Correction: Time-, space- and energy-resolved in situ characterization of catalysts by X-ray absorption spectroscopy.

Correction for 'Time-, space- and energy-resolved in situ characterization of catalysts by X-ray absorption spectroscopy' by Stefan Peters et al., Chem. Commun., 2023, 59, 12120-12123, https://doi.org/10.1039/D3CC03277A.

Heterogenized Molecular Electrocatalyst Based on a Hydroxo-Bridged Binuclear Copper(II) Phenanthroline Compound for Selective Reduction of CO2 to Ethylene.

Molecular copper catalysts have emerged as promising candidates for the electrochemical reduction of CO2 . Notable features of such systems include the ability of Cu to generate C2+  products and the well-defined active sites that allow for targeted structural tuning. However, the frequently observed in situ formation of Cu nanoclusters has undermined the advantages of the molecular frameworks. It is therefore desirable to develop Cu-based catalysts that retain their molecular structures during electrolysis. In this context, a heterogenized binuclear hydroxo-bridged phenanthroline Cu(II) compound with a short Cu···Cu distance is reported as a simple yet efficient catalyst for electrogeneration of ethylene and other C2 products. In an aqueous electrolyte, the catalyst demonstrates remarkable performance, with excellent Faradaic efficiency for C2 products (62%) and minimal H2 evolution (8%). Furthermore, it exhibits high stability, manifested by no observable degradation during 15 h of continuous electrolysis. The preservation of the atomic distribution of the active sites throughout electrolysis is substantiated through comprehensive characterizations, including X-ray photoelectron and absorption spectroscopy, scanning and transmission electron microscopy, UV-vis spectroscopy, as well as control experiments. These findings establish a solid foundation for further investigations into targeted structural tuning, opening new avenues for enhancing the catalytic performance of Cu-based molecular electrocatalysts.

Experiment and Theory in Concert To Unravel the Remarkable Electronic Properties of Na-Doped Eu11Zn4Sn2As12: A Layered Zintl Phase.

Low-dimensional materials have unique optical, electronic, mechanical, and chemical properties that make them desirable for a wide range of applications. Nano-scaling materials to confine transport in at least one direction is a common method of designing materials with low-dimensional electronic structures. However, bulk materials give rise to low-dimensional electronic structures when bonding is highly anisotropic. Layered Zintl phases are excellent candidates for investigation due to their directional bonding, structural variety, and tunability. However, the complexity of the structure and composition of many layered Zintl phases poses a challenge for producing phase-pure bulk samples to characterize. Eu11Zn4Sn2As12 is a layered Zintl phase of significant complexity that is of interest for its magnetic, electronic, and thermoelectric properties. To prepare phase-pure Eu11-xNaxZn4Sn2As12, a binary EuAs phase was employed as a precursor, along with NaH. Experimental measurements reveal low thermal conductivity and a high Seebeck coefficient, while theoretical electronic structure calculations reveal a transition from a 3D to 2D electronic structure with increasing carrier concentration. Simulated thermoelectric properties also indicate anisotropic transport, and thermoelectric property measurements confirm the nonparabolicity of the relevant bands near the Fermi energy. Thermoelectric efficiency is known to improve as the dimensionality of the electronic structure is decreased, making this a promising material for further optimization and opening the door to further exploitation of layered Zintl phases with low-dimensional electronic structures for thermoelectric applications.

Low-Temperature Hydrogenation of CO2 to Methanol in Water on ZnO-Supported CuAu Nanoalloys.

Optimizing processes and materials for the valorization of CO2 to hydrogen carriers or platform chemicals is a key step for mitigating global warming and for the sustainable use of renewables. We report here on the hydrogenation of CO2 in water on ZnO-supported CuAu nanoalloys, based on ≤7 mol % Au. Cux Auy /ZnO catalysts were characterized using 197 Au Mössbauer, in situ X-ray absorption (Au LIII - and Cu K-edges), and ambient pressure X-ray photoelectron (APXP) spectroscopic methods together with X-ray diffraction and high-resolution electron microscopy. At 200 °C, the conversion of CO2 showed a significant increase by 34 times (from 0.1 to 3.4 %) upon increasing Cu93 Au7 loading from 1 to 10 wt %, while maintaining methanol selectivity at 100 %. Limited CO selectivity (4-6 %) was observed upon increasing temperature up to 240 °C but associated with a ≈3-fold increase in CO2 conversion. Based on APXPS during CO2 hydrogenation in an H2 O-rich mixture, Cu segregates preferentially to the surface in a mainly metallic state, while slightly charged Au submerges deeper into the subsurface region. These results and detailed structural analyses are topics of the present contribution.

Time-, space- and energy-resolved in situ characterization of catalysts by X-ray absorption spectroscopy.

A setup for dispersive X-ray absorption spectroscopy (XAS) with spatial, temporal and energy resolution is presented. Through investigation of a Mo/HZSM-5 catalyst during the dehydroaromatization of methane we observed a reduction gradient along the packed bed. Our new method represents an unprecedented addition to the analytical toolbox for in situ characterizations.

Structural Evolution of Iron-Loaded Metal-Organic Framework Catalysts for Continuous Gas-Phase Oxidation of Methane to Methanol.

Catalytic partial oxidation of methane presents a promising route to convert the abundant but environmentally undesired methane gas to liquid methanol with applications as an energy carrier and a platform chemical. However, an outstanding challenge for this process remains in developing a catalyst that can oxidize methane selectively to methanol with good activity under continuous flow conditions in the gas phase using O2 as an oxidant. Here, we report a Fe catalyst supported by a metal-organic framework (MOF), Fe/UiO-66, for the selective and on-stream partial oxidation of methane to methanol. Kinetic studies indicate the continuous production of methanol at a superior reaction rate of 5.9 × 10-2 µmolMeOH gFe-1 s-1 at 180 °C and high selectivity toward methanol, with the catalytic turnover verified by transient methane isotopic measurements. Through an array of spectroscopic characterizations, electron-deficient Fe species rendered by the MOF support is identified as the probable active site for the reaction.

Unveiling the CO Oxidation Mechanism over a Molecularly Defined Copper Single-Atom Catalyst Supported on a Metal-Organic Framework.

Elucidating the reaction mechanism in heterogeneous catalysis is critically important for catalyst development, yet remains challenging because of the often unclear nature of the active sites. Using a molecularly defined copper single-atom catalyst supported by a UiO-66 metal-organic framework (Cu/UiO-66) allows a detailed mechanistic elucidation of the CO oxidation reaction. Based on a combination of in situ/operando spectroscopies, kinetic measurements including kinetic isotope effects, and density-functional-theory-based calculations, we identified the active site, reaction intermediates, and transition states of the dominant reaction cycle as well as the changes in oxidation/spin state during reaction. The reaction involves the continuous reactive dissociation of adsorbed O2 , by reaction of O2,ad with COad , leading to the formation of an O atom connecting the Cu center with a neighboring Zr4+ ion as the rate limiting step. This is removed in a second activated step.

Reversible Growth of Gold Nanoparticles in the Low-Temperature Water-Gas Shift Reaction.

Supported gold nanoparticles are widely studied catalysts and are among the most active known for the low-temperature water-gas shift reaction, which is essential in fuel and energy applications, but their practical application has been limited by their poor thermal stability. The catalysts deactivate on-stream via the growth of small Au nanoparticles. Using operando X-ray absorption and in situ scanning transmission electron microscopy, we report direct evidence that this process can be reversed by carrying out a facile oxidative treatment, which redisperses the gold nanoparticles and restores catalytic activity. The use of in situ methods reveals the complex dynamics of supported gold nanoparticles under reaction conditions and demonstrates that gold catalysts can be easily regenerated, expanding their scope for practical application.

Oxygen vacancies in Ru/TiO2 - drivers of low-temperature CO2 methanation assessed by multimodal operando spectroscopy.

Hydrogenation of CO2 is very attractive for transforming this greenhouse gas into valuable high energy density compounds. In this work, we developed a highly active and stable Ru/TiO2 catalyst for CO2 methanation prepared by a solgel method that revealed much higher activity in methanation of CO2 (ca. 4-14 times higher turnover frequencies at 140-210°C) than state-of-the-art Ru/TiO2 catalysts and a control sample prepared by wetness impregnation. This is attributed to a high concentration of O-vacancies, inherent to the solgel methodology, which play a dual role for 1) activation of CO2 and 2) transfer of electrons to interfacial Ru sites as evident from operando DRIFTS and in situ EPR investigations. These results suggest that charge transfer from O-vacancies to interfacial Ru sites and subsequent electron donation from filled metal d-orbitals to antibonding orbitals of adsorbed CO are decisive factors in boosting the CO2 methanation activity.

Fundamental Aspects of Ceria Supported Au Catalysts Probed by In Situ/Operando Spectroscopy and TAP Reactor Studies.

The discovery of the activity of dispersed gold nanoparticles three decades ago paved the way for a new era in catalysis. The unusual behavior of these catalysts sparked many questions about their working mechanism. In particular, Au/CeO2 proved to be an efficient catalyst in several reactions such as CO oxidation, water gas shift, and CO2 reduction. Here, by employing findings from operando X-ray absorption spectroscopy at the near and extended Au and Ce LIII energy edges, we focus on the fundamental aspects of highly active Au/CeO2 catalysts, mainly in the CO oxidation for understanding their complex structure-reactivity relationship. These results were combined with findings from in situ diffuse reflectance FTIR and Raman spectroscopy, highlighting the changes of adlayer and ceria defects. For a comprehensive understanding, the spectroscopic findings will be supplemented by results of the dynamics of O2 activation obtained from Temporal Analysis of Products (TAP). Merging these results illuminates the complex relationship among the oxidation state, size of the Au nanoparticles, the redox properties of CeO2 support, and the dynamics of O2 activation.

Raising the COx Methanation Activity of a Ru/γ-Al2 O3 Catalyst by Activated Modification of Metal-Support Interactions.

Ru/Al2 O3 is a highly stable, but less active catalyst for methanation reactions. Herein we report an effective approach to significantly improve its performance in the methanation of CO2 /H2 mixtures. Highly active and stable Ru/γ-Al2 O3 catalysts were prepared by high-temperature treatment in the reductive reaction gas. Operando/in situ spectroscopy and STEM imaging reveals that the strongly improved activity, by factors of 5 and 14 for CO and CO2 methanation, is accompanied by a flattening of the Ru nanoparticles and the formation of highly basic hydroxylated alumina sites. We propose a modification of the metal-support interactions (MSIs) as the origin of the increased activity, caused by modification of the Al2 O3 surface in the reductive atmosphere and an increased thermal mobility of the Ru nanoparticles, allowing their transfer to modified surface sites.

Influence of CO on the Activation, O-Vacancy Formation, and Performance of Au/ZnO Catalysts in CO2 Hydrogenation to Methanol.

The impact of CO on the activation and reaction characteristics of Au/ZnO catalysts in methanol synthesis from a CO2/H2 mixture was studied by kinetic, near ambient pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy at the O K-edge, together with in situ Foureir transform infrared measurements. Transient measurements under up to industrial reaction conditions (50 bar, 240 °C) show a pronounced transient increase of the activity for methanol formation from CO2/H2 after exposure to a CO/H2 reaction gas mixture, while the steady-state activity is similar to that observed directly after oxidative pretreatment. For the reaction in CO/H2, the much longer activation phase is accompanied by formation of CO2 due to reaction of CO with the ZnO catalyst support. This leads to O-vacancy formation on the support at an extent significantly higher than in CO2/H2. The consequences of these findings on the mechanistic understanding of methanol formation from CO2/H2 on Au/ZnO and for ZnO-supported catalysts in general are discussed.

Morphology-Engineered Highly Active and Stable Ru/TiO2 Catalysts for Selective CO Methanation.

Ru/TiO2 catalysts exhibit an exceptionally high activity in the selective methanation of CO in CO2 - and H2 -rich reformates, but suffer from continuous deactivation during reaction. This limitation can be overcome through the fabrication of highly active and non-deactivating Ru/TiO2 catalysts by engineering the morphology of the TiO2 support. Using anatase TiO2 nanocrystals with mainly {001}, {100}, or {101} facets exposed, we show that after an initial activation period Ru/TiO2 -{100} and Ru/TiO2 -{101} are very stable, while Ru/TiO2 -{001} deactivates continuously. Employing different operando/in situ spectroscopies and ex situ characterizations, we show that differences in the catalytic stability are related to differences in the metal-support interactions (MSIs). The stronger MSIs on the defect-rich TiO2 -{100} and TiO2 -{101} supports stabilize flat Ru nanoparticles, while on TiO2 -{001} hemispherical particles develop. The former MSIs also lead to electronic modifications of Ru surface atoms, reflected by the stronger bonding of adsorbed CO on those catalysts than on Ru/TiO2 -{001}.

Synthesis, structural and morphological characterizations of nano-Ru-based perovskites/RGO composites.

Highly-dispersed Ru-based perovskites supported on reduced graphene oxide (A-RG) nanocomposites are prepared using different A-metal salts (Sr(NO3)2, Ba(NO3)2 and Ca(NO3)2). The procedure is based on a redox reaction between the metal precursors and graphene oxide (GO) using two different routes of reaction initiation: through thermal heating or by microwave-assisted heating. The resulting nanocomposites do not require further calcination, making this method less energy-demanding. In addition, no additional chemical reagents are required for either the GO reduction or the metal precursor oxidation, leading to an overall simple and direct synthesis method. The structure and morphology of the as-prepared A-RG (non-calcined) nanocomposites are characterized using various structural analyses including XRD, XPS, SEM/EDX and HR-TEM. Changing metal A in the perovskite as well as the "activation method" resulted in significant structural and morphological changes of the formed composites. SrRuO3 and BaRuO3 in combination with RuO2 are obtained using a conventional combustion method, while SrRuO3 (~1 nm size) in combination with Ru nanoparticles are successfully prepared using microwave irradiation. For the first time, a microwave-assisted synthesis method (without calcination) was used to form crystalline nano-CaRuO3.

Negative Charging of Au Nanoparticles during Methanol Synthesis from CO2 /H2 on a Au/ZnO Catalyst: Insights from Operando IR and Near-Ambient-Pressure XPS and XAS Measurements.

The electronic and structural properties of Au/ZnO under industrial and idealized methanol synthesis conditions have been investigated. This was achieved by kinetic measurements in combination with time-resolved operando infrared (DRIFTS) as well as in situ near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and X-ray absorption near-edge spectroscopy (XANES) measurements at the O K-edge together with high-resolution electron microscopy. The adsorption of CO during the reaction revealed the presence of negatively charged Au nanoparticles/Au sites during the initial phase of the reaction. Near-ambient-pressure XPS and XANES demonstrate the build-up of O vacancies during the reaction, which goes along with a substantial increase in the rate of methanol formation. The results are discussed in comparison with previous findings for Cu/ZnO and Au/ZnO catalysts.

Highly Active and Stable Single-Atom Cu Catalysts Supported by a Metal-Organic Framework.

Single-atom catalysts are often considered as the ultimate design principle for supported catalysts, due to their unique geometric and electronic properties and their highly efficient use of precious materials. Here, we report a single-atom catalyst, Cu/UiO-66, prepared by a covalent attachment of Cu atoms to the defect sites at the zirconium oxide clusters of the metal-organic framework (MOF) UiO-66. Kinetic measurements show this catalyst to be highly active and stable under realistic reaction conditions for two important test reactions, the oxidation of CO at temperatures up to 350 °C, which makes this interesting for application in catalytic converters for cars, and for CO removal via selective oxidation of CO in H2-rich feed gases, where it shows an excellent selectivity of about 100% for CO oxidation. Time-resolved operando spectroscopy measurements indicate that the activity of the catalyst is associated with atomically dispersed, positively charged ionic Cu species. Density functional theory (DFT) calculations in combination with experimental data show that Cu binds to the MOF by -OH/-OH2 ligands capping the defect sites at the Zr oxide clusters.

Improved Performance of Ru/γ-Al2O3 Catalysts in the Selective Methanation of CO in CO2-Rich Reformate Gases upon Transient Exposure to Water-Containing Reaction Gas.

To better understand the role of water in the selective methanation of CO in CO2-rich reformate gases on Ru/Al2O3 catalysts, the influence of exposing these catalysts to H2O-rich reformate gases on their reaction characteristics in transient experiments was investigated by employing kinetic and in situ spectroscopic measurements as well as ex situ catalyst characterization. Transient exposure of the ruthenium catalyst to wet reaction gas (5 or 15% H2O) results in significantly enhanced activity and selectivity for CO methanation in subsequent reactions in dry reformate compared with activation and reaction in dry reformate directly. Operando X-ray absorption spectroscopy results reveal that this is in accordance with a significant decrease in ruthenium particle size, which is stable during subsequent reaction in dry reformate. The implications of these data and additional results from in situ IR spectroscopy on the role and influence of H2O on the reaction, also in technical applications, are discussed.

High Selectivity of Supported Ru Catalysts in the Selective CO Methanation­Water Makes the Difference.

The selectivity for CO methanation is a decisive aspect for the practical application of the methanation reaction for the removal of CO from CO2-rich H2 fuel gases produced via hydrocarbon reforming. We show that increasing the water content in the feed gas, up to technically relevant levels of 30%, significantly increases the selectivity of supported Ru catalysts compared with operation in (almost) dry gas, while in operando EXAFS measurements reveal a gradual decrease in the Ru particle size with increasing amounts of water in the gas feed. Consequences of these findings and related IR spectroscopic data for the mechanistic understanding and practical applications are outlined.

Computational investigation and synthesis of a sol-gel imprinted material for sensing application of some biologically active molecules.

A hybrid sol-gel material was molecularly imprinted with a group of neurotransmitters. Imprinted material is a sol-gel thin film that is spin coated on the surface of a glassy carbon electrode. Imprinted films were characterized electrochemically using cyclic voltammetry (CV) and the encapsulated molecules were extracted from the films and complementary molecular cavities are formed that enable their rebind. The films were tested in their corresponding template solutions for rebinding using square wave voltammetry (SWV). Computational approach for exploring the primary intermolecular forces between templates and hydrolyzed form of the precursor monomer, tetraethylorthosilicate (TEOS), were carried out using Hartree-Fock method (HF). Interaction energy values were computed for each adduct formed between a monomer and a template. Analysis of the optimized conformations of various adducts could explain the mode of interaction between the templates and the monomer units. We found that interaction via the amino group is the common mode among the studied compounds and the results are in good agreement with the electrochemical measurements.

Smart electrochemical sensor for some neurotransmitters using imprinted sol-gel films.

A hybrid sol-gel material formed by acid hydrolysis of a mixture of tetraethylorthosilicate (TEOS) and phenyltriethylorthosilicate (PTEOS) as functional monomers was imprinted by tyramine and dopamine as template molecules for the purpose of molecular recognition. Imprinted materials were spin coated as thin films on the surface of glassy carbon electrodes and then were characterized using cyclic voltammetry (CV). After extraction of the encapsulated molecules, imprinted films were tested in solutions of their templates and other molecules. Rebinding experiments were followed by electrochemical characterization using square wave voltammetry (SWV). Imprinted films showed higher affinities toward their template molecules compared to other structurally similar molecules especially for tyramine imprinted film. With the exception of tyramine and norepinephrine, the interference level did not exceed 5% for all compounds studied for dopamine-imprinted films. Tyramine-imprinted films however showed high affinity to tyramine with dopamine 40% interference. Some factors related to the rebinding ability process like pH of solution, concentration of template were studied. The sensing surface lifetime extended to 2 weeks with decay in response signal that ranged from 22%, 40% to 60% for dopamine, tyramine and norepinephrine, respectively. The standard deviation from the mean of measurements for the repeated experiments is 7.4%. Electrochemical impedance spectroscopy (EIS) measurements confirmed the results obtained by electrochemical measurements. Morphological characteristics of the imprinted thin films and their thickness were investigated using scanning electron microscope (SEM).