Identifying Performance Descriptors in CO2 Hydrogenation over Iron-Based Catalysts Promoted with Alkali Metals.

Alkali metal promoters have been widely employed for preparation of heterogeneous catalysts used in many industrially important reactions. However, the fundamentals of their effects are usually difficult to access. Herein, we unravel mechanistic and kinetic aspects of the role of alkali metals in CO2 hydrogenation over Fe-based catalysts through state-of-the-art characterization techniques, spatially resolved steady-state and transient kinetic analyses. The promoters affect electronic properties of iron in iron carbides. These carbide characteristics determine catalyst ability to activate H2 , CO and CO2 . The Allen scale electronegativity of alkali metal promoter was successfully correlated with the rates of CO2 hydrogenation to higher hydrocarbons and CH4 as well as with the rate constants of individual steps of CO or CO2 activation. The derived knowledge can be valuable for designing and preparing catalysts applied in other reactions where such promoters are also used.

Bridging experiment and theory: enhancing the electrical conductivities of soft-templated niobium-doped mesoporous titania films.

Theoretical calculations suggest a strong dependence of electrical conductivity and doping concentration in transition-metal doped titania. Herein, we present a combined theoretical and experimental approach for the prediction of relative phase stability and electrical conductivity in niobium-doped titania as model system. Our method paves the way towards the development of materials with improved electrical properties.

Atomic-Scale Observation of the Metal-Promoter Interaction in Rh-Based Syngas-Upgrading Catalysts.

The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO2 utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic-scale study of metal-promoter interactions in silica-supported Rh, Rh-Mn, and Rh-Mn-Fe catalysts by aberration-corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh-Mn/SiO2 catalyst, the addition of Fe results in the formation of bimetallic Rh-Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided.

Tracking Catalyst Redox States and Reaction Dynamics in Ni-Fe Oxyhydroxide Oxygen Evolution Reaction Electrocatalysts: The Role of Catalyst Support and Electrolyte pH.

Ni-Fe oxyhydroxides are the most active known electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolytes and are therefore of great scientific and technological importance in the context of electrochemical energy conversion. Here we uncover, investigate, and discuss previously unaddressed effects of conductive supports and the electrolyte pH on the Ni-Fe(OOH) catalyst redox behavior and catalytic OER activity, combining in situ UV-vis spectro-electrochemistry, operando electrochemical mass spectrometry (DEMS), and in situ cryo X-ray absorption spectroscopy (XAS). Supports and pH > 13 strongly enhanced the precatalytic voltammetric charge of the Ni-Fe oxyhydroxide redox peak couple, shifted them more cathodically, and caused a 2-3-fold increase in the catalytic OER activity. Analysis of DEMS-based faradaic oxygen efficiency and electrochemical UV-vis traces consistently confirmed our voltammetric observations, evidencing both a more cathodic O2 release and a more cathodic onset of Ni oxidation at higher pH. Using UV-vis, which can monitor the amount of oxidized Ni+3/+4 in situ, confirmed an earlier onset of the redox process at high electrolyte pH and further provided evidence of a smaller fraction of Ni+3/+4 in mixed Ni-Fe centers, confirming the unresolved paradox of a reduced metal redox activity with increasing Fe content. A nonmonotonic super-Nernstian pH dependence of the redox peaks with increasing Fe content-displaying Pourbaix slopes as steep as -120 mV/pH-suggested a two proton-one electron transfer. We explain and discuss the experimental pH effects using refined coupled (PCET) and decoupled proton transfer-electron transfer (PT/ET) schemes involving negatively charged oxygenate ligands generated at Fe centers. Together, we offer new insight into the catalytic reaction dynamics and associated catalyst redox chemistry of the most important class of alkaline OER catalysts.

Detection of the electronic structure of iron-(iii)-oxo oligomers forming in aqueous solutions.

The nature of the small iron-oxo oligomers in iron-(iii) aqueous solutions has a determining effect on the chemical processes that govern the formation of nanoparticles in aqueous phase. Here we report on a liquid-jet photoelectron-spectroscopy experiment for the investigation of the electronic structure of the occurring iron-oxo oligomers in FeCl3 aqueous solutions. The only iron species in the as-prepared 0.75 M solution are Fe3+ monomers. Addition of NaOH initiates Fe3+ hydrolysis which is followed by the formation of iron-oxo oligomers. At small enough NaOH concentrations, corresponding to approximately [OH]/[Fe] = 0.2-0.25 ratio, the iron oligomers can be stabilized for several hours without engaging in further aggregation. Here, we apply a combination of non-resonant as well as iron 2p and oxygen 1s resonant photoelectron spectroscopy from a liquid microjet to detect the electronic structure of the occurring species. Specifically, the oxygen 1s partial electron yield X-ray absorption (PEY-XA) spectra are found to exhibit a peak well below the onset of liquid water and OH- (aq) absorption. The iron 2p absorption gives rise to signal centered between the main absorption bands typical for aqueous Fe3+. Absorption bands in both PEY-XA spectra are found to correlate with an enhanced photoelectron peak near 20 eV binding energy, which demonstrates the sensitivity of resonant photoelectron (RPE) spectroscopy to mixing between iron and ligand orbitals. These various signals from the iron-oxo oligomers exhibit maximum intensity at [OH]/[Fe] = 0.25 ratio. For the same ratio, we observe changes in the pH as well as in complementary Raman spectra, which can be assigned to the transition from monomeric to oligomeric species. At approximately [OH]/[Fe] = 0.3 we begin to observe particles larger than 1 nm in radius, detected by small-angle X-ray scattering.

New Approach on Quantification of Porosity of Thin Films via Electron-Excited X-ray Spectra.

One of the crucial characteristics of functionalized thin films is their porosity (i.e., the ratio between the pore volume and the volume of the whole film). Due to the very low amount of material per coated area corresponding to thin films, it is a challenge for analytics to measure the film porosity. In this work, we present an approach to determine the porosity of thin films by means of electron probe microanalysis (EPMA) either by wavelength-dispersive X-ray spectrometry (WDX) or by energy-dispersive X-ray spectrometry (EDX) with a scanning electron microscope (SEM). The procedure is based on the calculation of the film mass deposition from electron-excited X-ray spectra. The mass deposition is converted into film density by division of measured film thickness. Finally, the film porosity is calculated from the measured film density and the density of bulk, nonporous film material. The general applicability of the procedure to determine the porosity is demonstrated on thin templated mesoporous TiO2 films, dip-coated on silicon wafer, with controlled porosity in the range of 15 to 50%. The high accuracy of the mass deposition as determined from X-ray spectra was validated with independent methods (ICP-OES and weighing). Furthermore, for the validation of the porosity results, ellipsometry, interference fringes method (IFM), and focused ion beam (FIB) cross sectioning were employed as independent techniques. Hence, the approach proposed in the present study is proven to be suited as a new analytical tool for accurate and relatively fast determination of the porosity of thin films.

New triblock copolymer templates, PEO-PB-PEO, for the synthesis of titania films with controlled mesopore size, wall thickness, and bimodal porosity.

The synthesis and properties of a series of new structure-directing triblock copolymers with PEO-PB-PEO structure (PEO = poly(ethylene oxide) and PB = polybutadiene) and their application as superior pore-templates for the preparation of mesoporous titania coatings are reported. Starting from either TiCl4 or from preformed TiO2 nanocrystalline building blocks, mesoporous crystalline titanium oxide films with a significant degree of mesoscopic ordered pores are derived, and the pore size can be controlled by the molecular mass of the template polymer. Moreover, the triblock copolymers form stable micelles already at very low concentration, i.e., prior to solvent evaporation during the evaporation-induced self-assembly process (EISA). Consequently, the thickness of pore walls can be controlled independently of pore size by changing the polymer-to-precursor ratio. Thus, unprecedented control of wall thickness in the structure of mesoporous oxide coatings is achieved. In addition, the micelle formation of the new template polymers is sufficiently distinct from that of typical commercial PPO-PEO-PPO polymers (Pluronics; PPO = poly(propylene oxide)), so that a combination of both polymers facilitates bimodal porosity via dual micelle templating.

Electrocatalysis using porous nanostructured materials.

The performance of electrochemical reactions depends strongly on the morphology and structure of the employed catalytic electrodes. Nanostructuring of the electrode surface represents a powerful tool to increase the electrochemically active surface area of the electrodes. Moreover, it can also facilitate faster diffusive mass transport inside three-dimensional electrodes. This minireview describes recent trends in the development of synthesis routes for porous nanostructured electrode materials and discusses the respective important electrocatalytic applications. The use of structure-directing agents will play a decisive role in the design and synthesis of improved catalysts.

Mesoporous WCx Films with NiO-Protected Surface: Highly Active Electrocatalysts for the Alkaline Oxygen Evolution Reaction.

Metal carbides are promising materials for electrocatalytic reactions such as water electrolysis. However, for application in catalysis for the oxygen evolution reaction (OER), protection against oxidative corrosion, a high surface area with facile electrolyte access, and control over the exposed active surface sites are highly desirable. This study concerns a new method for the synthesis of porous tungsten carbide films with template-controlled porosity that are surface-modified with thin layers of nickel oxide (NiO) to obtain active and stable OER catalysts. The method relies on the synthesis of soft-templated mesoporous tungsten oxide (mp. WOx ) films, a pseudomorphic transformation into mesoporous tungsten carbide (mp. WCx ), and a subsequent shape-conformal deposition of finely dispersed NiO species by atomic layer deposition (ALD). As theoretically predicted by density functional theory (DFT) calculations, the highly conductive carbide support promotes the conversion of Ni2+ into Ni3+ , leading to remarkably improved utilization of OER-active sites in alkaline medium. The obtained Ni mass-specific activity is about 280 times that of mesoporous NiOx (mp. NiOx ) films. The NiO-coated WCx catalyst achieves an outstanding mass-specific activity of 1989 A gNi -1 in a rotating-disc electrode (RDE) setup at 25 °C using 0.1 m KOH as the electrolyte.

Mechanism of gold nanoparticle formation in the classical citrate synthesis method derived from coupled in situ XANES and SAXS evaluation.

Although gold nanoparticles (GNP) are among the most intensely studied nanoscale materials, the actual mechanisms of GNP formation often remain unclear due to limited accessibility to in situ-derived time-resolved information about precursor conversion and particle size distribution. Overcoming such limitations, a method is presented that analyzes the formation of nanoparticles via in situ SAXS and XANES using synchrotron radiation. The method is applied to study the classical GNP synthesis route via the reduction of tetrachloroauric acid by trisodium citrate at different temperatures and reactant concentrations. A mechanism of nanoparticle formation is proposed comprising different steps of particle growth via both coalescence of nuclei and further monomer attachment. The coalescence behavior of small nuclei was identified as one essential factor in obtaining a narrow size distribution of formed particles.

Role of Water in Phase Transformations and Crystallization of Ferrihydrite and Hematite.

The oxides, hydroxides, and oxo-hydroxides of iron belong to the most abundant materials on earth. They also feature a wide range of practical applications. In many environments, they can undergo facile phase transformations and crystallization processes. Water appears to play a critical role in many of these processes. Despite numerous attempts, the role of water has not been fully revealed yet. We present a new approach to study the influence of water in the crystallization and phase transformations of iron oxides. The approach employs model-type iron oxide films that comprise a defined homogeneous nanostructure. The films are exposed to air containing different amounts of water reaching up to pressures of 10 bar. Ex situ analysis via scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray diffraction is combined with operando near-ambient pressure X-ray photoelectron spectroscopy to follow water-induced changes in hematite and ferrihydrite. Water proves to be critical for the nucleation of hematite domains in ferrihydrite, the resulting crystallite orientation, and the underlying crystallization mechanism.

A meta-analysis of catalytic literature data reveals property-performance correlations for the OCM reaction.

Decades of catalysis research have created vast amounts of experimental data. Within these data, new insights into property-performance correlations are hidden. However, the incomplete nature and undefined structure of the data has so far prevented comprehensive knowledge extraction. We propose a meta-analysis method that identifies correlations between a catalyst's physico-chemical properties and its performance in a particular reaction. The method unites literature data with textbook knowledge and statistical tools. Starting from a researcher's chemical intuition, a hypothesis is formulated and tested against the data for statistical significance. Iterative hypothesis refinement yields simple, robust and interpretable chemical models. The derived insights can guide new fundamental research and the discovery of improved catalysts. We demonstrate and validate the method for the oxidative coupling of methane (OCM). The final model indicates that only well-performing catalysts provide under reaction conditions two independent functionalities, i.e. a thermodynamically stable carbonate and a thermally stable oxide support.

Catalytic properties of MIL-101.

A very high catalytic activity in the cyanosilylation reaction was observed for MIL-101, a chromium based metal-organic framework; moreover, MIL-101 is also a remarkably stable support for palladium in hydrogenation reactions, with significantly higher activity than e.g. palladium on activated carbon.

Oxygen Evolution Catalysts Based on Ir-Ti Mixed Oxides with Templated Mesopore Structure: Impact of Ir on Activity and Conductivity.

The efficient generation of hydrogen via water electrolysis requires highly active oxygen evolution catalysts. Among the active metals, iridium oxide provides the best compromise in terms of activity and stability. The limited availability and usage in other applications demands an efficient utilization of this precious metal. Forming mixed oxides with titania promises improved Ir utilization, but often at the cost of a low catalyst surface area. Moreover, the role of Ir in establishing a sufficiently conductive mixed oxide has not been elucidated so far. We report a new approach for the synthesis of Ir/TiOx mixed-oxide catalysts with defined template-controlled mesoporous structure, low crystallinity, and superior oxygen evolution reaction (OER) activity. The highly accessible pore system provides excellent Ir dispersion and avoids transport limitations. A controlled variation of the oxides Ir content reveals the importance of the catalysts electrical conductivity: at least 0.1 S m-1 are required to avoid limitations owing to slow electron transport. For sufficiently conductive oxides a clear linear correlation between Ir surface sites and OER currents can be established, where all accessible Ir sites equally contribute to the reaction. The optimized catalysts outperform Ir/TiOx materials reported in literature by about a factor of at least four.

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions.

In the future, (electro-)chemical catalysts will have to be more tolerant towards a varying supply of energy and raw materials. This is mainly due to the fluctuating nature of renewable energies. For example, power-to-chemical processes require a shift from steady-state operation towards operation under dynamic reaction conditions. This brings along a number of demands for the design of both catalysts and reactors, because it is well-known that the structure of catalysts is very dynamic. However, in-depth studies of catalysts and catalytic reactors under such transient conditions have only started recently. This requires studies and advances in the fields of 1) operando spectroscopy including time-resolved methods, 2) theory with predictive quality, 3) kinetic modelling, 4) design of catalysts by appropriate preparation concepts, and 5) novel/modular reactor designs. An intensive exchange between these scientific disciplines will enable a substantial gain of fundamental knowledge which is urgently required. This concept article highlights recent developments, challenges, and future directions for understanding catalysts under dynamic reaction conditions.

Iridium Oxide Coatings with Templated Porosity as Highly Active Oxygen Evolution Catalysts: Structure-Activity Relationships.

Iridium oxide is the catalytic material with the highest stability in the oxygen evolution reaction (OER) performed under acidic conditions. However, its high cost and limited availability demand that IrO2 is utilized as efficiently as possible. We report the synthesis and OER performance of highly active mesoporous IrO2 catalysts with optimized surface area, intrinsic activity, and pore accessibility. Catalytic layers with controlled pore size were obtained by soft-templating with micelles formed from amphiphilic block copolymers poly(ethylene oxide)-b-poly(butadiene)-b-poly(ethylene oxide). A systematic study on the influence of the calcination temperature and film thickness on the morphology, phase composition, accessible surface area, and OER activity reveals that the catalytic performance is controlled by at least two independent factors, that is, accessible surface area and intrinsic activity per accessible site. Catalysts with lower crystallinity show higher intrinsic activity. The catalyst surface area increases linearly with film thickness. As a result of the templated mesopores, the pore surface remains fully active and accessible even for thick IrO2 films. Even the most active multilayer catalyst does not show signs of transport limitations at current densities as high as 75 mA cm(-2) .

Turkevich in New Robes: Key Questions Answered for the Most Common Gold Nanoparticle Synthesis.

This contribution provides a comprehensive mechanistic picture of the gold nanoparticle synthesis by citrate reduction of HAuCl4, known as Turkevich method, by addressing five key questions. The synthesis leads to monodisperse final particles as a result of a seed-mediated growth mechanism. In the initial phase of the synthesis, seed particles are formed onto which the residual gold is distributed during the course of reaction. It is shown that this mechanism is a fortunate coincidence created by a favorable interplay of several chemical and physicochemical processes which initiate but also terminate the formation of seed particles and prevent the formation of further particles at later stages of reaction. Since no further particles are formed after seed particle formation, the number of seeds defines the final total particle number and therefore the final size. The gained understanding allows illustrating the influence of reaction conditions on the growth process and thus the final size distribution.

Antireflective coatings with adjustable refractive index and porosity synthesized by micelle-templated deposition of MgF2 sol particles.

Minimizing efficiency losses caused by unwanted light reflection at the interface between lenses, optical instruments and solar cells with the surrounding medium requires antireflective coatings with adequate refractive index and coating thickness. We describe a new type of antireflective coating material with easily and independently tailorable refractive index and coating thickness based on the deposition of colloidal MgF2 nanoparticles. The material synthesis employs micelles of amphiphilic block copolymers as structure directing agent to introduce controlled mesoporosity into MgF2 film. The coatings thickness can be easily adjusted by the applied coating conditions. The coatings refractive index is determined by the materials porosity, which is controlled by the amount of employed pore template. The refractive index can be precisely tuned between 1.23 and 1.11, i.e., in a range that is not accessible to nonporous inorganic materials. Hence, zero reflectance conditions can be established for a wide range of substrate materials.

Formation mechanism of colloidal silver nanoparticles: analogies and differences to the growth of gold nanoparticles.

The formation mechanisms of silver nanoparticles using aqueous silver perchlorate solutions as precursors and sodium borohydride as reducing agent were investigated based on time-resolved in situ experiments. This contribution addresses two important issues in colloidal science: (i) differences and analogies between growth processes of different metals such as gold and silver and (ii) the influence of a steric stabilizing agent on the growth process. The results reveal that a growth due to coalescence is a fundamental growth principle if the monomer-supplying chemical reaction is faster than the actual particle formation.

Broad-spectrum enhancement of polymer composite dielectric constant at ultralow volume fractions of silica-supported copper nanoparticles.

A new strategy for the synthesis of high permittivity polymer composites is demonstrated based on well-defined spatial distribution of ultralow amounts of conductive nanoparticles. The spatial distribution was realized by immobilizing Cu nanoparticles within the pore system of silica microspheres, preventing direct contact between individual Cu particles. Both Cu-loaded and unloaded silica microspheres were then used as fillers in polymer composites prepared with thermoplastic SEBS rubber as the matrix. With a metallic Cu content of about 0.10 vol % [corrected] in the composite, a relative increase of 94% in real permittivity was obtained. No Cu-induced relaxations were observed in the dielectric spectrum within the studied frequency range of 0.1 Hz to 1 MHz. When related to the amount of conductive nanoparticles, the obtained composites achieve the highest broad-spectrum enhancement of permittivity ever reported for a polymer-based composite.