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

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

Whole Genome Sequence of Dermacoccus abyssi MT1.1 Isolated from the Challenger Deep of the Mariana Trench Reveals Phenazine Biosynthesis Locus and Environmental Adaptation Factors

Dermacoccus abyssi strain MT1.1T is a piezotolerant actinobacterium that was isolated from Mariana Trench sediment collected at a depth of 10898 m. The organism was found to produce ten dermacozines (A‒J) that belonged to a new phenazine family and which displayed various biological activities such as radical scavenging and cytotoxicity. Here, we report on the isolation and identification of a new dermacozine compound, dermacozine M, the chemical structure of which was determined using 1D and 2D-NMR, and high resolution MS. A whole genome sequence of the strain contained six secondary metabolite-biosynthetic gene clusters (BGCs), including one responsible for the biosynthesis of a family of phenazine compounds. A pathway leading to the biosynthesis of dermacozines is proposed. Bioinformatic analyses of key stress-related genes provide an insight into how the organism adapted to the environmental conditions that prevail in the deep-sea

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

Biotechnological and ecological potential of 'Micromonospora provocatoris' sp. nov., a gifted strain isolated from the Challenger Deep of the Mariana Trench

A Micromonospora strain, isolate MT25T, was recovered from a sediment collected from the Challenger Deep of the Mariana Trench using a selective isolation procedure. The isolate produced two major metabolites, n-acetylglutaminyl glutamine amide and desferrioxamine B, the chemical structures of which were determined using 1D and 2D-NMR, including 1H-15N HSQC and 1H-15N HMBC 2D-NMR, as well as high resolution MS. A whole genome sequence of the strain showed the presence of ten natural product-biosynthetic gene clusters, including one responsible for the biosynthesis of desferrioxamine B. Whilst 16S rRNA gene sequence analyses showed that the isolate was most closely related to the type strain of Micromonospora chalcea, a whole genome sequence analysis revealed it to be most closely related to Micromonospora tulbaghiae 45142T. The two strains were distinguished using a combination of genomic and phenotypic features. Based on these data, it is proposed that strain MT25T (NCIMB 15245T, TISTR 2834T) be classified as Micromonospora provocatoris sp. nov. Analysis of the genome sequence of strain MT25T (genome size 6.1 Mbp) revealed genes predicted to responsible for its adaptation to extreme environmental conditions that prevail in deep-sea sediments

Operando investigations of particle size and support effects during the selective CO methanation over oxide supported Ru nanoparticles in idealized and realistic H2 feed gases

In addition to the increasing importance in technical applications of the selective CO methanation, it is also an ideal model reaction for testing the catalytic performance of supported Ru catalysts in hydrogenation reactions. The focus of the present work is the molecular scale understanding of the relationship between structure and catalytic performance of supported Ru catalysts, with emphasis on the disentanglement of metal particle size effects from the metal-support interaction for non-reducible (zeolite and Al2O3) and reducible (TiO2) oxide support materials. The findings and mechanistic insights drawn from these studies were obtained using a multi-analytical approach, employing state of the art time on-stream reaction kinetic experiments, as well as time resolved operando diffuse reflectance FTIR and X-ray absorption fine structure (XAFS) spectroscopy. These measurements were supplemented by a detailed elucidation of the composition and structural properties of the catalysts, studied by ex situ characterization techniques, including X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM) imaging, and inductively coupled plasma optical emission spectroscopy (ICP-OES)

Review of CO2 Reduction on Supported Metals (Alloys) and Single-Atom Catalysts (SACs) for the Use of Green Hydrogen in Power-to-Gas Concepts

The valorization of carbon dioxide by diverting it into useful chemicals through reduction has recently attracted much interest due to the pertinent need to curb increasing global warming, which is mainly due to the huge increase of CO2 emissions from domestic and industrial activities. This approach would have a double benefit when using the green hydrogen generated from the electrolysis of water with renewable electricity (solar and wind energy). Strategies for the chemical storage of green hydrogen involve the reduction of carbon dioxide to value-added products such as methane, syngas, methanol, and their derivatives. The reduction of CO2 at ambient pressure to methane or carbon monoxide are rather facile processes that can be easily used to store renewable energy or generate an important starting material for chemical industry. While the methanation pathway can benefit from existing infrastructure of natural gas grids, the production of syngas could be also very essential to produce liquid fuels and olefins, which will also be in great demand in the future. In this review, we focus on the recent advances in the thermocatalytic reduction of CO2 at ambient pressure to basically methane and syngas on the surface of supported metal nanoparticles, single-atom catalyst (SACs), and supported bimetallic alloys. Basically, we will concentrate on activity, selectivity, stability during reaction, support effects, metal-support interactions (MSIs), and on some recent approaches to control and switch the CO2 reduction selectivity between methane and syngas. Finally, we will discuss challenges and requirements for the successful introduction of these processes in the cycle of renewable energies. All these aspects are discussed in the frame of sustainable use of renewable energies

Review of CO₂ Reduction on Supported Metals (Alloys) and Single-Atom Catalysts (SACs) for the Use of Green Hydrogen in Power-to-Gas Concepts

The valorization of carbon dioxide by diverting it into useful chemicals through reduction has recently attracted much interest due to the pertinent need to curb increasing global warming, which is mainly due to the huge increase of CO2 emissions from domestic and industrial activities. This approach would have a double benefit when using the green hydrogen generated from the electrolysis of water with renewable electricity (solar and wind energy). Strategies for the chemical storage of green hydrogen involve the reduction of carbon dioxide to value-added products such as methane, syngas, methanol, and their derivatives. The reduction of CO2 at ambient pressure to methane or carbon monoxide are rather facile processes that can be easily used to store renewable energy or generate an important starting material for chemical industry. While the methanation pathway can benefit from existing infrastructure of natural gas grids, the production of syngas could be also very essential to produce liquid fuels and olefins, which will also be in great demand in the future. In this review, we focus on the recent advances in the thermocatalytic reduction of CO2 at ambient pressure to basically methane and syngas on the surface of supported metal nanoparticles, single-atom catalyst (SACs), and supported bimetallic alloys. Basically, we will concentrate on activity, selectivity, stability during reaction, support effects, metal-support interactions (MSIs), and on some recent approaches to control and switch the CO2 reduction selectivity between methane and syngas. Finally, we will discuss challenges and requirements for the successful introduction of these processes in the cycle of renewable energies. All these aspects are discussed in the frame of sustainable use of renewable energies

Enhancement of AC high voltage measurements’ uncertainty using a high voltage divider calibration method

This paper discusses enhancing of the measurements’ uncertainty for AC high voltage up to 100 kV. This is achieved by using a high voltage divider calibration method. Voltage measurements have been carried out at the Egyptian national institute for standards (NIS), using a high voltage measuring system (Phenix-KVM100), that consists of a high voltage divider and a voltage display. The voltage divider and display have been calibrated in low and high voltage ranges. Reference standard digital voltmeter and a multifunction calibrator have been used to calibrate the KVM100 for achieving accurate and traceable results. All calibrations have been performed automatically using Laboratory Virtual Instrument Engineering Workbench (LabVIEW) programs specially designed for this task. Uncertainty budget has been evaluated to get the measurements’ expanded uncertainties