Quo Vadis Dry Reforming of Methane?—A Review on Its Chemical, Environmental, and Industrial Prospects

In recent years, the catalytic dry reforming of methane (DRM) has increasingly come into academic focus. The interesting aspect of this reaction is seemingly the conversion of CO2 and methane, two greenhouse gases, into a valuable synthesis gas (syngas) mixture with an otherwise unachievable but industrially relevant H2/CO ratio of one. In a possible scenario, the chemical conversion of CO2 and CH4 to syngas could be used in consecutive reactions to produce synthetic fuels, with combustion to harness the stored energy. Although the educts of DRM suggest a superior impact of this reaction to mitigate global warming, its potential as a chemical energy converter and greenhouse gas absorber has still to be elucidated. In this review article, we will provide insights into the industrial maturity of this reaction and critically discuss its applicability as a cornerstone in the energy transition. We derive these insights from assessing the current state of research and knowledge on DRM. We conclude that the entire industrial process of syngas production from two greenhouse gases, including heating with current technologies, releases at least 1.23 moles of CO2 per mol of CO2 converted in the catalytic reaction. Furthermore, we show that synthetic fuels derived from this reaction exhibit a negative carbon dioxide capturing efficiency which is similar to burning methane directly in the air. We also outline potential applications and introduce prospective technologies toward a net-zero CO2 strategy based on DRM

In situ and operando electron microscopy in heterogeneous catalysis - insights into multi-scale chemical dynamics

This review features state-of-the-art in situ and operando electron microscopy (EM) studies of heterogeneous catalysts in gas and liquid environments during reaction. Heterogeneous catalysts are important materials for the efficient production of chemicals/fuels on an industrial scale and for energy conversion applications. They also play a central role in various emerging technologies that are needed to ensure a sustainable future for our society. Currently, the rational design of catalysts has largely been hampered by our lack of insight into the working structures that exist during reaction and their associated properties. However, elucidating the working state of catalysts is not trivial, because catalysts are metastable functional materials that adapt dynamically to a specific reaction condition. The structural or morphological alterations induced by chemical reactions can also vary locally. A complete description of their morphologies requires that the microscopic studies undertaken span several length scales. EMs, especially transmission electron microscopes, are powerful tools for studying the structure of catalysts at the nanoscale because of their high spatial resolution, relatively high temporal resolution, and complementary capabilities for chemical analysis. Furthermore, recent advances have enabled the direct observation of catalysts under realistic environmental conditions using specialized reaction cells. Here, we will critically discuss the importance of spatially-resolved operando measurements and the available experimental setups that enable (1) correlated studies where EM observations are complemented by separate measurements of reaction kinetics or spectroscopic analysis of chemical species during reaction or (2) real-time studies where the dynamics of catalysts are followed with EM and the catalytic performance is extracted directly from the reaction cell that is within the EM column or chamber. Examples of current research in this field will be presented. Challenges in the experimental application of these techniques and our perspectives on the field's future directions will also be discussed

Insights into Chemical Dynamics and Their Impact on the Reactivity of Pt Nanoparticles during CO Oxidation by Operando TEM

The functionality of heterogeneous catalysts is influenced by a delicate interplay of multiple parameters, including morphology and structure, chemical potential gradients and related dynamics. Here, we report on how these factors are interconnected. Combining time-resolved transmission electron microscopy imaging and selected area electron diffraction with online conversion detection, CO oxidation over Pt nanoparticles was studied at a pressure of 700 mbar and temperatures up to 500 °C. The different interactions between reactants and catalysts over the entire range of catalytic conversion were investigated. Chemical dynamics in this reaction were found to consist of both morphological transformations and fluctuating structural dynamics. Morphological transformations were observed mostly in low activity regimes, leading to nanoparticles with increased stable surface facets. Meanwhile structural changes were observed during high activity regimes where the partial pressures remained constant. Furthermore, the observed changes were found to occur in both the bulk and the surface of the catalyst. Catalytic cycling revealed that morphological transformations and structural dynamics have different implications on the reactivity and are mostly irreversible

Electrostatic attraction of nanoobjects - a versatile strategy towards mesostructured transition metal compounds

This highlight summarizes current challenges of mesostructuring and focuses on the scope and the potential of the ELAN – (electrostatic attraction of nanoobjects) strategy in mesostructuring of transition metal compounds. It discusses the limitations of this concept and highlights prominent examples. ELAN exploits the Coulomb attraction between inorganic precursors and polymeric templates in order to prevent macrophase separation. Essential requirements for ELAN are tailor-made, mesoscopic polyelectrolytic templates and charged molecular oligo-ions or stable colloids carrying a surface charge. The ELAN-strategy is highly reliable and opens the way to crystalline, mesoporous transition metal compounds with predefined polymorphism. It also provides the possibility to adjust wall chemistry and reactivity as well as the flexibility to synthesise different mesostructures (spheres, non-woven arrays or hexagonally ordered phases)

Intense, carrier frequency and bandwidth tunable quasi single-cycle pulses from an organic emitter covering the Terahertz frequency gap

In Terahertz (THz) science, one of the long-standing challenges has been the formation of spectrally dense, single-cycle pulses with tunable duration and spectrum across the frequency range of 0.1-15 THz (THz gap). This frequency band, lying between the electronically and optically accessible spectra hosts important molecular fingerprints and collective modes which cannot be fully controlled by present strong-field THz sources. We present a method that provides powerful single-cycle THz pulses in the THz gap with a stable absolute phase whose duration can be continuously selected between 68 fs and 1100 fs. The loss-free and chirp-free technique is based on optical rectification of a wavelength-tunable pump pulse in the organic emitter HMQ-TMS that allows for tuning of the spectral bandwidth from 1 to more than 7 octaves over the entire THz gap. The presented source tunability of the temporal carrier frequency and spectrum expands the scope of spectrally dense THz sources to time-resolved nonlinear THz spectroscopy in the entire THz gap. This opens new opportunities towards ultrafast coherent control over matter and light

Enhancing the Catalytic Activity of Palladium Nanoparticles via Sandwich-Like Confinement by Thin Titanate Nanosheets

As atomically thin oxide layers deposited on flat (noble) metal surfaces have been proven to have a significant influence on the electronic structure and thus the catalytic activity of the metal, we sought to mimic this architecture at the bulk scale. This could be achieved by intercalating small positively charged Pd nanoparticles of size 3.8 nm into a nematic liquid crystalline phase of lepidocrocite-type layered titanate. Upon intercalation the galleries collapsed and Pd nanoparticles were captured in a sandwichlike mesoporous architecture showing good accessibility to Pd nanoparticles. On the basis of X-ray photoelectron spectroscopy (XPS) and CO diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) Pd was found to be in a partially oxidized state, while a reduced Ti species indicated an electronic interaction between nanoparticles and nanosheets. The close contact of titanate sandwiching Pd nanoparticles, moreover, allows for the donation of a lattice oxygen to the noble metal (inverse spillover). Due to the metal–support interactions of this peculiar support, the catalyst exhibited the oxidation of CO with a turnover frequency as high as 0.17 s–1 at a temperature of 100 °C

Mesostructured ZnO/Au nanoparticle composites with enhanced photocatalytic activity

Ease of catalyst separation from reaction mixtures represents a significant advantage in heterogeneous photocatalytic wastewater treatment. However, the activity of the catalyst strongly depends on its surface-to-volume ratio. Here, we present an approach based on cylindrical polybutadiene-block-poly(2-vinylpyridine) polymer brushes as template, which can be simultaneously loaded with zinc oxide (ZnO) and gold (Au) nanoparticles. Pyrolytic template removal of the polymer yields in mesostructured ZnO/Au composites, showing higher efficiencies in the photocatalytic degradation of ciprofloxacin and levofloxacin (generic antibiotics present in clinical wastewater) as compared to neat mesostructured ZnO. Upscaling of the presented catalyst is straightforward promising high technical relevance

Strong Metal–Support Interactions between Copper and Iron Oxide during the High‐Temperature Water‐Gas Shift Reaction

The commercial high‐temperature water‐gas shift (HT‐WGS) catalyst consists of CuO‐Cr2O3‐Fe2O3, where Cu functions as a chemical promoter to increase the catalytic activity, but its promotion mechanism is poorly understood. In this work, a series of iron‐based model catalysts were investigated with in situ or pseudo in situ characterization, steady‐state WGS reaction, and density function theory (DFT) calculations. For the first time, a strong metal‐support interaction (SMSI) between Cu and FeOx was directly observed. During the WGS reaction, a thin FeOx overlayer migrates onto the metallic Cu particles, creating a hybrid surface structure with Cu‐FeOx interfaces. The synergistic interaction between Cu and FeOx not only stabilizes the Cu clusters, but also provides new catalytic active sites that facilitate CO adsorption, H2O dissociation, and WGS reaction. These new fundamental insights can potentially guide the rational design of improved iron‐based HT‐WGS catalysts

SnBrP-A SnIP-type representative in the Sn-Br-P system

One-dimensional semiconductors are interesting materials due to their unique structural features and anisotropy, which grant them intriguing optical, dielectric and mechanical properties. In this work, we report on SnBrP, a lighter homologue of the first inorganic double helix compound SnIP. This class of compounds is characterized by intriguing mechanical and electronic properties, featuring a high flexibility without modulation of physical properties. Semiconducting SnBrP can be synthesized from red phosphorus, tin and tin(II)bromide at elevated temperatures and crystallizes as red-orange, cleavable needles. Raman measurements pointed towards a double helical building unit in SnBrP, showing similarities to the SnIP structure. After taking PL measurements, HR-TEM, and quantum chemical calculations into account, we were able to propose a sense full structure model for SnBrP