce both the mean Co particle diameter and the size distribution but that the Mn remains dispersed on the support after the activation step. Density functional theory calculations show that the slower surface diffusion of Mn is likely due to the lower number of energetically accessible sites for the Mn on the titania support and that favorable Co-Mn interactions likely cause greater dispersion and slower sintering of Co in the Mn-promoted catalyst. These mechanistic insights into how the introduction of Mn tunes the Co nanoparticle size can be applied to inform the design of future-supported nanoparticle catalysts for FT and other heterogeneous catalytic processes.

Dynamic restructuring of nickel sulfides for electrocatalytic hydrogen evolution reaction

Transition metal chalcogenides have been identified as low-cost and efficient electrocatalysts to promote the hydrogen evolution reaction in alkaline media. However, the identification of active sites and the underlying catalytic mechanism remain elusive. In this work, we employ operando X-ray absorption spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy to elucidate that NiS undergoes an in-situ phase transition to an intimately mixed phase of Ni3S2 and NiO, generating highly active synergistic dual sites at the Ni3S2/NiO interface. The interfacial Ni is the active site for water dissociation and OH* adsorption while the interfacial S acts as the active site for H* adsorption and H2 evolution. Accordingly, the in-situ formation of Ni3S2/NiO interfaces enables NiS electrocatalysts to achieve an overpotential of only 95 ± 8 mV at a current density of 10 mA cm−2. Our work highlighted that the chemistry of transition metal chalcogenides is highly dynamic, and a careful control of the working conditions may lead to the in-situ formation of catalytic species that boost their catalytic performance.

An electrochemical flow cell for operando XPS and NEXAFS investigation of solid–liquid interfaces

Suitable reaction cells are critical for operando near ambient pressure (NAP) soft x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) studies. They enable tracking the chemical state and structural properties of catalytically active materials under realistic reaction conditions, and thus allow a better understanding of charge transfer at the liquid–solid interface, activation of reactant molecules, and surface intermediate species. In order to facilitate such studies, we have developed a top-side illuminated operando spectro-electrochemical flow cell for synchrotron-based NAP-XPS/-NEXAFS studies. Our modular design uses a non-metal (PEEK) body, and replaceable membranes which can be either of x-ray transparent silicon nitride (SiN x ) or of water permeable polymer membrane materials (e.g. NafionTM). The design allows rapid sample exchange and simultaneous measurements of total electron yield, Auger electron yield and fluorescence-yield. The developed system is highly modular and can be used in the laboratory or directly at the beamline for operando XPS/ x-ray absorption spectroscopy investigations of surfaces and interfaces. We present examples to demonstrate the capabilities of the flow cell. These include an operando NEXAFS study of the Cu-redox chemistry using a SiN x /Ti-Au/Cu working electrode assembly (WEA) and a NAP-XPS/-NEXAFS study of water adsorption on a NafionTM polymer membrane based WEA (NafionTM/C/IrO x catalyst). More importantly, the spectro-electrochemical flow cell is available for user community of B07 beamlines at Diamond Light Source.

Redox dynamics and surface structures of an active palladium catalyst during methane oxidation

Catalysts based on palladium are among the most effective in the complete oxidation of methane. Despite extensive studies and notable advances, the nature of their catalytically active species and conceivable structural dynamics remains only partially understood. Here, we combine operando transmission electron microscopy (TEM) with near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT) calculations to investigate the active state and catalytic function of Pd nanoparticles (NPs) under methane oxidation conditions. We show that the particle size, phase composition and dynamics respond appreciably to changes in the gas-phase chemical potential. In combination with mass spectrometry (MS) conducted simultaneously with in situ observations, we uncover that the catalytically active state exhibits phase coexistence and oscillatory phase transitions between Pd and PdO. Aided by DFT calculations, we provide a rationale for the observed redox dynamics and demonstrate that the emergence of catalytic activity is related to the dynamic interplay between coexisting phases, with the resulting strained PdO having more favorable energetics for methane oxidation.

Stabilization of High-Pressure Phase of Face-Centered Cubic Lutetium Trihydride at Ambient Conditions.

Superconductivity at room temperature and near-ambient pressures is a highly sought-after phenomenon in physics and materials science. A recent study reported the presence of this phenomenon in N-doped lutetium hydride [Nature 615, 244 (2023)], however, subsequent experimental and theoretical investigations have yielded inconsistent results. This study undertakes a systematic examination of synthesis methods involving high temperatures and pressures, leading to insights into the impact of the reaction path on the products and the construction of a phase diagram for lutetium hydrides. Notably, the high-pressure phase of face-centered cubic LuH3 (fcc-LuH3) is maintained to ambient conditions through a high-temperature and high-pressure method. Based on temperature and anharmonic effects corrections, the lattice dynamic calculations demonstrate the stability of fcc-LuH3 at ambient conditions. However, no superconductivity is observed above 2K in resistance and magnetization measurements in fcc-LuH3 at ambientpressure. This work establishes a comprehensive synthesis approach for lutetium hydrides, thereby enhancing the understanding of the high-temperature and high-pressure method employed in hydrides with superconductivity deeply.

Carbon Nanotubes as a Solid-State Electron Mediator for Visible-Light-Driven Z-Scheme Overall Water Splitting.

So-called Z-scheme systems, which typically comprise an H2 evolution photocatalyst (HEP), an O2 evolution photocatalyst (OEP), and an electron mediator, represent a promising approach to solar hydrogen production via photocatalytic overall water splitting (OWS). The electron mediator transferring photogenerated charges between the HEP and OEP governs the performance of such systems. However, existing electron mediators suffer from low stability, corrosiveness to the photocatalysts, and parasitic light absorption. In the present work, carbon nanotubes (CNTs) were shown to function as an effective solid-state electron mediator in a Z-scheme OWS system. Based on the high stability and good charge transfer characteristics of CNTs, this system exhibited superior OWS performance compared with other systems using more common electron mediators. The as-constructed system evolved stoichiometric amounts of H2 and O2 at near-ambient pressure with a solar-to-hydrogen energy conversion efficiency of 0.15%. The OWS reaction was also promoted in the case that this CNT-based Z-scheme system was immobilized on a substrate. Hence, CNTs are a viable electron mediator material for large-scale Z-scheme OWS systems.

Importance of Metal-Support Interactions for CO2 Hydrogenation: An Operando Near-Ambient Pressure X-ray Photoelectron Spectroscopy Study on Gold-Loaded In2O3 and CeO2 Catalysts.

Metal-support interactions, which are essential for the design of supported metal catalysts, used, e.g., for CO2 activation, are still only partially understood. In this study of gold-loaded In2O3 and CeO2 catalysts during CO2 hydrogenation using near-ambient pressure X-ray photoelectron spectroscopy, supported by near edge X-ray absorption fine structure, we demonstrate that the role of the noble metal strongly depends upon the choice of the support material. Temperature-dependent analyses of X-ray photoelectron spectra under reaction conditions reveal that gold is reduced on CeO2, enabling direct H2 activation, but oxidized on In2O3, leading to decreased activity of Au/In2O3 compared to bare In2O3. At elevated temperatures, the catalytic activity of the In2O3 catalysts strongly increases as a result of facilitated CO2 and (In2O3-based) H2 activation, while the catalytic activity of Au/CeO2 is limited by reoxidation by CO2. Our results underline the importance of operando studies for understanding metal-support interactions to enable a rational support selection in the future.

Low-temperature gas sensing mechanism in β-Ga2O3 nanostructures revealed by near-ambient pressure XPS

Ga2O3 is a promising gas-sensing material that can operate over a wide temperature range. However, despite its relevance for practical applications, there is a lack of understanding regarding its sensing mechanism at temperatures below 800 °C. To reveal the sensing mechanism, GaOOH nanorods were grown on β-Ga2O3 seed layers by chemical bath deposition, then converted to β-Ga2O3 by annealing in the air at 500 °C, and the surface properties were investigated by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) in the presence of oxidizing/reducing gases. Time-stable shifts in the XPS spectra were used to estimate the relative changes in conductivity in compliance with the ionosorption model. Our results indicate that the sensing mechanism at lower temperatures is governed by redox reactions, leading to an increase/decrease in the conductivity for reducing/oxidizing gases. Furthermore, we provide a detailed description of the ethanol-sensing mechanism at different temperatures.

Assessing the feasibility of near-ambient conditions superconductivity in the Lu-N-H system

The report of near-ambient superconductivity in nitrogen-doped lutetium hydrides (Lu-N-H) has generated a great interest. However, conflicting results raised doubts regarding superconductivity. Here, we combine high-throughput crystal structure predictions with a fast predictor of superconducting critical temperature (Tc) based on electron localization function to shed light on the properties of Lu-N-H at 1 GPa. None of the predicted structures supports high-temperature superconductivity and the inclusion of nitrogen in the crystal structure predictions leads to more insulating structures than metallic ones in quantity. Despite the lack of near-ambient superconductivity, we consider alternative metastable templates and study their Tc and dynamical stability including quantum anharmonic effects. Lu4H11N exhibits a Tc of 100 K at only 20 GPa, a large increase compared to 30 K of its parent LuH3. Interestingly, it has a similar X-ray pattern to the experimental one. The LaH10-like LuH10 and CaH6-like LuH6 become high-temperature superconductors at 175 GPa and 100 GPa, with Tc of 286 K and 246 K, respectively. Our findings suggest that high-temperature superconductivity is not possible in stable phases at near-ambient pressure. However, at a slightly enhanced pressure of 20 GPa, high-Tc superconductivity emerges in Lu-H-N, and metastable room-temperature superconducting templates persist at high pressures.

Water-Mediated Charge Transfer and Electron Localization in a Co3Fe2 Cyanide-Bridged Trigonal Bipyramidal Complex.

The effects of temperature and chemical environment on a pentanuclear cyanide-bridged, trigonal bipyramidal molecular paramagnet have been investigated. Using element- and oxidation state-specific near-ambient pressure X-ray photoemission spectroscopy (NAP-XPS) to probe charge transfer and second order, nonlinear vibrational spectroscopy, which is sensitive to symmetry changes based on charge (de)localization coupled with DFT, a detailed picture of environmental effects on charge-transfer-induced spin transitions is presented. The molecular cluster, Co3Fe2(tmphen)6(μ-CN)6(t-CN)6, abbrev. Co3Fe2, shows changes in electronic behavior depending on the chemical environment. NAP-XPS shows that temperature changes induce a metal-to-metal charge transfer (MMCT) in Co3Fe2 between a Co and Fe center, while cycling between ultrahigh vacuum and 2 mbar of water at constant temperature causes oxidation state changes not fully captured by the MMCT picture. Sum frequency generation vibrational spectroscopy (SFG-VS) probes the role of the cyanide ligand, which controls the electron (de)localization via the superexchange coupling. Spectral shifts and intensity changes indicate a change from a charge delocalized, Robin-Day class II/III high spin state to a charge-localized, class I low spin state consistent with DFT. In the presence of a H-bonding solvent, the complex adopts a localized electronic structure, while removal of the solvent delocalizes the charges and drives an MMCT. This change in Robin-Day classification of the complex as a function of chemical environment results in reversible switching of the dipole moment, analogous to molecular multiferroics. These results illustrate the important role of the chemical environment and solvation on underlying charge and spin transitions in this and related complexes.