Near-ambient Pressure X-ray Photoelectron Spectroscopy Research Articles

Oxidation of Aqueous H3PO3 on Pt Studied By X-Ray Spectroscopies

High-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) employing a phosphoric acid H3PO4-doped membrane are considered to be promising sustainable electrochemical energy storage. The high-temperature operation has several advantages, such as a higher tolerance to CO poisoning, allowing coupling of HT-PEMFCs with reformers [1-3], as well the possibility for heat and electric energy co-generation [1,2]. However, during operation, phosphorus oxo-acids (e.g.: H3PO3) are generated on the anode. These impurities adsorb on the Pt catalyst [4-6], thus possibly negatively affecting the HT-PEMFCs performance. A detailed understanding of the H3PO3-catalyst (Pt) interaction is hence necessary for further HT-PEMFC optimization. However, besides an investigation of the H3PO3 adsorption behavior on Pt [6,7], literature on the behavior of the H3PO3 in contact with Pt (with/without polarization) is scarce.In this work, the oxidation mechanism of H3PO3 was investigated using a combination of in situ x-ray spectroscopy techniques that directly probe the H3PO3/Pt interface interaction, complemented by ex situ x-ray photoelectron spectroscopy (XPS) and ion-exchange chromatography (IEC). IEC gave insights into the effect of Pt on the stability of deaerated aqueous H3PO3 solutions. XPS was conducted on H3PO3/support structures (including Au and Pt supports) to determine to what extent the support affects the H3PO3 oxidation. Furthermore, in-situ dip and pull near-ambient pressure (NAP-)XPS was conducted to investigate the state of H3PO3 at the H3PO3/Pt interface and in solution bulk. It was observed that at the H3PO3/Pt interface, H3PO3 was chemically oxidized to H3PO4, while in the bulk solution it remains stable, as shown in Figure 1. Moreover, in situ x-ray absorption spectroscopy at the P K-edge was conducted at different concentrations of H3PO3 in aqueous solutions (i.e., different amounts of H2O) in contact with Pt, to determine the role of H2O in the oxidation of H3PO3. A higher degree of oxidation was observed for the less concentrated H3PO3, implying that H2O participates in the oxidation mechanism of H3PO3 to H3PO4.

Tuning Strong Metal–Support Interaction Kinetics on Pt-Loaded TiO2(110) by Choosing the Pressure: A Combined Ultrahigh Vacuum/Near-Ambient Pressure XPS Study

Pt catalyst particles on reducible oxide supports often change their activity significantly at elevated temperatures due to the strong metal-support interaction (SMSI), which induces the formation of an encapsulation layer around the noble metal particles. However, the impact of oxidizing and reducing treatments at elevated pressures on this encapsulation layer remains controversial, partly due to the 'pressure gap' between surface science studies and applied catalysis. In the present work, we employ synchrotron-based near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) to study the effect of O$_2$ and H$_2$ on the SMSI-state of well-defined Pt/TiO$_2$(110) catalysts at pressures of up to 0.1 Torr. By tuning the O$_2$ pressure, we can either selectively oxidize the TiO$_2$ support or both the support and the Pt particles. Catalyzed by metallic Pt, the encapsulating oxide overlayer grows rapidly in 1x10$^{-5}$ Torr O$_2$, but orders of magnitudes less effective at higher O$_2$ pressures, where Pt is in an oxidic state. While the oxidation/reduction of Pt particles is reversible, they remain embedded in the support once encapsulation has occurred.

Interaction of molecular nitrogen with vanadium oxide in the absence and presence of water vapor at room temperature: Near-ambient pressure XPS.

Interactions of N2 at oxide surfaces are important for understanding electrocatalytic nitrogen reduction reaction (NRR) mechanisms. Interactions of N2 at the polycrystalline vanadium oxide/vapor interface were monitored at room temperature and total pressures up to 10-1 Torr using Near-Ambient Pressure X-ray Photoelectron Spectroscopy (NAP-XPS). The oxide film was predominantly V(IV), with V(III) and V(V) components. XPS spectra were acquired in environments of both pure N2 and equal pressures of N2 and H2O vapor. In pure N2, broad, partially resolved N1s features were observed at binding energies of 401.0 and 398.7eV, with a relative intensity of ∼3:1, respectively. These features remained upon subsequent pumpdown to 10-9 Torr. The observed maximum N surface coverage was ∼1.5 × 1013cm-2-a fraction of a monolayer. In the presence of equal pressures of H2O, the adsorbed N intensity at 10-1 Torr is ∼25% of that observed in the absence of H2O. The formation of molecularly adsorbed H2O was also observed. Density functional theory-based calculations suggest favorable absorption energies for N2 bonding to both V(IV) and V(III) cation sites but less so for V(V) sites. Hartree-Fock-based cluster calculations for N2-V end-on adsorption show that experimental XPS doublet features are consistent with the calculated shake-up and normal, final ionic configurations for N2 end-on bonding to V(III) sites but not V(IV) sites. The XPS spectra of vanadium oxide transferred in situ between electrochemical and UHV environments indicate that the oxide surfaces studied here are stable upon exposure to the electrolyte under NRR-relevant conditions.

CO2-Assisted Oxidative Dehydrogenation of Propane over VOx/In2O3 Catalysts: Interplay between Redox Property and Acid–Base Interactions

In this work, a series of VOx-loaded In2O3 catalysts were prepared, and their catalytic performance was evaluated for CO2-assisted oxidative dehydrogenation of propane (CO2-ODHP) and compared with In2O3 alone. The optimal composition is obtained on 3.4V/In2O3 (surface V density of 3.4V nm–2), which exhibited not only a higher C3H6 selectivity than other V/In catalysts and In2O3 under isoconversion conditions but also an improved reaction stability. To elucidate the catalyst structure–activity relationship, the VOx/In2O3 catalysts were characterized by chemisorption [NH3-temperature-programmed desorption (TPD), NH3-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), CO2-TPD, and CO2-DRIFTS], H2-temperature-programmed reduction (TPR), in situ Raman spectroscopy, UV–vis diffuse reflectance spectroscopy, near-ambient pressure X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and further examined using density functional theory. The In–O–V structure and the extent of oligomerization, which play a crucial role in improving selectivity and stability, were identified in the VOx/In2O3 catalysts. In particular, the presence of surface VOx (i) inhibits the deep reduction of In2O3, thereby preserving the activity, (ii) neutralizes the excess basicity on In2O3, thus suppressing propane dry reforming and achieving a higher propylene selectivity, and (iii) introduces additional redox sites that participate in the dehydrogenation reaction by utilizing CO2 as a soft oxidant. The present work provides insights into developing selective, stable, and robust metal-oxide catalysts for CO2-ODHP by controlling the conversion of reagents via desired pathways through the interplay between acid–base interactions and redox properties.

Unraveling Catalytic Reaction Mechanism by In Situ Near Ambient Pressure X-ray Photoelectron Spectroscopy

Probing surface chemistry during reactions closer to realistic conditions is crucial for the understanding of mechanisms in heterogeneous catalysis. Near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is one of the state-of-the-art surface-sensitive techniques used to characterize catalyst surfaces in gas phases. This Perspective begins with a brief overview of the development of the NAP-XPS technique and its representative applications in identifying the active sites at a molecular level. Next, recent in situ NAP-XPS investigations of several model catalysts in the CO2 hydrogenation reaction are mainly discussed. Finally, we highlight the major challenges facing NAP-XPS and future improvements to facilities for probing intermediates with higher resolutions under real ambient pressure reactions in heterogeneous catalysis.

Direct detection of self-reconstruction-accelerated oxygen evolution activity in MoCoNi hydroxides

The exploration of cost-effective oxygen evolution reaction (OER) catalysts is valuable for high-performance water electrolysis in alkaline electrolytes. Surface reconstruction can endow earth-abundant multimetal oxides/hydroxides with noble-metal-comparable OER activity, because their electronic structures can be spontaneously regulated towards favorable adsorption energies of oxygen-containing OER intermediates in electrolysis. However, the direct detection of subtly modified electronic structures is very challenging because of the rather rapid surface-reconstruction process. Herein, Mo-based CoNi hydroxide marked with the most universal surface-reconstructed OER catalyst is selected as a model material for investigating the surface-reconstruction-accelerated OER activity. The surface-reconstructed MoCoNi catalyst exhibits a superior OER activity with a low overpotential (282 mV) at 10 mA/cm2 and a small Tafel slope of 49.3 mV/dec. Moreover, the oxygen-vacancy-rich catalyst shows a commercial RuO2-comparable stability for OER process over 100 h. Thanks to the advantage of vacuum-connected glove box and near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) system, the subtle changes of potential-dependent oxygen vacancies and neighboring metal centers are directly detected by NAP-XPS characterization, which clearly reveals the surface-reconstruction-induced evolution of oxygen vacancies and electronic structure of neighboring metal centers in MoCoNi catalyst. Based on the morphological observation and spectroscopy characterization, the DFT model of self-reconstructed Co-NiOOH catalyst with oxygen vacancy is established, and comprehensive theoretic simulations confirm that the surface-constructed oxygen vacancies benefit the regulation of electronic structure of neighboring metal atoms with favorable binding affinity to OER intermediates.

Introducing Brønsted acid sites to accelerate the bridging-oxygen-assisted deprotonation in acidic water oxidation

Oxygen evolution reaction (OER) consists of four sequential proton-coupled electron transfer steps, which suffer from sluggish kinetics even on state-of-the-art ruthenium dioxide (RuO2) catalysts. Understanding and controlling the proton transfer process could be an effective strategy to improve OER performances. Herein, we present a strategy to accelerate the deprotonation of OER intermediates by introducing strong Brønsted acid sites (e.g. tungsten oxides, WOx) into the RuO2. The Ru-W binary oxide is reported as a stable and active iridium-free acidic OER catalyst that exhibits a low overpotential (235 mV at 10 mA cm−2) and low degradation rate (0.014 mV h−1) over a 550-hour stability test. Electrochemical studies, in-situ near-ambient pressure X-ray photoelectron spectroscopy and density functional theory show that the W-O-Ru Brønsted acid sites are instrumental to facilitate proton transfer from the oxo-intermediate to the neighboring bridging oxygen sites, thus accelerating bridging-oxygen-assisted deprotonation OER steps in acidic electrolytes. The universality of the strategy is demonstrated for other Ru-M binary metal oxides (M = Cr, Mo, Nb, Ta, and Ti).

(Keynote) Mechanistic Understanding of the Activity of Atomically Dispersed Transition Metal-Nitrogen-Carbon Catalysts in Oxygen, Carbon Dioxide or Nitrogen Electro-Reduction

Over the last two decades, platinum group metal-free (PGM-free) catalysts are attracting increasing attention and finding applications in several important process across many electrochemical energy technologies. Among those PGM-free materials, atomically dispersed (AD) transition metal-nitrogen-carbon (M-N-C) catalysts are gaining exceptional popularity as they demonstrate very high (for this class of materials) activity in oxygen reduction reaction (ORR)1 and are the only cathode catalysts suitable for both proton exchange membrane fuel cells (PEMFC) and alkaline, including anion/hydroxyl exchange membrane fuel cells (AFC, AEMFC/HEMFC). Over the last few years, M-N-C catalysts have shown promising activity in carbon dioxide reduction reaction (CO2RR).2 In this case, varying the transition metal in M-N-Cs opens routes for controlling the selectivity towards a list of C1 and C2 products. There are recent reports on catalytic activity of AD M-N-C materials in direct electro-reduction of molecular nitrogen (N2RR) or reactions of reduction of nitrates, nitrites or various nitrogen oxides (NOx). We have systematically investigated all these processes having as a base the M-N-C catalysts synthesized by sacrificial support method (SSM) – a hard template approach with transition metal salt and charge-transfer organic salt (nicarbazin) mixed by ball-milling, pyrolyzed at high temperature in inert atmosphere and then etched in HF after cooling. In most cases a secondary (similar) pyrolysis was performed to refine the material and ensure its AD character.The makeup and structure of the active site/sites of the AD M-N0C electrocatalysts, including geometry (coordination) and chemistry (composition and oxidation state) remain contentious to this day. There is an emerging agreement however, that the transition metal (at least for the 2nd row transitions meals) is immediately associated with (liganded by) the nitrogen functionalities, displayed on the surface if the carbonaceous substrate. It is almost universally accepted that N-coordinated AD transition metal ions, either as in-plane or edge-type defect in “graphene” sheet, are the main/principal active sites. This is often combined with a broadly accepted hypothesis that micro-porous surface area plays a critical role forming edge-type, intercalational active sites while meso-porous interface is most-likely associated with the in-plane, substitutional AD metal sites. Candidate structures participating in reativity towards O2, CO2 or nitrogen species include a list of nitrogen-containg and oxygen-containng moeties in the carbonaceous matrix. The carbon itself displays various degrees of graphitization, depending on the transition metal used in M-N-C synthesis. Additional complexity in this calss of caralysts study comes from the fact that many samples are not strictly AD materials. They often contain incorporated metal nano-particles, corresponding (native) oxides and/or carbides and nitrides (oxocabides and oxonitrides have been observed as well).These “unrefined” M-N-C materials are often used in practice and the corresponding nano-particle components of the de-facto nanocomposites do alter substantially the reactivity and selectivity of the catalysts in all these electro-reduction reactions.This talk discusses the mechanistic aspects of M-N-C catalysts in ORR, CO2RR, N2RR and electroreduction of nitrogen-containing oxo-species, obtained when cross-referencing electrochemical activity results obtained in rotating disk and rotating ring-disk electrodes setting (RDE/RRDE) with those observed in near-ambient pressure X-ray photo-electron spectroscopy (NAP-XPS) and supported by density functional theory calculations of the reagents adsorption on AD transition metal or nitrogen- or oxygen-containing moieties from the carbonaceous matrix of the M-N-Cs. The later are of particular importance as significant reactivity has been observed for most of those processes when metal-free, nitrogen-doped carbon (N-C) catalysts are used.3 We will present a case that outlines the reactivity of M-N-C in those important electro-reduction reactions in terms of (i) role of the AD transition metal, (ii) role of the surface N-groups as co-catalysts/alternative sites (iii) role of surface oxides as co-catalysts or hydrophilic/hydrophobic properties descriptor, the last being also critically dependent on morphology.4

(Invited) Gold Electrodes Emersed from Aqueous Electrolytes: A Kelvin Probe and Infrared Spectroscopy Approach

The study of the electric double layer (solid/liquid interface) is of crucial importance for an in-depth understanding electrochemical processes. However, the electrochemical interface (or interphase) is usually buried under a barrier of bulk water which is blocking direct access for most analytical tools. One way to enable direct access is e.g. the emersed electrode concept. For this, electrodes are emersed under potential control from the electrolyte into an inert atmosphere. It was shown in prior works for emersion into UHV [1] and into humid nitrogen [2] that the electrochemical double layer seems to be kept more or less intact during this process. However, thus an electrochemical double layer is obtained that is vertically confined to just one or two monolayers, depending on the humidity of the environment. The Kelvin probe technique can be employed for measuring the resulting electrode potential of such emersed electrodes [3], often providing a linear correlation between applied potentials during the electrochemical polarization and the potentials determined after emersing the sample from the electrolyte [2]. An open question is the role of the amount of water molecules in the double layer on the electrode potential [1,2]. A powerful technique for the investigation of the structure of the water molecules in the double layer region is infrared spectroscopy. Since infrared spectroscopy techniques (using an ATR set-up) can also be applied for characterization of the electrode immersed bulk electrolyte [4], a direct comparison between these two cases is possible.For this work, NaClO4 and H2SO4 diluted aqueous solutions were used as electrolytes, which both present anions with similar specific adsorption [5]. The Kelvin probe tip was calibrated against an Ag/AgCl/KCl homemade reference electrode [6]. Different atmosphere conditions (relative humidity) were used and their effect on the emersed electrode was investigated by Kelvin probe and IR spectroscopy. Furthermore, studies employing Near Ambient Pressure X-Ray Photoelectron Spectroscopy (NAP-XPS) technique have been conducted in order to detect the presence of anions and cations in the electrochemical double-layer and also for in operando studies with different atmosphere conditions.Literature:[1] H. Neff, R. Kötz, J. Electroanal. Chem. 1983, 151, 305.[2] Z. Samec, B. W. Johnson, K. Doblhofer, Surf. Sci. 1992, 264, 440.[3] M. Rohwerder, F. Turcu, Electrochim. Acta 2007, 53, 290.[4] K. Ataka, T. Yotsuyanagi, M. Osawa, J. Phys. Chem. 1996, 100, 10664.[5] D. D. Bodé Jr., T. N. Andersen, H. Eyring, J. Phys. Chem. 1967, 71, 792.[6] M. Uebel, A. Vimalanandan, A. Laaboudi, S. Evers, M. Stratmann, D. Diesing, M. Rohwerder, Langmuir 2017, 33, 10807.

Interfacial Water in the SARS Spike Protein: Investigating the Interaction with Human ACE2 Receptor and In Vitro Uptake in A549 Cells.

The severity of global pandemic due to severe acute respiratory syndrome coronavirus-2 (SARS–CoV-2) has engaged the researchers and clinicians to find the key features triggering the viral infection to lung cells. By utilizing such crucial information, researchers and scientists try to combat the spread of the virus. Here, in this work, we performed in silico analysis of the protein–protein interactions between the receptor-binding domain (RBD) of the viral spike protein and the human angiotensin-converting enzyme 2 (hACE2) receptor to highlight the key alteration that happened from SARS-CoV to SARS-CoV-2. We analyzed and compared the molecular differences between spike proteins of the two viruses using various computational approaches such as binding affinity calculations, computational alanine, and molecular dynamics simulations. The binding affinity calculations showed that SARS-CoV-2 binds a little more firmly to the hACE2 receptor than SARS-CoV. The major finding obtained from molecular dynamics simulations was that the RBD–ACE2 interface is populated with water molecules and interacts strongly with both RBD and ACE2 interfacial residues during the simulation periods. The water-mediated hydrogen bond by the bridge water molecules is crucial for stabilizing the RBD and ACE2 domains. Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) confirmed the presence of vapor and molecular water phases in the protein–protein interfacial domain, further validating the computationally predicted interfacial water molecules. In addition, we examined the role of interfacial water molecules in virus uptake by lung cell A549 by binding and maintaining the RBD/hACE2 complex at varying temperatures using nanourchins coated with spike proteins as pseudoviruses and fluorescence-activated cell sorting (FACS) as a quantitative approach. The structural and dynamical features presented here may serve as a guide for developing new drug molecules, vaccines, or antibodies to combat the COVID-19 pandemic.

Enhanced dissociation activation of CO2 on the Bi/Cu(1 1 1) interface by the synergistic effect

Thermocatalytic CO2 reduction reaction (CO2RR) is one of the promising strategies to mitigate CO2 emissions. Meanwhile, understanding the reduction mechanism of CO2 on the catalyst surface is imperative for advancing catalyst design and the eventual industrialization under mild conditions. In this work, the catalytic role of bismuth/copper interface towards CO2RR is elaborately investigated via a combination of near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS), ambient-pressure scanning tunneling microscopy (NAP-STM) and density function theory (DFT). It is demonstrated that the initial deposition of Bi on Cu results in the formation of Bi-Cu heterogenous structure, while the interface is buried at the thick coverage. Upon CO2 exposure, Bi is oxidized at interface due to the activation of CO2 on Cu sites and subsequent migration of oxygen to Bi, while Cu+ is induced afterwards in annealing acting as the further dissociation site. Compared with the pure Cu(111), the fraction of oxidation including both lattice and defective oxygen is significantly higher on the Bi/Cu interface, indicating the synergistic effect of Bi-Cu interface in the activation of CO2. Thus, our work clearly reveals the dissociation site evolution of the Bi-Cu bimetallic heterostructure and might promote the design of Cu-based catalysts for advancing thermocatalytic CO2RR.

Observation of Potential-Induced Hydration on the Surface of Ceramic Proton Conductors Using In Situ Near-Ambient Pressure X-ray Photoelectron Spectroscopy.

Interactions of ceramic proton conductors with the environment under operating conditions play an essential role on material properties and device performance. It remains unclear how the chemical environment of material, as modulated by the operating condition, affects the proton conductivity. Combining near-ambient pressure X-ray photoelectron spectroscopy and impedance spectroscopy, we investigate the chemical environment changes of oxygen and the conductivity of BaZr0.9Y0.1O3-δ under operating condition. Changes in O 1s core level spectra indicate that adding water vapor pressure increases both hydroxyl groups and active proton sites at undercoordinated oxygen. Applying external potential further promotes this hydration effect, in particular, by increasing the amount of undercoordinated oxygen. The enhanced hydration is accompanied by improved proton conductivity. This work highlights the effects of undercoordinated oxygen for improving the proton conductivity in ceramics.

Distinct Crystal-Facet-Dependent Behaviors for Single-Atom Palladium-On-Ceria Catalysts: Enhanced Stabilization and Catalytic Properties.

High-performance, fully atomically dispersed single-atom catalysts (SACs) are promising candidates for next-generation industrial catalysts. However, it remains a great challenge to avoid the aggregation of isolated atoms into nanoparticles during the preparation and application of SACs. Here, the evolution of Pd species is investigated on different crystal facets of CeO2 , and vastly different behaviors on the single-atomic dispersion of surface Pd atoms are surprisingly discovered. In situ X-ray photoelectron spectroscopy (XPS), in situ near-ambient-pressure-XPS (NAP-XPS), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and X-ray absorption spectroscopy (XAS) reveal that, in a reducing atmosphere, more oxygen vacancies are generated on the (100) facet of CeO2 , and Pd atoms can be trapped and thus feature atomic dispersion; by contrast, on the CeO2 (111) facet, Pd atoms will readily aggregate into clusters (Pdn ). Furthermore, Pd1 /CeO2 (100) gives a high selectivity of 90.3% for the catalytic N-alkylation reaction, which is 2.8 times higher than that for Pdn /CeO2 (111). This direct evidence demonstrates the crucial role of crystal-facet effects in the preparation of metal-atom-on-metal-oxide SACs. This work thus opens an avenue for the rational design and targeted synthesis of ultrastable and sinter-resistant SACs.

In situ NAP-XPS study of CO2 and H2O adsorption on cerium oxide thin films

Insights of CO2 and H2O activation on cerium oxide based catalysts are of great interest to many important catalytic processes, which are widely studied in model systems under ultrahigh vacuum conditions. Here, in situ near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) was used to study CO2 and H2O adsorption on fully oxidized CeO2 and partially reduced CeO2−x surfaces. It is found that CO2 only weakly interacts with the stoichiometric CeO2 but strongly adsorbs on partially reduced CeO2−x surfaces with surface carbonate formation. H2O dissociatively adsorbs reversely on the CeO2 surface with H2O exposure pressure above 1 × 10−3 mbar, while H2O strongly dissociates on the partially reduced CeO2−x surfaces. The surface dissociated OH and H species are stable on the CeO2−x surface up to 600 K. Both CO2 and H2O adsorption cause clear reoxidation of partially reduced CeO2−x. This study provides new insights into CO2 and H2O interaction with cerium oxide surfaces at near ambient pressure conditions.

Synergistic Effects of a CeO2/SmMn2O5-H Diesel Oxidation Catalyst Induced by Acid-Selective Dissolution Drive the Catalytic Oxidation Reaction.

A diesel oxidation catalyst (DOC) is installed upstream of an exhaust after-treatment line to remove CO and hydrocarbons and generate NO2. The catalyst should possess both good oxidation ability and thermal stability because it sits after the engine. We present a novel high-performance DOC with high steam resistance and thermal stability. A selective dissolution method is adopted to modify the surface physicochemical environment of CeO2-SmMn2O5. The X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, Raman, electron paramagnetic resonance, hydrogen temperature-programmed reduction, and temperature-programmed desorption results reveal that surface Sm cations are partially removed with the exposure of more Mn4+ and Ce3+ cations and the presence of active surface oxygen species. This mechanism benefits the oxygen transformation from Ce to Mn and promotes the Ce3+ + Mn4+ ↔ Ce4+ + Mn3+ redox cycle according to the in situ near-ambient pressure X-ray photoelectron spectroscopy and in situ diffuse reflectance infrared Fourier transformation spectroscopy results. Under laboratory-simulated diesel combustion conditions, the catalyst demonstrates excellent low-temperature oxidation catalytic activity (CO and C3H6 conversion: T100 = 250 °C) compared to a Pt-based catalyst (CO and C3H6 conversion: T100 = 310 °C) with a WHSV of 120,000 mL g-1 h-1. Specifically, NO conversion reaches 68% when the temperature is approximately 300 °C.

Inorganic‐Organic Hybrid Anion Conducting Membranes Based on Ammonium‐Functionalized Polyethylene Pyrrole‐Polyethylene Ketone Copolymer

AbstractNew inorganic‐organic hybrid anion exchange membranes are produced after incorporation of tantalum oxide into trimethylammonium‐functionalized polyethylene pyrrole‐co‐polyethylene ketone (functionalized polyketone, FPK), obtained by the chemical modification of a polyketone polymer. The influence of tantalum oxide fillers on the properties of the synthesized membranes is investigated. The interaction between inorganic fillers and the polymer chains is studied using Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR‐FTIR). The thermal analysis of the FPK membranes reveals they are thermally stable at up to 250°C. However, the incorporation of the inorganic fillers reduces the thermal stability. Modulated Differential Scanning Calorimetry (MDSC) results indicate that the inclusion of inorganic fillers leads to an increase in crystallinity. This study reports that the properties of the bulk polymer can be tuned by controlling the degree of functionalization and content of inorganic fillers, as confirmed by Near Ambient Pressure X‐Ray Photoelectron Spectroscopy (NAP‐XPS) studies. Finally, Broadband Electrical Spectroscopy (BES) studies demonstrate that the hybrid membranes are characterized by several polarization phenomena contributing to the overall ion conductivity of the material, which at RT is of 1.46 and 1.61 mS cm−1 for the FPK cast membrane and the hybrid membrane with 5.0 wt.% of Ta2O5 filler, respectively.

The effect of lanthanum in Cu/La(-Zr)-Si oxide catalysts for aqueous ethanol conversion into 1,3-butadiene

This paper presents the results of an investigation of three (Cu/La-Si and Cu/Zr-Si) and four (Cu/La-Zr-Si) component oxide systems in aqueous ethanol conversion into 1,3-butadiene, with special accent to the effect of lanthanum in the catalyst composition. The catalysts were characterized by HRTEM, SEM, DR UV−vis, in situ near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), FTIR with pyridine, and TPD-CO2. The high (≥65%) 1,3-butadiene selectivity is achieved during the conversion of both rectified and aqueous ethanol over the studied catalysts. Catalyst activity of the four-component oxide systems depends on an introduction order of the components, which determines acid-base characteristics of the surface. A modification of the Cu/Zr-Si catalyst with lanthanum increases their activity in aqueous ethanol conversion into 1,3-butadiene. The positive effect of lanthanum addition into Cu/Zr-Si catalyst can be explained by the formation of lanthanum-containing base sites like [La–Ö–Si] and [La–Ö–H] being tolerant to the action of water. The differences in the interaction of reaction intermediates with surface Zr- and La-containing sites are found out by C 1 s NAP-XPS measurements, and the effect of H2O on adsorption of carbon coke, ethoxy species and acetaldehyde over the catalyst surface is shown.

Copper promotion of chromium-doped iron oxide water-gas shift catalysts under industrially relevant conditions

Copper promotion of chromium-doped iron oxide prepared via co-precipitation for high-temperature water–gas shift (WGS) catalysis is investigated. Low-temperature Mössbauer spectra demonstrate that copper doping delays hematite (α-Fe2O3) formation in the fresh catalyst, favoring the formation of small crystallites of ferrihydrite (Fe5HO8∙4 H2O). Catalysts are treated under industrial WGS conditions at 360 °C (activity evaluation) and 450 °C (ageing) at 2 and 25 bar. Mössbauer spectra show that chromium is incorporated in octahedral sites of the active magnetite (Fe3O4) phase, resulting in a partially oxidized structure. Copper doping did not affect the bulk magnetite structure of the activated catalyst, which points to the presence of a separate copper phase. Near-ambient pressure XPS shows that copper is in the metallic state. XPS of discharged catalysts evidenced that reaction at elevated pressure resulted in the surface reduction of Fe3+ to Fe2+. Copper promotion enhances CO conversion under high-temperature WGS conditions.

Near-Ambient Pressure XPS and MS Study of CO Oxidation over Model Pd-Au/HOPG Catalysts: The Effect of the Metal Ratio.

In this study, the dependence of the catalytic activity of highly oriented pyrolytic graphite (HOPG)-supported bimetallic Pd-Au catalysts towards the CO oxidation based on the Pd/Au atomic ratio was investigated. The activities of two model catalysts differing from each other in the initial Pd/Au atomic ratios appeared as distinctly different in terms of their ignition temperatures. More specifically, the PdAu-2 sample with a lower Pd/Au surface ratio (~0.75) was already active at temperatures less than 150 °C, while the PdAu-1 sample with a higher Pd/Au surface ratio (~1.0) became active only at temperatures above 200 °C. NAP XPS revealed that the exposure of the catalysts to a reaction mixture at RT induces the palladium surface segregation accompanied by an enrichment of the near-surface regions of the two-component Pd-Au alloy nanoparticles with Pd due to adsorption of CO on palladium atoms. The segregation extent depends on the initial Pd/Au surface ratio. The difference in activity between these two catalysts is determined by the presence or higher concentration of specific active Pd sites on the surface of bimetallic particles, i.e., by the ensemble effect. Upon cooling the sample down to room temperature, the reverse redistribution of the atomic composition within near-surface regions occurs, which switches the catalyst back into inactive state. This observation strongly suggests that the optimum active sites emerge under reaction conditions exclusively, involving both high temperature and a reactive atmosphere.

Surface Reconstruction of a Mullite-Type Catalyst via Selective Dissolution for NO Oxidation

We present a facile selective dissolution method for the surface modification of SmMn2O5 mullite (SMO) to increase the exposed sites for NO oxidation on the premise of excellent thermal stability. Surface Sm cations are partially removed during the treatment (SMO-H), leading to the exposure of B-site cations with higher electronegativity and oxygen vacancies. Under laboratory-simulated diesel combustion conditions, the SMO-H exhibits higher NO oxidation activity than the SMO and is comparable to that of the Pt/Al catalyst under a gas hourly space velocity (GHSV) of 120 000 mL g–1 h–1. In addition, the SMO-H possesses good thermal and steam stability during a 50 h test at 300 °C. X-ray absorption spectroscopy (XAS) and electron paramagnetic resonance (EPR) spectroscopy results reveal that the SMO-H presents more Mn4+O6 octahedral groups and oxygen vacancies than the SMO. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), and density functional theory (DFT) calculations show that the valence of surface Mn decreased after NO capture up to 300 °C and fulfilled the adsorption procedure as nitrite and/or nitrate species when O2 is involved in the flue gas. The results indicate that Mn-terminated surface rather than Sm-terminated one is the major adsorption site for NO.