The surface of supported heterogeneous catalysts often contains adsorbed water and hydroxyl groups even when water is not directly added to the reaction stream. Nonetheless, the reactivity of adsorbed water and hydroxyl groups is rarely considered. We demonstrate that water and hydroxyl groups can not only directly participate in the catalytic oxidation processes but are also able to generate and stabilize the catalytically active metal-oxide interface. We show that the reduction of Pt-Fe-supported catalysts with hydrogen in the presence of adsorbed water or steam allows for achieving one of the highest preferential carbon monoxide oxidation activities at ambient temperature. These conditions create active iron-associated hydroxyl groups next to platinum nanoparticles with enhanced reactivity towards carbon monoxide oxidation. Density functional theory calculations suggest that hydroxylation of oxidic iron species stabilizes the FeO_x(OH)_y/Pt interface, via strong metal-support interaction, which is confirmed by chemisorption measurements. Kinetic experiments, including those with ¹⁸O-labeled water, in combination with operando infrared spectroscopy, show that water and hydroxyl groups directly participate in preferential carbon monoxide oxidation. A quantitative correlation between the catalytic activity of Pt-FeO_x(OH)_y/γ-Al₂O₃ catalysts and the Fe²⁺ concentration, obtained using operando X-ray absorption spectroscopy, shows that the number of active Fe²⁺ sites and the carbon monoxide oxidation rate per active site can be significantly increased by water-assisted pretreatment with hydrogen. This work provides a new example of positive role of strong metal-support interaction for the design of more active catalysts.

The structure of copper sites formed under an oxidative environment and their evolution in the course of the reaction with methane at elevated temperature was investigated by means of Cu K-edge X-ray absorption spectroscopy for a series of copper-containing MFI, MOR, and FAU zeolites. The pretreatment in oxygen at 723 K leads to the formation of copper(II)-oxo sites, whose nature depends on the framework type. Dimeric species are formed in CuMFI material, dimeric and monomeric sites coexist in CuMOR, and agglomerated copper-oxo nanoclusters are found in large-pore copper-containing faujasite (CuFAU). For all studied materials, the reaction with methane resulted in the exclusive formation of copper(I) species; no formation of metallic copper was detected even at 748 K. The nature of formed copper(I) species is governed by the structure of corresponding copper(II) centers. In particular, monomeric and dimeric copper(II)-oxo sites hosted in CuMOR and CuMFI are transformed into isolated copper(I) cations coordinated to ion-exchange positions of the zeolite. Contrarily, copper(II)-oxo clusters present in CuFAU undergo restructuring with only a partial loss of extra-framework oxygen and form aggregated species with a structure similar to that of bulk copper(I) oxide.

Fossil-free ironmaking is indispensable for reducing massive anthropogenic CO ₂ emissions in the steel industry. Hydrogen-based direct reduction (HyDR) is among the most attractive solutions for green ironmaking, with high technology readiness. The underlying mechanisms governing this process are characterized by a complex interaction of several chemical (phase transformations), physical (transport), and mechanical (stresses) phenomena. Their interplay leads to rich microstructures, characterized by a hierarchy of defects ranging across several orders of magnitude in length, including vacancies, dislocations, internal interfaces, and free surfaces in the form of cracks and pores. These defects can all act as reaction, nucleation, and diffusion sites, shaping the overall reduction kinetics. A clear understanding of the roles and interactions of these dynamically-evolving nano-/microstructure features is missing. Gaining better insights into these effects could enable improved access to the microstructure-based design of more efficient HyDR methods, with potentially high impact on the urgently needed decarbonization in the steel industry.

In this work, adsorption of nitrogen monoxide (NO) and carbon monoxide (CO) probe molecules on various copper sites in a range of zeolites is studied. The structures of copper sites, binding energies, and vibrational frequencies of adsorbed probe molecules are calculated using density functional theory (DFT). This allows mapping vibrational spectra regions to specific copper species as a function of the zeolite topology and Si/Al ratio. CO can adsorb on Cu⁺ions by forming mono- and dicarbonyls or on copper ions bonded to methoxy species by forming methoxy-monocarbonyls, which exhibit a blue shift in wavenumbers. The stretching frequencies of adsorbed NO generally increase in the following order: [CuOH]⁺< [Cu₂O]²⁺/[Cu₂O₂]²⁺< [Cu²⁺] < [Cu_n + 1On]²⁺/[CunOn]²⁺(n> 3) < [Cu₃O₂]²⁺/[Cu₃O₃]²⁺. The shift values between different species vary between 5 and 20 cm^-1, showing the possibility for structure assignment based on infrared frequencies. Zeolite frameworks with smaller pores exhibit a shift of vibrational bands of adsorbed NO toward lower frequencies because of the confinement effect of the zeolite pore structure. Zeolites with larger pores stabilize the copper species of higher nuclearity. Our data indicate that the tabulated infrared frequencies of adsorbed CO and NO may be used to assign zeolitic copper speciation from experimental data.

The performance of functional materials is either driven or limited by nanoscopic heterogeneities distributed throughout the material’s volume. To better our understanding of these materials, we need characterization tools that allow us to determine the nature and distribution of these heterogeneities in their native geometry in 3D. Here, we introduce a method based on x-ray near-edge spectroscopy, ptychographic x-ray computed nanotomography, and sparsity techniques. The method allows the acquisition of quantitative multimodal tomograms of representative sample volumes at sub–30 nm half-period spatial resolution within practical acquisition times, which enables local structure refinements in complex geometries. To demonstrate the method’s capabilities, we investigated the transformation of vanadium phosphorus oxide catalysts with industrial use. We observe changes from the micrometer to the atomic level and the formation of a location-specific defect so far only theorized. These results led to a reevaluation of these catalysts used in the production of plastics.

The direct conversion of methane to methanol using oxygen is a challenging but potentially rewarding pathway towards utilizing methane. By using a stepwise chemical looping approach, copper-exchanged zeolites can convert methane to methanol, but productivity is still too low for viable implementation. However, if the nature of the active site could be elucidated, that information could be used to design more effective catalysts. By employing anomalous X-ray powder diffraction with support from theory and other X-ray techniques, we have derived a quantitative and spatial description of the highly selective, active copper sites in zeolite omega (Cu-omega). This is the first comprehensive description of the structure of non-copper-oxo active species and will provide a pivotal model for future development for materials for methane to methanol conversion.

The metal-support interaction plays a critical role in heterogeneous catalysis. Under reducing conditions, oxidic supports may interact with supported metal particles, by either forming an oxide overlayer or an alloy. The structure of both the support and the nanoparticle, as well as of the interface itself, changes in response to varying environmental conditions. Here, we present a fullyab initioapproach to predict the structures and energetics of such systems for a range of transition metals (Me = Cu, Ru, Pd, Ag, Rh, Os, Ir, Pt, Au) supported on titania surfaces as a function of gas atmosphere composition. The competing formation of a monolayer comprising fully oxidized titania (TiO₂), its reduced forms (Ti₂O₃, TiO), and the Ti-Me surface alloy, is investigated. The stability of each of these phases is found to be very sensitive to the environmental conditions and the supported metal. Encapsulation of metal, also known as classical strong metal-support interaction (SMSI), was predicted by thermodynamic driving force analysis. We show that a simple parameter, the Ti-Me alloy formation energy, is a good descriptor for the strength of the interaction between metal substrates and reduced titania monolayers and has predictive power towards the conditions under which an overlayer is stable. The presented thermochemical data and phase diagram analysis can be used to identify the structure and stability of supported metal catalysts under realistic conditions.

Catalytic systems based on supported noble metals are extensively studied because of their widespread application. Discussions remain about the nature of the active species, whether they are atomically dispersed or nanoparticles, and their reactivity. In this work, combining in situ/operando spectroscopy with theoretical modeling, we propose a phase diagram of atomically dispersed platinum on ceria, demonstrating that it reversibly changes from PtIVO2 to PtIIO as a function of temperature and oxygen partial pressure. The phase diagram helps identify the stability domain of each species, while spectroscopies provide a quantitative evaluation depending on the reaction conditions. Finally, our results show that high-temperature activation in the presence of steam of supported atomically dispersed platinum enhances the activity toward low-temperature carbon monoxide oxidation because it promotes aggregation into nanoparticles. This work highlights the structure-activity relationship in supported metal catalysts and proposes a suitable approach to determine the amount of each species before the investigation of the reaction mechanism.

Copper-exchanged zeolites are a class of redox-active materials that find application in the selective catalytic reduction of exhaust gases of diesel vehicles and, more recently, the selective oxidation of methane to methanol. However, the structure of the active copper-oxo species present in zeolites under oxidative environments is still a subject of debate. Herein, we make a comprehensive study of copper species in copper-exchanged zeolites with MOR, MFI, BEA, and FAU frameworks and for different Si/Al ratios and copper loadings using X-ray absorption spectroscopy. Only obtaining high quality EXAFS data, collected at largek-values and measured under cryogenic conditions, in combination with wavelet transform analysis enables the discrimination between the copper-oxo species having different structures. The zeolite topology strongly affects the copper speciation, ranging from monomeric copper species to copper-oxo clusters, hosted in zeolites of different topologies. In contrast, the variation of the Si/Al ratio or copper loading in mordenite does not lead to significant differences in XAS spectra, suggesting that a change, if any, in the structure of copper species in these materials is not distinguishable by EXAFS.

In this critical review we examine the current state of our knowledge in respect of the nature of the active sites in copper containing zeolites for the selective conversion of methane to methanol. We consider the varied experimental evidence arising from the application of X-ray diffraction, and vibrational, electronic, and X-ray spectroscopies that exist, along with the results of theory. We aim to establish both what is known regarding these elusive materials and how they function, and also where gaps in our knowledge still exist, and offer suggestions and strategies as to how these might be closed such that the rational design of more effective and efficient materials of this type for the selective conversion of methane might proceed further.

In spite of numerous works in the field of chemical valorization of carbon dioxide into methanol, the nature of high activity of Cu/ZnO catalysts, including the reaction mechanism and the structure of the catalyst active site, remains the subject of intensive debate. By using high-pressure operando techniques: steady-state isotope transient kinetic analysis coupled with infrared spectroscopy, together with time-resolved X-ray absorption spectroscopy and X-ray powder diffraction, and supported by electron microscopy and theoretical modeling, we present direct evidence that zinc formate is the principal observable reactive intermediate, which in the presence of hydrogen converts into methanol. Our results indicate that the copper–zinc alloy undergoes oxidation under reaction conditions into zinc formate, zinc oxide and metallic copper. The intimate contact between zinc and copper phases facilitates zinc formate formation and its hydrogenation by hydrogen to methanol.

Heterogeneous catalysts play a pivotal role in the chemical industry. The strong metal-support interaction (SMSI), which affects the catalytic activity, is a phenomenon researched for decades. However, detailed mechanistic understanding on real catalytic systems is lacking. Here, this surface phenomenon was studied on an actual platinum-titania catalyst by state-of-the-art in situ electron microscopy, in situ X-ray photoemission spectroscopy and in situ X-ray diffraction, aided by density functional theory calculations, providing a novel real time view on how the phenomenon occurs. The migration of reduced titanium oxide, limited in thickness, and the formation of an alloy are competing mechanisms during high temperature reduction. Subsequent exposure to oxygen segregates the titanium from the alloy, and a thicker titania overlayer forms. This role of oxygen in the formation process and stabilization of the overlayer was not recognized before. It provides new application potential in catalysis and materials science.

A direct route to convert methane into high-value commodities, such as methanol, with high selectivity is one of the primary challenges in modern chemistry. Copper-exchanged zeolites show remarkable selectivity in the chemical looping process. Although multiple copper species have been proposed as active, an in situ spectroscopic investigation is difficult, because of their similar fingerprints. We used ambient pressure X-ray photoelectron spectroscopy to investigate an actual powder sample. We could discriminate between different types of active species involved in the conversion of methane to methanol over two different copper-exchanged zeolites, namely, mordenite and mazzite. After activation at 400 °C in oxygen, we followed the reaction in situ at 200 °C, switching from methane to water, and followed by a second cycle with anaerobic activation. Our experimental results, combined with theoretical calculations, prove that Cu(II) sites bound to extra-framework oxygen are involved in the reaction, and that their structure, formation, and stabilization depend on the type of zeolite and on the Si/Al ratio. ©

Direct methane functionalization and, in particular, the selective partial oxidation to methanol, remains an eminent challenge and a field of competitive research. The conversion of methane to methanol over transition-metal-containing zeolites using molecular oxygen is a promising and extensively studied process. Herein, we scrutinize some oft-cited assumptions in this topic—which include the labelling of the process as biomimetic, the debate regarding the industrial viability of direct methane-oxidation systems and the claim that methane is difficult to activate—and delineate the extent to which these are scientifically robust. We highlight both the merits and pitfalls of such statements and point out the hazards associated with their improper use. By examining these misconceptions, we build an outlook for future research, highlighting the need to optimize materials and process conditions for the stepwise approach and to further explore catalytic processes that explicitly employ strategies for the preservation of methanol.

Development of a suitable mild-condition process for direct conversion of methane to methanol faces multiple challenges, the principal ones being the higher reactivity of the primary oxidation products and the need for temperature swings in the typically employed chemical looping procedures. To circumvent these problems, the use of water as a mild oxidant has been recently suggested, leading to the concurrent formation of molecular hydrogen. By means of ab initio calculations, we address the experimentally observed features of the reaction to identify possible reaction pathways of such hydrogen release. We propose that, along with a strong stabilizing effect of water, short-lived [Cu-H] intermediate species play a crucial role in the mechanism of the reaction. Proton transfer from the Brønsted acid site of the zeolite framework via an adsorbed water molecule to the Cu^I species generates a [Cu-H] intermediate, which then facilitates the release of molecular hydrogen. This allows the reaction to proceed over a relatively low-energy transition state configuration. At the same time, excess of water leads to increased complexity of the concerted transition state, which results in hindering of the hydrogen transfer and increase of the corresponding energy barrier.

Through the combination of density functional theory calculations and ab initio atomistic thermodynamics modeling, we demonstrate that atomically dispersed platinum species on ceria can adopt a range of local coordination configurations and oxidation states that depend on the surface structure and environmental conditions. Unsaturated oxygen atoms on ceria surfaces play the leading role in stabilization of PtO_x species. Any mono-dispersed Pt⁰ species are thermodynamically unstable compared to bulk platinum, and oxidation of Pt⁰ to Pt²⁺ or Pt⁴⁺ is necessary to stabilize mono-dispersed platinum atoms. Reduction to Pt⁰ leads to sintering. Both Pt²⁺ and Pt⁴⁺ prefer to form the square-planar [PtO₄] configuration. The two most stable Pt²⁺ species on the (223) and (112) surfaces are thermodynamically favorable between 300 and 1200 K. The most stable Pt⁴⁺ species on the (100) surface tends to desorb from the surface as gas phase above 950 K. The resulting phase diagrams of the atomically dispersed platinum in PtO_x clusters on various ceria surfaces under a range of experimentally relevant conditions can be used to predict dynamic restructuring of atomically dispersed platinum catalysts and design new catalysts with engineered properties.

Samples of the zeolite mordenite with different Si/Al ratios were used to synthesize materials with monomeric and oligomeric copper sites that are active in the direct conversion of methane into methanol. A comparison of two reactivation protocols with oxygen (aerobic oxidation) and water (anaerobic oxidation), respectively, revealed that such copper–oxo species possess different reactivity towards methane and water. We show for the first time that oligomeric copper species exhibit high activity under both aerobic and anaerobic activation conditions, whereas monomeric copper sites produce methanol only in aerobic processes.