The Enigma of Methanol Synthesis by Cu/ZnO/Al2O3-Based Catalysts.

The activity and durability of the Cu/ZnO/Al2O3 (CZA) catalyst formulation for methanol synthesis from CO/CO2/H2 feeds far exceed the sum of its individual components. As such, this ternary catalytic system is a prime example of synergy in catalysis, one that has been employed for the large scale commercial production of methanol since its inception in the mid 1960s with precious little alteration to its original formulation. Methanol is a key building block of the chemical industry. It is also an attractive energy storage molecule, which can also be produced from CO2 and H2 alone, making efficient use of sequestered CO2. As such, this somewhat unusual catalyst formulation has an enormous role to play in the modern chemical industry and the world of global economics, to which the correspondingly voluminous and ongoing research, which began in the 1920s, attests. Yet, despite this commercial success, and while research aimed at understanding how this formulation functions has continued throughout the decades, a comprehensive and universally agreed upon understanding of how this material achieves what it does has yet to be realized. After nigh on a century of research into CZA catalysts, the purpose of this Review is to appraise what has been achieved to date, and to show how, and how far, the field has evolved. To do so, this Review evaluates the research regarding this catalyst formulation in a chronological order and critically assesses the validity and novelty of various hypotheses and claims that have been made over the years. Ultimately, the Review attempts to derive a holistic summary of what the current body of literature tells us about the fundamental sources of the synergies at work within the CZA catalyst and, from this, suggest ways in which the field may yet be further advanced.

Water structures on acidic zeolites and their roles in catalysis.

The local reaction environment of catalytic active sites can be manipulated to modify the kinetics and thermodynamic properties of heterogeneous catalysis. Because of the unique physical-chemical nature of water, heterogeneously catalyzed reactions involving specific interactions between water molecules and active sites on catalysts exhibit distinct outcomes that are different from those performed in the absence of water. Zeolitic materials are being applied with the presence of water for heterogeneous catalytic reactions in the chemical industry and our transition to sustainable energy. Mechanistic investigation and in-depth understanding about the behaviors and the roles of water are essentially required for zeolite chemistry and catalysis. In this review, we focus on the discussions of the nature and structures of water adsorbed/stabilized on Brønsted and Lewis acidic zeolites based on experimental observations as well as theoretical calculation results. The unveiled functions of water structures in determining the catalytic efficacy of zeolite-catalyzed reactions have been overviewed and the strategies frequently developed for enhancing the stabilization of zeolite catalysts are highlighted. Recent advancement will contribute to the development of innovative catalytic reactions and the rationalization of catalytic performances in terms of activity, selectivity and stability with the presence of water vapor or in condensed aqueous phase.

Operando Photoelectron Photoion Coincidence Spectroscopy to Detect Short-lived Intermediates in Catalysis.

Understanding the reaction mechanism is critical yet challenging in heterogeneous catalysis. Reactive intermediates, e.g., radicals and ketenes, are short-lived and often evade detection. In this review, we summarize recent developments with operando photoelectron photoion coincidence (PEPICO) spectroscopy as a versatile tool capable of detecting elusive intermediates. PEPICO combines the advantages of mass spectrometry and the isomer-selectivity of threshold photoelectron spectroscopy. Recent applications of PEPICO in understanding catalyst synthesis and catalytic reaction mechanisms involving gaseous and surface-confined radical and ketene chemistry will be summarized.

Cyclohexane Oxidative Dehydrogenation on Graphene-Oxide-Supported Cobalt Ferrite Nanohybrids: Effect of Dynamic Nature of Active Sites on Reaction Selectivity.

In this work, we investigated cyclohexane oxidative dehydrogenation (ODH) catalyzed by cobalt ferrite nanoparticles supported on reduced graphene oxide (RGO). We aim to identify the active sites that are specifically responsible for full and partial dehydrogenation using advanced spectroscopic techniques such as X-ray photoelectron emission microscopy (XPEEM) and X-ray photoelectron spectroscopy (XPS) along with kinetic analysis. Spectroscopically, we propose that Fe3+/Td sites could exclusively produce benzene through full cyclohexane dehydrogenation, while kinetic analysis shows that oxygen-derived species (O*) are responsible for partial dehydrogenation to form cyclohexene in a single catalytic sojourn. We unravel the dynamic cooperativity between octahedral and tetrahedral sites and the unique role of the support in masking undesired active (Fe3+/Td) sites. This phenomenon was strategically used to control the abundance of these species on the catalyst surface by varying the particle size and the wt % content of the nanoparticles on the RGO support in order to control the reaction selectivity without compromising reaction rates which are otherwise extremely challenging due to the much favorable thermodynamics for complete dehydrogenation and complete combustion under oxidative conditions.

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper-Containing Mordenite: Insights into Reaction Mechanism and Product Protection.

Copper(II)-containing mordenite (CuMOR) is capable of activation of C-H bonds in C1 -C3 alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time-resolved Cu K-edge X-ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π-complexes of olefins with CuI sites, formed upon reduction of CuII -oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.

In Situ Neutron Diffraction of Zn-MOF-74 Reveals Nanoconfinement-Induced Effects on Adsorbed Propene.

Even though confinement was identified as a common element of selective catalysis and simulations predicted enhanced properties of adsorbates within microporous materials, experimental results on the characterization of the adsorbed phase are still rare. In this study, we provide experimental evidence of the increase of propene density in the channels of Zn-MOF-74 by 16(2)% compared to the liquid phase. The ordered propene molecules adsorbed within the pores of the MOF have been localized by in situ neutron powder diffraction, and the results are supported by adsorption studies. The formation of a second adsorbate layer, paired with nanoconfinement-induced short intermolecular distances, causes the efficient packing of the propene molecules and results in an increase of olefin density.

Deciphering the Mechanism of Crystallization of UiO-66 Metal-Organic Framework.

Zirconium-containing metal-organic framework (MOF) with UiO-66 topology is an extremely versatile material, which finds applications beyond gas separation and catalysis. However, after more than 10 years after the first reports introducing this MOF, understanding of the molecular-level mechanism of its nucleation and growth is still lacking. By means of in situ time-resolved high-resolution mass spectrometry, Zr K-edge X-ray absorption spectroscopy, magic-angle spinning nuclear magnetic resonance spectroscopy, and X-ray diffraction it is showed that the nucleation of UiO-66 occurs via a solution-mediated hydrolysis of zirconium chloroterephthalates, whose formation appears to be autocatalytic. Zirconium-oxo nodes form directly and rapidly during the synthesis, the formation of pre-formed clusters and stable non-stoichiometric intermediates are not observed. The nuclei of UiO-66 possess identical to the crystals local environment, however, they lack long-range order, which is gained during the crystallization. Crystal growth is the rate-determining step, while fast nucleation controls the formation of the small crystals of UiO-66 with a narrow size distribution of about 200 nanometers.

Tuning the zeolite acidity enables selectivity control by suppressing ketene formation in lignin catalytic pyrolysis.

Unveiling catalytic mechanisms at a molecular level aids rational catalyst design and selectivity control for process optimization. In this study, we find that the Brønsted acid site density of the zeolite catalyst efficiently controls the guaiacol catalytic pyrolysis mechanism. Guaiacol demethylation to catechol initiates the reaction, as evidenced by the detected methyl radicals. The mechanism branches to form either fulvenone (c-C5H4 = C = O), a reactive ketene intermediate, by catechol dehydration, or phenol by acid-catalyzed dehydroxylation. At high Brønsted acid site density, fulvenone formation is inhibited due to surface coordination configuration of its precursor, catechol. By quantifying reactive intermediates and products utilizing operando photoelectron photoion coincidence spectroscopy, we find evidence that ketene suppression is responsible for the fivefold phenol selectivity increase. Complementary fulvenone reaction pathway calculations, along with 29Si NMR-MAS spectroscopy results corroborate the mechanism. The proposed, flexible operando approach is applicable to a broad variety of heterogeneous catalytic reactions.

Dynamical Equilibrium between Brønsted and Lewis Sites in Zeolites: Framework-Associated Octahedral Aluminum.

While the structures of Brønsted acid sites (BAS) in zeolites are well understood, those of Lewis acid sites (LAS) remain an active area of investigation. Under hydrated conditions, the reversible formation of framework-associated octahedral aluminum has been observed in zeolites in the acidic form. However, the structure and formation mechanisms are currently unknown. In this work, combined experimental 27 Al NMR spectroscopy and computational data reveal for the first time the details of the zeolite framework-associated octahedral aluminium. The octahedral LAS site becomes kinetically allowed and thermodynamically stable under wet conditions in the presence of multiple nearby BAS sites. The critical condition for the existence of such octahedral LAS appears to be the availability of three protons: at lower proton concentration, either by increasing the Si/Al or by ion-exchange to non-acidic form, the tetrahedral BAS becomes thermodynamically more stable. This work resolves the question about the nature and reversibility of framework-associated octahedral aluminium in zeolites.

Assessing the Productivity of the Direct Conversion of Methane-to-Methanol over Copper-Exchanged Zeolite Omega (MAZ) via Oxygen Looping.

The methane-to-methanol (MtM) conversion via the oxygen looping approach using copper-exchanged zeolites has been extensively studied over the last decade. While a lot of research has focussed on maximizing yield and selectivity, little has been directed toward productivity-a metric far more meaningful for evaluating industrial potential. Using copper-exchanged zeolite omega (Cu-omega), a material highly active and selective for the MtM conversion using the isothermal oxygen looping approach, we show that this material exhibits unprecedented potential for industrial valorization. In doing so, we also present a novel methodology combining operando XAS and mass spectrometry for the screening of materials for the MtM conversion in oxygen looping mode.

Tandem Hydroformylation-Aldol Condensation Reaction Enabled by Zn-MOF-74.

The tandem hydroformylation-aldol condensation (tandem HF-AC) reaction offers an efficient synthetic route to the synthesis of industrially relevant products. The addition of Zn-MOF-74 to the cobalt-catalyzed hydroformylation of 1-hexene enables tandem HF-AC under milder pressure and temperature conditions than the aldox process, where zinc salts are added to cobalt-catalyzed hydroformylation reactions to promote aldol condensation. The yield of the aldol condensation products increases by up to 17 times compared to that of the homogeneous reaction without MOF and up to 5 times compared to the aldox catalytic system. Both Co2 (CO)8 and Zn-MOF-74 are required to significantly enhance the activity of the catalytic system. Density functional theory simulations and Fourier-transform infrared experiments show that heptanal, the product of hydroformylation, adsorbs on the open metal site (OMS) of Zn-MOF-74, thereby increasing the electrophilic character of the carbonyl carbon atom and facilitating the condensation.

Controlling the Strong Metal-Support Interaction Overlayer Structure in Pt/TiO2 Catalysts Prevents Particle Evaporation.

Platinum nanoparticles (NPs) supported by titania exhibit a strong metal-support interaction (SMSI)[1] that can induce overlayer formation and encapsulation of the NP's with a thin layer of support material. This encapsulation modifies the catalyst's properties, such as increasing its chemoselectivity[2] and stabilizing it against sintering.[3] Encapsulation is typically induced during high-temperature reductive activation and can be reversed through oxidative treatments.[1] However, recent findings indicate that the overlayer can be stable in oxygen.[4, 5] Using in situ transmission electron microscopy, we investigated how the overlayer changes with varying conditions. We found that exposure to oxygen below 400 °C caused disorder and removal of the overlayer upon subsequent hydrogen treatment. In contrast, elevating the temperature to 900 °C while maintaining the oxygen atmosphere preserved the overlayer, preventing platinum evaporation when exposed to oxygen. Our findings demonstrate how different treatments can influence the stability of nanoparticles with or without titania overlayers. expanding the concept of SMSI and enabling noble metal catalysts to operate in harsh environments without evaporation associated losses during burn-off cycling.

Platinum-Iron(II) Oxide Sites Directly Responsible for Preferential Carbon Monoxide Oxidation at Ambient Temperature: An Operando X-ray Absorption Spectroscopy Study.

Operando X-ray absorption spectroscopy identified that the concentration of Fe2+ species in the working state-of-the-art Pt-FeOx catalysts quantitatively correlates to their preferential carbon monoxide oxidation steady-state reaction rate at ambient temperature. Deactivation of such catalysts with time on stream originates from irreversible oxidation of active Fe2+ sites. The active Fe2+ species are presumably Fe+2 O-2 clusters in contact with platinum nanoparticles; they coexist with spectator trivalent oxidic iron (Fe3+ ) and metallic iron (Fe0 ) partially alloyed with platinum. The concentration of active sites and, therefore, the catalyst activity strongly depends on the pretreatment conditions. Fe2+ is the resting state of the active sites in the preferential carbon monoxide oxidation cycle.

The Extent of Platinum-Induced Hydrogen Spillover on Cerium Dioxide.

Hydrogen spillover from metal nanoparticles to oxides is an essential process in hydrogenation catalysis and other applications such as hydrogen storage. It is important to understand how far this process is reaching over the surface of the oxide. Here, we present a combination of advanced sample fabrication of a model system and in situ X-ray photoelectron spectroscopy to disentangle local and far-reaching effects of hydrogen spillover in a platinum-ceria catalyst. At low temperatures (25-100 °C and 1 mbar H2) surface O-H formed by hydrogen spillover on the whole ceria surface extending microns away from the platinum, leading to a reduction of Ce4+ to Ce3+. This process and structures were strongly temperature dependent. At temperatures above 150 °C (at 1 mbar H2), O-H partially disappeared from the surface due to its decreasing thermodynamic stability. This resulted in a ceria reoxidation. Higher hydrogen pressures are likely to shift these transition temperatures upward due to the increasing chemical potential. The findings reveal that on a catalyst containing a structure capable to promote spillover, hydrogen can affect the whole catalyst surface and be involved in catalysis and restructuring.

Alumina-Supported NiMo Hydrotreating Catalysts-Aspects of 3D Structure, Synthesis, and Activity.

Preparation conditions have a vital effect on the structure of alumina-supported hydrodesulfurization (HDS) catalysts. To explore this effect, we prepared two NiMoS/Al2O3 catalyst samples with the same target composition using different chemical sources and characterizing the oxidic NiMo precursors and sulfided and spent catalysts to understand the influence of catalyst structure on performance. The sample prepared from ammonium heptamolybdate and nickel nitrate (sample A) contains Mo in the oxidic precursor predominantly in tetrahedral coordination in the form of crystalline domains, which show low reducibility and strong metal-support interactions. This property influences the sulfidation process such that the sulfidation processes of Ni and Mo occur tendentially separately with a decreased efficiency to form active Ni-Mo-S particles. Moreover, inactive unsupported MoS2 particles or isolated NiS x species are formed, which are either washed off during catalytic reaction or aggregated to larger particles as seen in scanning transmission electron microscopy/energy-dispersive X-ray spectroscopy (STEM/EDX). The oxidic precursor of the sample synthesized using nickel carbonate and molybdenum trioxide as metal sources (sample B), however, contains Mo in octahedral coordination and shows higher reducibility of the metal species as well as weaker metal-support interactions than that of sample A; these properties allow an efficient sulfidation of Mo and Ni such that formation of active Ni-Mo-S particles is the main product. Ptychographic X-ray computed tomography (PXCT) and STEM and EDX measurements show that the structure formed during sulfidation is stable under operation conditions. The structural differences explain the HDS activity difference between these two samples and explain why sample B is much active than sample A.

Hydrogen Interaction with Oxide Supports in the Presence and Absence of Platinum.

Oxides are essential catalysts and supports for noble metal catalysts. Their interaction with hydrogen enables, e.g., their use as a hydrogenation catalyst. Among the oxides considered reducible, substantial differences exist in their capability to activate hydrogen and how the oxide structure transforms due to this interaction. Noble metals, like platinum, generally enhance the oxide reduction by hydrogen spillover. This work presents a systematic temperature-programmed reduction study (300 to 873 K) of iron oxide, ceria, titania, zirconia, and alumina, with and without supported platinum. For all catalysts, platinum enhances the reducibility of the oxide. However, there are pronounced differences among all catalysts.

Operando PEPICO unveils the catalytic fast pyrolysis mechanism of the three methoxyphenol isomers.

The development of lignin valorization processes such as catalytic fast pyrolysis (CFP) to produce fine chemicals and fuels leads to a more sustainable future. The implementation of CFP is enabled by understanding the chemistry of lignin constituents, which, however, requires thorough mechanistic investigations by detecting reactive species. In this contribution, we investigate the CFP of the three methoxyphenol (MP) isomers over H-ZSM-5 utilizing vacuum ultraviolet synchrotron radiation and operando photoelectron photoion coincidence (PEPICO) spectroscopy. All isomers demethylate at first to yield benzenediols, from which dehydroxylation reactions proceed to produce phenol and benzene. Additional pathways to form benzene proceed over cyclopentadiene, methylcyclopentadiene, and fulvene intermediates. The detection of trace amounts of methanol in the product stream suggests a demethoxylation reaction to yield phenol. Guaiacol (2- or ortho-MP) exhibits slightly higher reactivity compared to 3-MP and 4-MP, due to the formation of the fulvenone ketene, which opens additional routes to benzene and phenol. When compared to benzenediol catalytic pyrolysis, the additional methyl group in MP leads to high conversion at lower reactor temperatures, which is mostly owed to the lower H3C-O vs. H-O bond energy and the possibility to demethoxylate to produce phenol.

Reply to "Comment on 'Liquid-Gas Interface of Iron Aqueous Solutions and Fenton Reagents'".

A Viewpoint regarding our recently published Letter in this Journal (Gladich et al. J. Phys. Chem. Lett. 13, 2994-3001) criticizes some of our conclusions. While a sentence in the abstract and one in the conclusion of the Letter might seem too conclusive, in the body text we objectively discussed experimental results obtained by means of three different surface-/interface-sensitive spectroscopies. Such results were supported by theoretical calculations. The aim of our work was not to criticize past results. On the contrary, we critically discussed our data taking into account those obtained in the past.