Catalysis Research Research Articles

10 Volumes ofChemCatChem, a Cross Section of Catalysis Research from ChemPubSoc Europe

10 Volumes of<i>ChemCatChem</i>, a Cross Section of Catalysis Research from ChemPubSoc Europe

Dual effects of water vapor on ceria-supported gold clusters.

Atomically precise nanocatalysts are currently being intensely pursued in catalysis research. Such nanocatalysts can serve as model catalysts for gaining fundamental insights into catalytic processes. In this work we report a discovery that water vapor provokes the mild removal of surface long-chain ligands on 25-atom Au25(SC12H25)18 nanoclusters in a controlled manner. Using the resultant Au25(SC12H25)18-x/CeO2 catalyst and CO oxidation as a probe reaction, we found that the catalytic activity of cluster/CeO2 is enhanced from nearly zero conversion of CO (in the absence of water) to 96.2% (in the presence of 2.3 vol% H2O) at the same temperature (100 °C). The cluster catalysts exhibit high stability during the CO oxidation process under moisture conditions (up to 20 vol% water vapor). Water vapor plays a dual role in gold cluster-catalyzed CO oxidation. FT-IR and XPS analyses in combination with density functional theory (DFT) simulations suggest that the "-SC12H25" ligands are easier to be removed under a water vapor atmosphere, thus generating highly active sites. Moreover, the O22- peroxide species constitutes the active oxygen species in CO oxidation, evidenced by Raman spectroscopy analysis and isotope experiments on the CeO2 and cluster/CeO2. The results also indicate the perimeter sites of the interface of Au25(SC12H25)18-x/CeO2 to be active sites for catalytic CO oxidation. The controlled exposure of active sites under mild conditions is of critical importance for the utilization of clusters in catalysis.

Consideration of the Aluminum Distribution in Zeolites in Theoretical and Experimental Catalysis Research

Research efforts in zeolite catalysis have become increasingly cognizant of the diversity in structure and function resulting from the distribution of framework aluminum atoms, through emerging reports of catalytic phenomena that fall outside those recognizable as the shape-selective ones emblematic of its earlier history. Molecular-level descriptions of how active-site distributions affect catalysis are an aspirational goal articulated frequently in experimental and theoretical research, yet they are limited by imprecise knowledge of the structure and behavior of the zeolite materials under interrogation. In experimental research, higher precision can result from more reliable control of structure during synthesis and from more robust and quantitative structural and kinetic characterization probes. In theoretical research, construction of models with specific aluminum locations and distributions seldom capture the heterogeneity inherent to the materials studied by experiment. In this Perspective, we disc...

Benjamin List

Benjamin List

Providing sustainable catalytic solutions for a rapidly changing world.

Catalysis is a key area of modern science and the recognition of its importance has been increasing in recent years. In view of this a Royal Society Discussion Meeting was held on 8–9 May 2017 bringing together many facets of the latest research in catalysis. The meeting was set out in four themes. The first theme Catalysis for Clean Energy was introduced by Professor Christopher Hardacre [1] (Manchester University, UK) who discussed non-thermal plasmas that enable the activation of catalysis at low temperature operation. Dr Sara Jacob [2] (Exxon Mobil, USA) described some new exciting work relevant to alkane oxidation concerning the use of dioxiranes in solution at low temperature. Professor Gianfranco Pacchioni [3] (Milan) showed the power of contemporary computational modelling techniques with new work on biomass conversion using TiO2 and ZrO2 and addressed the question of why catalyst reduction aids the process. Professor …

Cobalt ferrite nanoparticles (CoFe2O4 MNPs) as catalyst and support: magnetically recoverable nanocatalysts in organic synthesis

Abstract Recovery and reusability of catalysts is an important aspect in modern catalysis research especially in organic synthesis. Compared to the conventional separation, magnetic separation has emerged as a robust, highly efficient, easy and rapid separation technique for products and catalysts. Cobalt ferrite nanoparticles are a well-known material, recognized as CoFe2O4 MNPs, and can be used as both catalyst and a versatile support for functionalization of metals, organocatalysts. In recent times, catalysis research has clearly experienced a renaissance in the area of utility of cobalt ferrite (CoFe2O4 MNPs) nanocatalysts based on their ability for recovery and reusability; the activity of these CoFe2O4 MNPs was investigated in a category of organic reactions. In this review, the fabrication, characterization, and application of cobalt ferrite (CoFe2O4 MNPs) nanocatalysts (CF-MNPs) in organic reactions have well summarized.

CAT-ACT-A new highly versatile x-ray spectroscopy beamline for catalysis and radionuclide science at the KIT synchrotron light facility ANKA.

CAT-ACT-the hard X-ray beamline for CATalysis and ACTinide/radionuclide research at the KIT synchrotron radiation facility ANKA-is dedicated to X-ray spectroscopy, including "flux hungry" photon-in/photon-out and correlative techniques and combines state-of-the-art optics with a unique infrastructure for radionuclide and catalysis research. Measurements can be performed at photon energies varying between 3.4 keV and 55 keV, thus encompassing the actinide M- and L-edge or potassium K-edge up to the K-edges of the lanthanide series such as cerium. Well-established X-ray absorption fine structure spectroscopy in transmission and fluorescence detection modes is available in combination with high energy-resolution X-ray emission spectroscopy or X-ray diffraction techniques. The modular beamline design with two alternately operated in-line experimental stations enables sufficient flexibility to adapt sample environments and detection systems to many scientific challenges. The ACT experimental station focuses on various aspects of nuclear waste disposal within the mission of the Helmholtz association to contribute to the solution of one of the greatest scientific and social challenges of our time-the safe disposal of heat producing, highly radioactive waste forms from nuclear energy production. It augments present capabilities at the INE-Beamline by increasing the flux and extending the energy range into the hard X-ray regime. The CAT experimental station focuses on catalytic materials, e.g., for energy-related and exhaust gas catalysis. Characterization of catalytically active materials under realistic reaction conditions and the development of in situ and operando cells for sample environments close to industrial reactors are essential aspects at CAT.

Direct observation of the nanoscale Kirkendall effect during galvanic replacement reactions

Galvanic replacement (GR) is a simple and widely used approach to synthesize hollow nanostructures for applications in catalysis, plasmonics, and biomedical research. The reaction is driven by the difference in electrochemical potential between two metals in a solution. However, transient stages of this reaction are not fully understood. Here, we show using liquid cell transmission electron microscopy that silver (Ag) nanocubes become hollow via the nucleation, growth, and coalescence of voids inside the nanocubes, as they undergo GR with gold (Au) ions at different temperatures. These direct in situ observations indicate that void formation due to the nanoscale Kirkendall effect occurs in conjunction with GR. Although this mechanism has been suggested before, it has not been verified experimentally until now. These experiments can inform future strategies for deriving such nanostructures by providing insights into the structural transformations as a function of Au ion concentration, oxidation state of Au, and temperature.

Independent tuning of size and coverage of supported Pt nanoparticles using atomic layer deposition

Synthetic methods that allow for the controlled design of well-defined Pt nanoparticles are highly desirable for fundamental catalysis research. In this work, we propose a strategy that allows precise and independent control of the Pt particle size and coverage. Our approach exploits the versatility of the atomic layer deposition (ALD) technique by combining two ALD processes for Pt using different reactants. The particle areal density is controlled by tailoring the number of ALD cycles using trimethyl(methylcyclopentadienyl)platinum and oxygen, while subsequent growth using the same Pt precursor in combination with nitrogen plasma allows for tuning of the particle size at the atomic level. The excellent control over the particle morphology is clearly demonstrated by means of in situ and ex situ X-ray fluorescence and grazing incidence small angle X-ray scattering experiments, providing information about the Pt loading, average particle dimensions, and mean center-to-center particle distance.

Application of Artificial Neural Networks for Catalysis: A Review

Machine learning has proven to be a powerful technique during the past decades. Artificial neural network (ANN), as one of the most popular machine learning algorithms, has been widely applied to various areas. However, their applications for catalysis were not well-studied until recent decades. In this review, we aim to summarize the applications of ANNs for catalysis research reported in the literature. We show how this powerful technique helps people address the highly complicated problems and accelerate the progress of the catalysis community. From the perspectives of both experiment and theory, this review shows how ANNs can be effectively applied for catalysis prediction, the design of new catalysts, and the understanding of catalytic structures.

Automated Transition State Search and Its Application to Diverse Types of Organic Reactions.

Transition state search is at the center of multiple types of computational chemical predictions related to mechanistic investigations, reactivity and regioselectivity predictions, and catalyst design. The process of finding transition states in practice is, however, a laborious multistep operation that requires significant user involvement. Here, we report a highly automated workflow designed to locate transition states for a given elementary reaction with minimal setup overhead. The only essential inputs required from the user are the structures of the separated reactants and products. The seamless workflow combining computational technologies from the fields of cheminformatics, molecular mechanics, and quantum chemistry automatically finds the most probable correspondence between the atoms in the reactants and the products, generates a transition state guess, launches a transition state search through a combined approach involving the relaxing string method and the quadratic synchronous transit, and finally validates the transition state via the analysis of the reactive chemical bonds and imaginary vibrational frequencies as well as by the intrinsic reaction coordinate method. Our approach does not target any specific reaction type, nor does it depend on training data; instead, it is meant to be of general applicability for a wide variety of reaction types. The workflow is highly flexible, permitting modifications such as a choice of accuracy, level of theory, basis set, or solvation treatment. Successfully located transition states can be used for setting up transition state guesses in related reactions, saving computational time and increasing the probability of success. The utility and performance of the method are demonstrated in applications to transition state searches in reactions typical for organic chemistry, medicinal chemistry, and homogeneous catalysis research. In particular, applications of our code to Michael additions, hydrogen abstractions, Diels-Alder cycloadditions, carbene insertions, and an enzyme reaction model involving a molybdenum complex are shown and discussed.

Molecular Structure and Confining Environment of Sn Sites in Single-Site Chabazite Zeolites

Chabazite (CHA) molecular sieves, which are industrial catalysts for the selective reduction of nitrogen oxides and the conversion of methanol into olefins, are also ideal materials in catalysis research because their crystalline frameworks contain one unique tetrahedral site. The presence of a single lattice site allows for more accurate descriptions of experimental data using theoretical models and consequently for precise structure–function relationships of active sites incorporated into framework positions. A direct hydrothermal synthesis route to prepare pure-silica chabazite molecular sieves substituted with framework Sn atoms (Sn-CHA) was developed, which is required to predominantly incorporate Sn within the crystalline lattice. Quantitative titration with Lewis bases (NH3, CD3CN, and pyridine) demonstrates that framework Sn atoms behave as Lewis acid sites which catalyze intermolecular propionaldehyde reduction and ethanol oxidation as well as glucose–fructose isomerization. Aqueous-phase glucose...

Selective C−H Bond Cleavage in Methane by Small Gold Clusters

AbstractMethane represents the major constituent of natural gas. It is primarily used only as a source of energy by means of combustion, but could also serve as an abundant hydrocarbon feedstock for high quality chemicals. One of the major challenges in catalysis research nowadays is therefore the development of materials that selectively cleave one of the four C−H bonds of methane and thus make it amenable for further chemical conversion into valuable compounds. By employing infrared spectroscopy and first‐principles calculations it is uncovered herein that the interaction of methane with small gold cluster cations leads to selective C−H bond dissociation and the formation of hydrido methyl complexes, H‐Aux+‐CH3. The distinctive selectivity offered by these gold clusters originates from a fine interplay between the closed‐shell nature of the d states and relativistic effects in gold. Such fine balance in fundamental interactions could prove to be a tunable feature in the rational design of a catalyst.

Coexistence of Physisorbed and Solvated HCl at Warm Ice Surfaces.

The interfacial ionization of strong acids is an essential factor of multiphase and heterogeneous chemistry in environmental science, cryospheric science, catalysis research and material science. Using near ambient pressure core level X-ray photoelectron spectroscopy, we directly detected a low surface coverage of adsorbed HCl at 253 K in both molecular and dissociated states. Depth profiles derived from XPS data indicate the results as physisorbed molecular HCl at the outermost ice surface and dissociation occurring upon solvation deeper in the interfacial region. Complementary X-ray absorption measurements confirm that the presence of Cl- ions induces significant changes to the hydrogen bonding network in the interfacial region. This study gives clear evidence for nonuniformity across the air-ice interface and questions the use of acid-base concepts in interfacial processes.

Ammonia Synthesis on Wool-Like Au, Pt, Pd, Ag, or Cu Electrode Catalysts in Nonthermal Atmospheric-Pressure Plasma of N2 and H2

Developing an ammonia synthesis process from N2 and H2 is of interest in the catalysis and hydrogen research community. Wool-like metal electrodes used to produce nonthermal plasma were determined to serve as efficient catalysts for ammonia synthesis under atmospheric pressure without heating. The catalytic activity of Pt, Pd, Ag, Cu, and Ni wools increased as the experiment was repeated, while that of Au, Fe, Mo, Ti, W, and Al was almost constant. The activity change was mainly due to migration of metals from the electrode to the inner wall of a silica reactor or increases in surface areas of metal catalysts. The order of the activity at each initial experiment was Au > Pt > Pd > Ag > Cu > Fe > Mo > Ni > W > Ti > Al. DFT calculations using Gaussian 09 and CASTEP were applied for energy changes in a reaction M3 + 1/2 N2 → M3N and in adsorption of a nitrogen atom on metal surface, in which M3 was a virtual minimum unit of the metal surface. The reactions were assumed to be an essential step in the ammonia ...

Epitaxial fabrication of two-dimensional NiSe2 on Ni(111) substrate

Two-dimensional (2D) transition metal dichalcogenides (TMDs) receive significant attention due to their intriguing physical properties for both fundamental research and potential applications in electronics, optoelectronics, and catalysis. A high-quality 2D film of NiSe2, a TMD material, is grown epitaxially by a single step direct selenization of a Ni(111) substrate. X-ray photoemission spectroscopy, low-energy electron diffraction, scanning tunneling microscopy, and density functional theory calculations are combined to confirm the formation and structure of the film, revealing a (√3 × √3) superlattice of the NiSe2 film formed on the (√7 × √7) superlattice of the substrate. Fabrication of this 2D NiSe2 film opens opportunities to research its applications, especially for electrocatalysis and energy storage devices.

Temporal Analysis of Products Experiments at Atmospheric Pressure: The Epoxidation of Ethylene on Silver

AbstractA high‐speed pulse reactor setup for the study of chemical reactions which are catalyzed by a fixed bed is described. The benefits of this method compared to stationary‐state measurements are demonstrated using the example of ethylene epoxidation on elemental silver. It is shown that the intrinsic catalyst reactivity depends strongly on oxygen loading and has a pronounced maximum for a loading of about 50 %. In contrast, the selectivity is independent thereof. The relevance of the method for research in catalysis and its relation to the well‐established temporal analysis of products approach are illustrated and discussed.

Stationary Probe Rotating Disk Electrode for in Situ Dissolution Studies

The development of clean, reliable and cost-effective electrochemical processes must be guided by three equally important fundamental principles: improving the catalytic activity of electrode materials, increasing their long-term stability in harsh electrochemical environments and high selectivity for targeted products. Although our current understanding on the electrochemical interface has rendered great improvement in activities for a range of energy related processes, such as those involved in Fuel Cells and Electrolyzers, we still lack the same level of control over the stability and selectivity aspects of the catalysis. One of the limitations is the ability to measure in situ and in real time how species are being generated while the reactions are taking place, a key element for understanding the dynamics of the processes beyond steady-state conditions. For that, we developed a unique experimental setup that adds to the existing rotating disk configuration the capability to observe the species produced during catalysis. The Stationary Probe Rotating Disk Electrode (SPRDE) enables a seamless connection between electrocatalysis and high-end mass spectrometers that gives us the opportunity to measure with precision the dissolution rates of almost any element of the periodic table (combination with ICP-MS). This new methodology offers advantages over flow cell systems and it can be readily applied in understanding electrochemical dissolution processes that occur during fuel cell and electrolyzer catalysis, dealloying processes, corrosion, and battery research.

High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts.

We report high-energy-resolution X-ray absorption spectroscopy detection of ethylene and CO ligands adsorbed on catalytically active iridium centers isolated on zeolite HY and on MgO supports. The data are supported by density functional theory and FEFF X-ray absorption near-edge modelling, together with infrared (IR) spectra. The results demonstrate that high-energy-resolution X-ray absorption spectra near the iridium LIII (2p3/2 ) edge provide clearly ascribable, distinctive signatures of the ethylene and CO ligands and illustrate effects of supports and other ligands. This X-ray absorption technique is markedly more sensitive than conventional IR spectroscopy for characterizing surface intermediates, and it is applicable to samples having low metal loadings and in reactive atmospheres and is expected to have an increasing role in catalysis research by facilitating the determination of mechanisms of solid-catalyzed reactions through identification of reaction intermediates in working catalysts.

Magnetic Fe3O4 nanoparticles supported imine/Thiophene‐nickel (II) complex: A new and highly active heterogeneous catalyst for the synthesis of polyhydroquinolines and 2, 3‐dihydroquinazoline‐4(1H)‐ones

A new magnetically separable nickel catalyst (Ni(NO3)2−Imine/Thiophene‐Fe3O4@SiO2) was readily prepared and structurally characterized by Fourier transform infrared spectroscopy (FT‐IR), Scanning electron microscopy (SEM), Energy‐dispersive X‐ray spectroscopy (EDX), Vibrating sample magnetometer (VSM), X‐Ray diffraction (XRD) and Atomic absorption spectroscopy (AAS). The Ni(NO3)2−Imine/Thiophene‐Fe3O4@SiO2 exhibited efficient catalytic activity in the synthesis of 2,3‐dihydroquinazoline‐4(1H)‐ones and polyhydroquinolines. Catalysis research under water and solvent‐free conditions makes also this synthetic protocol ideal and fascinating from the environmental point of view. The catalyst can be magnetically recovered after the reaction and can be reused for many times without appreciable decrease in activity.