Combined high-resolution fluorescence detection X-ray absorption near-edge spectroscopy, X-ray diffraction, and X-ray emission spectroscopy have been employed under operando conditions to obtain detailed new insight into the nature of the Mo species on zeolite ZSM-5 during methane dehydroaromatization. The results show that isolated Mo–oxo species present after calcination are converted by CH₄ into metastable MoC_xO_y species, which are primarily responsible for C₂H_x/C₃H_x formation. Further carburization leads to MoC₃ clusters, whose presence coincides with benzene formation. Both sintering of MoC₃ and accumulation of large hydrocarbons on the external surface, evidenced by fluorescence-lifetime imaging microscopy, are principally responsible for the decrease in catalytic performance. These results show the importance of controlling Mo speciation to achieve the desired product formation, which has important implications for realizing the impact of CH₄ as a source for platform chemicals.

Structure–activity relationships in heterogeneous catalysis are challenging to be measured on a single-particle level. For the first time, one X-ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm-resolved X-ray diffraction (μ-XRD) and X-ray excited optical fluorescence (μ-XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ-XEOF) were correlated with local crystallinity and framework Al content, determined by μ-XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X-ray induced fluorescence of organic molecules formed at the reactive centers.

A novel laboratory setup for combined operando X-ray diffraction and Raman spectroscopy of catalytic solids with online product analysis by gas chromatography is presented. The setup can be used with a laboratory-based X-ray source, which results in important advantages in terms of time-on-stream that can be measured, compared to synchrotron-based experiments. The data quality was much improved by the use of a relatively high-energy MoK_α radiation instead of the more conventional CuK_α radiation. We have applied the instrument to study the long-term deactivation of Co/TiO₂ Fischer–Tropsch synthesis (FTS) catalysts. No sign of Co sintering or bulk oxidation was found during the experiments. However, part of the metallic Co was converted into cobalt carbide (Co₂C), at elevated pressure (10 bar). Furthermore, graphitic-like coke species are clearly formed during FTS at atmospheric pressure, whereas at elevated pressure fluorescence hampered the interpretation of the measured Raman spectra.

A diffuse reflectance infrared Fourier-transform (DRIFT) study has been conducted at 373 K and 1 bar on an industrial Cr/Ti/SiO₂ Phillips-type catalyst modified with, and without, triethylaluminium (TEAl) as co-catalyst. The reaction rate of the polymerization of ethylene, as monitored by the increase in the methylene stretching band of the growing polyethylene (PE), has been investigated as a function of the titanium content. After an initial period of mixed kinetics, with the reaction rate significantly higher for the TEAl-modified catalysts compared with the non-modified catalysts, the polymerization proceeded as a pseudo-zero-order reaction with a reaction rate that increased as a function of titanium loading. Furthermore, it was found that the higher Ti loading caused the appearance of more acidic hydroxyl groups and modified the Cr sites by making them more Lewis acidic, ultimately shortening the induction time and increasing the initial polymerization rate.

Structure–activity relationships in heterogeneous catalysis are challenging to be measured on a single-particle level. For the first time, one X-ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm-resolved X-ray diffraction (μ-XRD) and X-ray excited optical fluorescence (μ-XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ-XEOF) were correlated with local crystallinity and framework Al content, determined by μ-XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X-ray induced fluorescence of organic molecules formed at the reactive centers.

Combined high-resolution fluorescence detection X-ray absorption near-edge spectroscopy, X-ray diffraction, and X-ray emission spectroscopy have been employed under operando conditions to obtain detailed new insight into the nature of the Mo species on zeolite ZSM-5 during methane dehydroaromatization. The results show that isolated Mo–oxo species present after calcination are converted by CH₄ into metastable MoC_xO_y species, which are primarily responsible for C₂H_x/C₃H_x formation. Further carburization leads to MoC₃ clusters, whose presence coincides with benzene formation. Both sintering of MoC₃ and accumulation of large hydrocarbons on the external surface, evidenced by fluorescence-lifetime imaging microscopy, are principally responsible for the decrease in catalytic performance. These results show the importance of controlling Mo speciation to achieve the desired product formation, which has important implications for realizing the impact of CH₄ as a source for platform chemicals.

Large zeolite crystals of ferrierite have been used to study the deactivation, at the single particle level, of the alkyl isomerisation catalysis of oleic acid and elaidic acid by a combination of visible micro-spectroscopy and fluorescence microscopy (both polarised wide-field and confocal modes). The large crystals did show the desired activity, albeit only traces of the isomerisation product were obtained and low conversions were achieved compared to commercial ferrierite powders. This limited activity is in line with their lower external non-basal surface area, supporting the hypothesis of pore mouth catalysis. Further evidence for the latter comes from visible micro-spectroscopy, which shows that the accumulation of aromatic species is limited to the crystal edges, while fluorescence microscopy strongly suggests the presence of polyenylic carbocations. Light polarisation associated with the spatial resolution of fluorescence microscopy reveals that these carbonaceous deposits are aligned only in the larger 10-MR channels of ferrierite at all crystal edges. The reaction is hence further limited to these specific pore mouths.

The synthesis of phase-pure Co-ZIF-9, an important cobalt-based zeolitic imidazolate framework, could be achieved by modification of the reported synthesis procedure through pH adjustment of the starting synthesis mixture. The phase-pure Co-ZIF-9 material obtained has been characterized by a combination of UV/Vis, FTIR, and Raman spectroscopy as well as by thermogravimetric analysis (TGA) and XRD and possesses a lower overall crystallinity. This can be explained by the addition of the base for the pH adjustment method. On the basis of these findings, a synthesis pathway for the formation of the secondary phase, cobalt formate, is proposed along with its relationship to the flexibility of the coordination environment of cobalt ions. The crystal structures of both phases have been determined by single-crystal X-ray crystallography, and the resolved structures also reflect the coordination flexibility of the framework cobalt ions.

A triethylaluminium(TEAl)-modified Phillips ethylene polymerisation Cr/Ti/SiO₂ catalyst has been developed with two distinct active regions positioned respectively in the inner core and outer shell of the catalyst particle. DRIFTS, EPR, UV-Vis-NIR DRS, STXM, SEM-EDX and GPC-IR studies revealed that the catalyst produces simultaneously two different polymers, i.e., low molecular weight linear-chain polyethylene in the Ti-abundant catalyst particle shell and high molecular weight short-chain branched polyethylene in the Ti-scarce catalyst particle core. Co-monomers for the short-chain branched polymer were generated in situ within the TEAl-impregnated confined space of the Ti-scarce catalyst particle core in close proximity to the active sites that produced the high molecular weight polymer. These results demonstrate that the catalyst particle architecture directly affects polymer composition, offering the perspective of making high-performance polyethylene from a single reactor system using this modified Phillips catalyst.

Microspectroscopic methods were explored to investigate binder effects occurring in ZSM-5-containing SiO₂- and Al₂O₃-bound millimetre-sized extrudates. Using thiophene as a selective probe for Brønsted acidity, coupled with time-resolved in situ UV/Vis and confocal fluorescence microspectroscopy, variations in reactivity and selectivity between the two distinct binder types were established. It was found that aluminium migration occurs in ZSM-5-containing Al₂O₃-bound extrudates, forming additional Brønsted acid sites. These sites strongly influence the oligomer selectivity, favouring the formation of thiol-like species (i.e., ring-opened species) in contrast to higher oligomers, predominantly formed on SiO₂-bound ZSM-5-containing extrudates. Not only were the location and distribution of these oligomers visualised by 3 D analysis, it was also observed that more conjugated species appeared to grow off the surface of the zeolite ZSM-5 crystals (containing less conjugated species) into the surrounding binder material. Furthermore, a higher binder content resulted in an increasing overall reactivity owing to the greater number of stored thiophene monomers available per Brønsted acid site.

Glycerol is an attractive renewable building block for the synthesis of polyglycerols, which find application in the cosmetic and pharmaceutical industries. The selective etherification of glycerol to higher oligomers was studied in the presence of CaO colloids and the data are compared with those obtained from NaOH and CaO. The materials were prepared by dispersing CaO, CaCO₃, or Ca(OH)₂ onto a carbon nanofiber (CNF) support. Colloidal nanoparticles were subsequently dispensed from the CNF into the reaction mixture to give CaO colloids that have a higher activity than equimolar amounts of bulk CaO and NaOH. Optimization of the reaction conditions allowed us to obtain a product with Gardner color number <2, containing no acrolein and minimal cyclic byproducts. The differences in the CaO colloids originating from CNF and bulk CaO were probed using light scattering and conductivity measurements. The results confirmed that the higher activity of the colloids originating from CaO/CNF was due to their more rapid formation and smaller size compared with colloids from bulk CaO. We thus have developed a practical method for the synthesis of polyglycerols containing low amounts of Ca.

Straightforward analysis of chemical processes on the nanoscale is difficult, as the measurement volume is linked to a discrete number of molecules, ruling out any ensemble averaging over rotation and diffusion processes. Raman spectroscopy is sufficiently selective for monitoring chemical changes, but is not sufficiently sensitive to be applied directly. Surface-enhanced Raman spectroscopy (SERS) can be applied for studying reaction kinetics, but adds additional variability in the signal as the enhancement factor is not the same for every location. A novel chemometric method described here separates reaction kinetics from short-term variability, based on the lack of fit in a principal-component analysis. We show that it is possible to study effects that occur on different time scales independently without data reduction using the photocatalytic reduction of p-nitrothiophenol as a showcase system. Using this approach a better description of the nanoscale reaction kinetics becomes available, while the short-term variations can be examined separately to examine reorientation and/or diffusion effects. It may even be possible to identify reaction intermediates through this approach. With only a limited number of reactive molecules in the studied volume, an intermediate on a SERS hot spot may temporarily dominate the spectrum. Now such events can be easily separated from the bulk conversion process by making use of this chemometric method.

The front cover artwork is provided by Prof. Bert Weckhuysen (Utrecht University, The Netherlands). The image outlines the experimental approach taken. Single Ag nanoparticles (grey) are deposited on a self-assembled monolayer of­ p-nitrothiophenol (pNTP, red) assembled on a flat Au substrate (yellow). The monolayer of pNTP can be reduced to p,p’-dimercaptoazobisbenzene (DMAB) through photocatalysis over plasmonic nanoparticles. By using a laser excitation of 785 nm (yellow arrow) the coupled plasmons of Au and Ag are excited and give sufficient surface enhanced Raman spectroscopy (SERS) enhancement effect to observe dynamics and kinetics over single nanoparticle hotspots. Read the full text of the article at 10.1002/cphc.201402709.

The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results.

A triethylaluminium(TEAl)-modified Phillips ethylene polymerisation Cr/Ti/SiO₂ catalyst has been developed with two distinct active regions positioned respectively in the inner core and outer shell of the catalyst particle. DRIFTS, EPR, UV-Vis-NIR DRS, STXM, SEM-EDX and GPC-IR studies revealed that the catalyst produces simultaneously two different polymers, i.e., low molecular weight linear-chain polyethylene in the Ti-abundant catalyst particle shell and high molecular weight short-chain branched polyethylene in the Ti-scarce catalyst particle core. Co-monomers for the short-chain branched polymer were generated in situ within the TEAl-impregnated confined space of the Ti-scarce catalyst particle core in close proximity to the active sites that produced the high molecular weight polymer. These results demonstrate that the catalyst particle architecture directly affects polymer composition, offering the perspective of making high-performance polyethylene from a single reactor system using this modified Phillips catalyst.

A variety of phosphated zeolite H-ZSM-5 samples are investigated by using a combination of Fourier transfer infrared (FTIR) spectroscopy, single pulse ²⁷Al, ²⁹Si, ³¹P, ¹H-³¹P cross polarization (CP), ²⁷Al-³¹P CP, and ²⁷Al 3Q magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, scanning transmission X-ray microscopy (STXM) and N₂ physisorption. This approach leads to insights into the physicochemical processes that take place during phosphatation. Direct phosphatation of H-ZSM-5 promotes zeolite aggregation, as phosphorus does not penetrate deep into the zeolite material and is mostly found on and close to the outer surface of the zeolite, acting as a glue. Phosphatation of pre-steamed H-ZSM-5 gives rise to the formation of a crystalline tridymite AlPO₄ phase, which is found in the mesopores of dealuminated H-ZSM-5. Framework aluminum species interacting with phosphorus are not affected by hydrothermal treatment. Dealuminated H-ZSM-5, containing AlPO₄, retains relatively more framework Al atoms and acid sites during hydrothermal treatment than directly phosphated H-ZSM-5.

Confocal fluorescence microscopy was employed to selectively visualize the dispersion and orientation of zeolite ZSM-5 domains inside a single industrially applied fluid catalytic cracking (FCC) catalyst particle. Large ZSM-5 crystals served as a model system together with the acid-catalyzed fluorostyrene oligomerization reaction to study the interaction of plane-polarized light with these anisotropic zeolite crystals. The distinction between zeolite and binder material, such as alumina, silica, and clay, within an individual FCC particle was achieved by utilizing the anisotropic nature of emitted fluorescence light arising from the entrapped fluorostyrene-derived carbocations inside the zeolite channels. This characterization approach provides a non-invasive way for post-synthesis characterization of an individual FCC catalyst particle in which the size, distribution, orientation, and amount of zeolite ZSM-5 aggregates can be determined. It was found that the amount of detected fluorescence light originating from the stained ZSM-5 aggregates corresponds to about 15 wt %. Furthermore, a statistical analysis of the emitted fluorescence light indicated that a large number of the ZSM-5 domains appeared in small sizes of about 0.015–0.25 μm², representing single zeolite crystallites or small aggregates thereof. This observation illustrated a fairly high degree of zeolite dispersion within the FCC binder material. However, the highest amount of crystalline material was aggregated into larger domains (ca. 1–5 μm²) with more or less similarly oriented zeolite crystallites. It is clear that this visualization approach may serve as a post-synthesis quality control on the dispersion of zeolite ZSM-5 crystallites within FCC particles.

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga³⁺ species are the active species and where Pt functions as a promoter.

The nature behind the promotional effect of phosphorus on the catalytic performance and hydrothermal stability of zeolite H-ZSM-5 has been studied using a combination of ²⁷Al and ³¹P MAS NMR spectroscopy, soft X-ray absorption tomography and n-hexane catalytic cracking, complemented with NH₃ temperature-programmed desorption and N₂ physisorption. Phosphated H-ZSM-5 retains more acid sites and catalytic cracking activity after steam treatment than its non-phosphated counterpart, while the selectivity towards propylene is improved. It was established that the stabilization effect is twofold. First, the local framework silico-aluminophosphate (SAPO) interfaces, which form after phosphatation, are not affected by steam and hold aluminum atoms fixed in the zeolite lattice, preserving the pore structure of zeolite H-ZSM-5. Second, the four-coordinate framework aluminum can be forced into a reversible sixfold coordination by phosphate. These species remain stationary in the framework under hydrothermal conditions as well. Removal of physically coordinated phosphate after steam-treatment leads to an increase in the number of strong acid sites and increased catalytic activity. We propose that the improved selectivity towards propylene during catalytic cracking can be attributed to local SAPO interfaces located at channel intersections, where they act as impediments in the formation of bulky carbenium ions and therefore suppress the bimolecular cracking mechanism.

Silica–magnesia (Si/Mg=1:1) catalysts were studied in the one-pot conversion of ethanol to butadiene. The catalyst synthesis method was found to greatly influence morphology and performance, with materials prepared through wet-kneading performing best both in terms of ethanol conversion and butadiene yield. Detailed characterization of the catalysts synthesized through co-precipitation or wet-kneading allowed correlation of activity and selectivity with morphology, textural properties, crystallinity, and acidity/basicity. The higher yields achieved with the wet-kneaded catalysts were attributed to a morphology consisting of SiO₂ spheres embedded in a thin layer of MgO. The particle size of the SiO₂ catalysts also influenced performance, with catalysts with smaller SiO₂ spheres showing higher activity. Temperature-programmed desorption (TPD) measurements showed that best butadiene yields were obtained with SiO₂–MgO catalysts characterized by an intermediate amount of acidic and basic sites. A Hammett indicator study showed the catalysts’ pK_a value to be inversely correlated with the amount of dehydration by-products formed. Butadiene yields could be further improved by the addition of 1 wt % of CuO as promoter to give butadiene yields and selectivities as high as 40 % and 53 %, respectively. The copper promoter boosts the production of the acetaldehyde intermediate changing the rate-determining step of the process. TEM-energy-dispersive X-ray (EDX) analyses showed CuO to be present on both the SiO₂ and MgO components. UV/Vis spectra of promoted catalysts in turn pointed at the presence of cluster-like CuO species, which are proposed to be responsible for the increased butadiene production.

Heterogeneous catalysis is a surface phenomenon. Yet, though the catalysis itself takes place on surfaces, the reactants and products rapidly take the form of another physical state, as either a liquid or a gas. Catalytic reactions within a self-assembled monolayer are confined within two dimensions, as the molecules involved do not leave the surface. Surface-enhanced Raman spectroscopy is an ideal technique to probe these self-assembled monolayers as it gives molecular information in a measured volume limited to the surface. We show how surface-enhanced Raman spectroscopy can be used to determine the reaction kinetics of a two-dimensional reaction. As a proof of principle, we study the photocatalytic reduction of p-nitrothiophenol. A study of the reaction rate and dilution effects leads to the conclusion that a dimerization must take place as one of the reaction steps.

The front cover artwork for Issue 3/2014 is provided by the Inorganic Chemistry and Catalysis group of Utrecht University. The image shows the concept of synchrotron-based IR and UV/Vis microspectroscopy monitoring a catalytic reaction on a single SAPO-34 crystal and the obtained spatially resolved information on the retained hydrocarbon species and crystal accessibility. See the Full Paper itself on http://dx.doi.org/10.1002/cctc.201300962.

A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga³⁺ species are the active species and where Pt functions as a promoter.

In situ synchrotron-based IR and UV/Vis micro-spectroscopy combined with isotopically labeled reactants have been used to identify the different hydrocarbon species formed as well as to assess the activity and accessibility of individual 50 μm-sized SAPO-34 crystals. For the methanol-to-olefins process, two reaction stages can be distinguished. The first involves the formation of methoxy species, protonated dimethyl ether, and polyalkylated benzene (PAB) carbocations, which do not affect the accessibility of the SAPO-34 crystal. In addition, methoxy species are very dynamic during this stage. The second stage is related to the formation of polyaromatic (PA) species concentrated in the outer rim of the crystal, which are bulky and interact with the acid sites and thus alter the overall accessibility of the crystal. In contrast, the ethanol-to-olefins process only consists of one major stage, as the formation of PAB and PA species cannot be separated. Furthermore, the formation of these species is more internal, and coke formation is mainly concentrated in a layer located in the inner part of the SAPO-34 crystal.

Combined operando UV/vis–Raman spectroscopy has been used to study the deactivation of CrO_x/Al₂O₃ catalyst extrudates in a pilot scale propane dehydrogenation reactor. For this purpose, UV/vis and Raman optical fiber probes have been designed, constructed and tested. The light absorption measured by operando UV/vis spectroscopy was used to correct for the effect of catalyst darkening. This makes operando Raman spectroscopy a quantitative technique to follow the formation of coke deposits on-line during the first hour of catalytic propane dehydrogenation process. The probe was used to study the coke deposition at the top and bottom of the reactor. Differences in the rate of coke deposition were observed, which were related to the local temperature of the catalyst bed. The chemical nature of the coke deposits formed on a catalyst extrudate, as expressed by the D₁/G ratio, was independent of reaction time as well as of the position of the catalyst extrudate within the reactor bed.

The methanol-to-olefins (MTO) process over H-SAPO-34 is investigated by using an operando approach combining UV/Vis and IR spectroscopies with on-line mass spectrometry. Methanol, methoxy, and protonated dimethyl ether are the major species during the induction period, whereas polyalkylated benzenes and polyaromatic species are encountered in the active stage of the MTO process. The accessibility of SAPO-34 is linked with the amount of methoxy species, whereas the formation of polyaromatic species that block the pores is the main cause of deactivation. Furthermore, the reaction pathways responsible for the formation of olefins and polyaromatics co-exist and compete during the whole MTO process, and both routes are directly related to the amount of surface polyalkylated benzene carbocations and methoxy species. Hence, a first-order kinetic model is proposed and comparable activation energies for both processes are obtained.

Neither the routes through which humin byproducts are formed, nor their molecular structure have yet been unequivocally established. A better understanding of the formation and physicochemical properties of humins, however, would aid in making biomass conversion processes more efficient. Here, an extensive multiple-technique-based study of the formation, molecular structure, and morphology of humins is presented as a function of sugar feed, the presence of additives (e.g., 1,2,4-trihydroxybenzene), and the applied processing conditions. Elemental analyses indicate that humins are formed through a dehydration pathway, with humin formation and levulinic acid yields strongly depending on the processing parameters. The addition of implied intermediates to the feedstocks showed that furan and phenol compounds formed during the acid-catalyzed dehydration of sugars are indeed included in the humin structure. IR spectra, sheared sum projections of solid-state 2DPASS ¹³C NMR spectra, and pyrolysis GC–MS data indicate that humins consist of a furan-rich polymer network containing different oxygen functional groups. The structure is furthermore found to strongly depend on the type of feedstock. A model for the molecular structure of humins is proposed based on the data presented.

The catalytic, deactivation, and regeneration characteristics of large coffin-shaped H-ZSM-5 crystals were investigated during the methanol-to-hydrocarbons (MTH) reaction at 350 and 500 °C. Online gas-phase effluent analysis and examination of retained material thereof were used to explore the bulk properties of large coffin-shaped zeolite H-ZSM-5 crystals in a fixed-bed reactor to introduce them as model catalysts for the MTH reaction. These findings were related to observations made at the individual particle level by using polarization-dependent UV-visible microspectroscopy and mass spectrometric techniques after reaction in an in situ microspectroscopy reaction cell. Excellent agreement between the spectroscopic measurements and the analysis of hydrocarbon deposits by means of retained hydrocarbon analysis and time-of-flight secondary-ion mass spectrometry of spent catalyst materials was observed. The obtained data reveal a shift towards more condensed coke deposits on the outer zeolite surface at higher reaction temperatures. Zeolites in the fixed-bed reactor setup underwent more coke deposition than those reacted in the in situ microspectroscopy reaction cell. Regeneration studies of the large zeolite crystals were performed by oxidation in O₂/inert gas mixtures at 550 °C. UV-visible microspectroscopic measurements using the oligomerization of styrene derivatives as probe reaction indicated that the fraction of strong acid sites decreased during regeneration. This change was accompanied by a slight decrease in the initial conversion obtained after regeneration. H-ZSM-5 deactivated more rapidly at higher reaction temperature.

The formation of hydrocarbon pool (HCP) species during methanol-to-olefin (MTO) and ethanol-to-olefin (ETO) processes have been studied on individual micron-sized SAPO-34 crystals with a combination of in situ UV/Vis, confocal fluorescence, and synchrotron-based IR microspectroscopic techniques. With in situ UV/Vis microspectroscopy, the intensity changes of the λ=400 nm absorption band, ascribed to polyalkylated benzene (PAB) carbocations, have been monitored and fitted with a first-order kinetics at low reaction temperatures. The calculated activation energy (E_a) for MTO, approximately 98 kJ mol⁻¹, shows a strong correlation with the theoretical values for the methylation of aromatics. This provides evidence that methylation reactions are the rate-determining steps for the formation of PAB. In contrast for ETO, the E_a value is approximately 60 kJ mol⁻¹, which is comparable to the E_a values for the condensation of light olefins into aromatics. Confocal fluorescence microscopy demonstrates that during MTO the formation of the initial HCP species are concentrated in the outer rim of the SAPO-34 crystal when the reaction temperature is at 600 K or lower, whereas larger HCP species are gradually formed inwards the crystal at higher temperatures. In the case of ETO, the observed egg-white distribution of HCP at 509 K suggests that the ETO process is kinetically controlled, whereas the square-shaped HCP distribution at 650 K is indicative of a diffusion-controlled process. Finally, synchrotron-based IR microspectroscopy revealed a higher degree of alkylation for aromatics for MTO as compared to ETO, whereas high reaction temperatures favor dealkylation processes for both the MTO and ETO processes.

Heterogeneous catalysts often consist of an active metal (oxide) in close contact with a support material and various promoter elements. Although macroscopic properties, such as activity, selectivity and stability, can be assessed with catalyst performance testing, the development of relevant, preferably quantitative structure–performance relationships require the use of advanced characterisation methods. Spectroscopic imaging in the hard X-ray region with nanometer-scale resolution has very recently emerged as a powerful approach to elucidate the hierarchical structure and related chemistry of catalytic solids in action under realistic reaction conditions. This X-ray-based chemical imaging method benefits from the combination of high resolution (∼30 nm) with large X-ray penetration and depth of focus, and the possibility for probing large areas with mosaic imaging. These capabilities make it possible to obtain spatial and temporal information on chemical changes in catalytic solids as well as a wide variety of other functional materials, such as fuel cells and batteries, in their full complexity and integrity. In this concept article we provide details on the method and setup of full-field hard X-ray spectroscopic imaging, illustrate its potential for spatiotemporal chemical imaging by making use of recent showcases, outline the pros and cons of this experimental approach and discuss some future directions for hierarchical functional materials research.

The development of new and improved processes for the synthesis of bio-based chemicals is one of the scientific challenges of our time. These new discoveries are not only important from an environmental point of view, but also represent an important economic opportunity, provided that the developed processes are selective and efficient. Bioethanol is currently produced from renewable resources in large amounts and, in addition to its use as biofuel, holds considerable promise as a building block for the chemical industry. Indeed, further improvements in production, both in terms of efficiency and feedstock selection, will guarantee availability at competitive prices. The conversion of bioethanol into commodity chemicals, in particular direct ‘drop-in’ replacements is, therefore, becoming increasingly attractive, provided that the appropriate (catalytic) technology is in place. The production of green and renewable 1,3-butadiene is a clear example of this approach. The Lebedev process for the one-step catalytic conversion of ethanol to butadiene has been known since the 1930s and has been applied on an industrial scale to produce synthetic rubber. Later, the availability of low-cost oil made it more convenient to obtain butadiene from petrochemical sources. The desire to produce bulk chemicals in a sustainable way and the availability of low-cost bioethanol in large volumes has, however, resulted in a renaissance of this old butadiene production process. This paper reviews the catalytic aspects associated with the synthesis of butadiene via the Lebedev process, as well as the production of other, mechanistically related bulk chemicals that can be obtained from (bio)ethanol.

The formation and nature of active sites for methanol conversion over solid acid catalyst materials are studied by using a unique combined spectroscopic and theoretical approach. A working catalyst for the methanol-to-olefin conversion has a hybrid organic–inorganic nature in which a cocatalytic organic species is trapped in zeolite pores. As a case study, microporous materials with the chabazite topology, namely, H-SAPO-34 and H-SSZ-13, are considered with trapped (poly)aromatic species. First-principle rate calculations on methylation reactions and in situ UV/Vis spectroscopy measurements are performed. The theoretical results show that the structure of the organic compound and zeolite composition determine the methylation rates: 1) the rate increases by 6 orders of magnitude if more methyl groups are added on benzenic species, 2) transition state selectivity occurs for organic species with more than one aromatic core and bearing more than three methyl groups, 3) methylation rates for H-SSZ-13 are approximately 3 orders of magnitude higher than on H-SAPO-34 owing to its higher acidity. The formation of (poly)aromatic cationic compounds can be followed by using in situ UV/Vis spectroscopy because these species yield characteristic absorption bands in the visible region of the spectrum. We have monitored the growth of characteristic peaks and derived activation energies of formation for various sets of (poly)aromatic compounds trapped in the zeolite host. The formation–activation barriers deduced by using UV/Vis microspectroscopy correlate well with the activation energies for the methylation of the benzenic species and the lower methylated naphthalenic species. This study shows that a fundamental insight at the molecular level can be obtained by using a combined in situ spectroscopic and theoretical approach for a complex catalyst of industrial relevance.

While cycling through a fluid catalytic cracking (FCC) unit, the structure and performance of FCC catalyst particles are severely affected. In this study, we set out to characterize the damage to commercial equilibrium catalyst particles, further denoted as ECat samples, and map the different pathways involved in their deactivation in a practical unit. The degradation was studied on a structural and a functional level. Transmission electron microscopy (TEM) of ECat samples revealed several structural features; including zeolite crystals that were partly or fully severed, mesoporous, macroporous, and/or amorphous. These defects were then correlated to structural features observed in FCC particles that were treated with different levels of hydrothermal deactivation. This allowed us not only to identify which features observed in ECat samples were a result of hydrothermal deactivation, but also to determine the severity of treatments resulting in these defects. For functional characterization of the ECat sample, the Brønsted acidity within individual FCC particles was studied by a selective fluorescent probe reaction with 4-fluorostyrene. Integrated laser and electron microscopy (iLEM) allowed correlating this Brønsted acidity to structural features by combining a fluorescence and a transmission electron microscope in a single set-up. Together, these analyses allowed us to postulate a plausible model for the degradation of zeolite crystals in FCC particles in the ECat sample. Furthermore, the distribution of the various deactivation processes within particles of different ages was studied. A rim of completely deactivated zeolites surrounding each particle in the ECat sample was identified by using iLEM. These zeolites, which were never observed in fresh or steam-deactivated samples, contained clots of dense structures. The structures are proposed to be carbonaceous deposits formed during the cracking process, and seem resistant towards burning off during catalyst regeneration.

Monometallic Pt and bimetallic Pt-Cu catalysts supported on Mg(Al)O mixed oxides, obtained by calcination of the corresponding layered double hydroxides (LDHs), were prepared and tested in the aqueous-phase reforming (APR) of glycerol. The effect of the Mg/Al ratio and calcination temperature of the LDH support, as well as the effect of varying Pt and Cu amounts on glycerol reforming, was investigated. The use of a basic support increases the selectivity to hydrogen and the use of a Pt-Cu bimetallic catalyst results in a decrease in alkane formation. The 0.9 wt. % Pt-0.4 wt. % Cu/Mg(Al)O_2.95 catalyst system with an Mg(Al)O mixed oxide support obtained by the calcination of the corresponding LDH material with Mg/Al ratio of 2.95 at 673 K, showed higher hydrogen selectivity (55.3 %) and lower methane production (1.9 %) after 5 h reaction than the benchmark Pt/Al₂O₃ catalyst (49.4 % and 5.6 %, respectively). Catalyst characterization by extended X-ray absorption fine structure (EXAFS) spectroscopy showed a bimetallic interaction between Pt and Cu. The bimetallic interaction is thought to be responsible for the lowered methane formation and, ultimately, the high hydrogen selectivity observed.

The effect of a severe steaming treatment on the physicochemical properties and catalytic performance of H-SAPO-34 molecular sieves during the methanol-to-hydrocarbons (MTH) reaction has been investigated with a combination of scanning transmission X-ray microscopy (STXM), catalytic testing, and bulk characterization techniques, including ammonia temperature programmed desorption and ²⁷Al and ²⁹Si magic angle spinning nuclear magnetic resonance. For this purpose, two samples, namely a calcined and a steamed H-SAPO-34 catalyst powder, have been compared. It has been found that calcined H-SAPO-34 displays a high selectivity towards light olefins, yet shows a poor stability as compared to a zeolite H-ZSM-5 catalyst. Moreover, in situ STXM at the carbon K-edge during the MTH reaction allows construction of nanoscale chemical maps of the hydrocarbon species formed within the H-SAPO-34 aggregates as a function of reaction time and steam post-treatment. It was found that there is an initial preferential formation of coke precursor species within the core of the H-SAPO-34 aggregates. For longer times on stream the formation of the coke precursor species is extended to the outer regions, progressively filling the entire H-SAPO-34 catalyst particle. In contrast, the hydrothermally treated H-SAPO-34 showed similar reaction selectivity, but decreased activity and catalyst stability with respect to its calcined counterpart. These variations in MTH performance are related to a faster and more homogeneous formation of coke precursor species filling up the entire steamed H-SAPO-34 catalyst particle. Finally, the chemical imaging capabilities of the STXM method at the Al and Si K-edge are illustrated by visualizing the silicon islands at the nanoscale before and after steaming H-SAPO-34.

Hydrodeoxygenation (HDO) studies over carbon nanofiber-supported (CNF) W₂C and Mo₂C catalysts were performed on guaiacol, a prototypical substrate to evaluate the potential of a catalyst for valorization of depolymerized lignin streams. Typical reactions were executed at 55 bar hydrogen pressure over a temperature range of 300–375 °C for 4 h in dodecane, using a batch autoclave system. Combined selectivities of up to 87 and 69 % to phenol and methylated phenolics were obtained at 375 °C for W₂C/CNF and Mo₂C/CNF at >99 % conversion, respectively. The molybdenum carbide-based catalyst showed a higher activity than W₂C/CNF and yielded more completely deoxygenated aromatic products, such as benzene and toluene. Catalyst recycling experiments, performed with and without regeneration of the carbide phase, showed that the Mo₂C/CNF catalyst was stable during reusability experiments. The most promising results were obtained with the Mo₂C/CNF catalyst, as it showed a much higher activity and higher selectivity to phenolics compared to W₂C/CNF.

Proteins sharing the same “2-His-1-carboxylate” structural motif have little amino acid sequence similarity and are able to perform many different reactions. Many factors have been cited to explain their different specificity and turnover rates, like protein environment, coordinated ligand geometry, electronic structure of the active site, etc. In this paper, we present a combined approach applying high-resolution XANES spectroscopy and theory simulations to different model complexes that mimic the binding modes of the amino acids to the metal site. Experiments were performed on three compounds showing three metal sites: ferrous hexacoordinate, ferric pentacoordinate and ferrous pentacoordinate. The first two compounds bear an N,N,O-tridentate 3,3-bis(1-alkylimidazol-2-yl)propionate ligand that features a monodentate carboxylate group. These complexes mimic the activity of extradiol dioxygenases but also exhibit intradiol cleavage activity. The third compound features a bidentate terphenylcarboxylate ligand and a sterically hindered bidentate N,N-donor, thus providing a good structural mimic of the ternary enzyme-tetrahydrobiopterin-substrate complex in pterin-dependent phenylalanine hydroxylase, which also contains a bidentate carboxylate. Modeling of high-resolution XANES on well-defined model complexes of different geometry can aid in protein structure elucidation. XANES gives the oxidation state and coordination number of the metal in the non-crystallized protein at natural pH. The accuracy of the results is limited by the core-hole and experimental broadenings. We found that high-resolution XANES experiments give increased resolution at the pre-edges, but limited improvement at the main edge. These high-resolution pre-edges can be accurately simulated by using crystal field multiplet theory (CFM). We show that by combining modelling and XANES simulations with FEFF8, detailed structural and chemical information can be obtained. We found that a short O2–metal distance for the carboxylate oxygen atom not bound to the metal causes a higher white line in Fe^II, which is similar to the results obtained for the pterin-dependent hydroxylase, tyrosine hydroxylase (TYH). Full-potential FDMNES simulations for each sample confirm the accuracy of the main results with muffin-tin approximation (FEFF8).

The incipient wetness impregnation steps of 3 mm cylindrical γ-Al₂O₃ pellets with Cr^III-nitrate and Cr^VI-oxide as precursors was investigated by using UV/Vis and Raman microspectroscopy. The speciation and microdistributions of metal-ion complexes in the pellets were followed in time after impregnation. Measurements on the catalyst bodies were performed by applying a scan-line on the surface of bisected pellets. The microdistributions of the Cr-ion complexes were altered by varying the pH, the ratio of the Cr^III-nitrate and Cr^VI-oxide and by including either citric acid or phosphoric acid to the impregnation solution. Three factors were found to be most influential: i) Hydrolysis of Cr^III complexes to yield solid Cr(OH)₃ near the exterior of the pellets, ii) electrostatic interaction between the support and the respective Cr^III and Cr^VI complexes, and iii) competitive adsorption of the additives. The opposite charge of the Cr^III and Cr^VI complexes was exploited to obtain differences in the overall Cr-ion complex microdistributions, for example, egg-shell, egg-yolk, egg-white, and uniform type of distributions.

With dwindling reserves of fossil feedstock as a resource for chemicals production, the fraction of chemicals and energy supplied by alternative, renewable resources, such as lignin, can be expected to increase in the foreseeable future. Here, we demonstrate a catalytic process to valorize lignin (exemplified with kraft, organosolv, and sugarcane bagasse lignin) using a mixture of cheap, bio-renewable ethanol and water as solvent. Ethanol/water mixtures readily solubilize lignin under moderate temperatures and pressures with little residual solids. The molecular weight of the dissolved lignins was shown to be reduced by gel permeation chromatography and quantitative HSQC NMR methods. The use of liquid-phase reforming of the solubilized lignin over a Pt/Al₂O₃ catalyst at 498 K and 58 bar is introduced to yield up to 17 % combined yield of monomeric aromatic oxygenates such as guaiacol and substituted guaiacols generating hydrogen as a useful by-product. Reduction of the lignin dissolved in ethanol/water using a supported transition metal catalyst at 473 K and 30 bar hydrogen yields up to 6 % of cyclic hydrocarbons and aromatics.

A time-resolved in situ micro-spectroscopic approach has been used to investigate the Brønsted acidic properties of fluid-catalytic-cracking (FCC) catalysts at the single particle level by applying the acid-catalysed styrene oligomerisation probe reaction. The reactivity of individual FCC components (zeolite, clay, alumina and silica) was monitored by UV/Vis micro-spectroscopy and showed that only clay and zeolites (Y and ZSM-5) contain Brønsted acid sites that are strong enough to catalyse the conversion of 4-fluorostyrene into carbocationic species. By applying the same approach to complete FCC catalyst particles, it has been found that the fingerprint of the zeolitic UV/Vis spectra is clearly recognisable. This almost exclusive zeolitic activity is confirmed by the fact that hardly any reactivity is observed for FCC particles that contain no zeolite. Confocal fluorescence microscopy images of FCC catalyst particles reveal inhomogeneously distributed micron-sized zeolite domains with a highly fluorescent signal upon reaction. By examining laboratory deactivated FCC catalyst particles in a statistical approach, a clear trend of decreasing fluorescence intensity, and thus Brønsted acidity, of the zeolite domains is observed with increasing severity of the deactivation method. By comparing the average fluorescence intensities obtained with two styrenes that differ in reactivity, it has been found that the Brønsted acid site strength within FCC catalyst particles containing ZSM-5 is more uniform than within those containing zeolite Y, as confirmed with temperature-programmed desorption of ammonia.

The solid acid-catalyzed hydrolysis of cellulose was studied under elevated temperatures and autogenous pressures using in situ ATR-IR spectroscopy. Standards of cellulose and pure reaction products, which include glucose, fructose, hydroxymethylfurfural (HMF), levulinic acid (LA), formic acid, and other compounds, were measured in water under ambient and elevated temperatures. A combination of spectroscopic and HPLC analysis revealed that the cellulose hydrolysis proceeds first through the disruption of the glycosidic linkages of cellulose to form smaller cellulose molecules, which are readily observed by their distinctive CO vibrational stretches. The continued disruption of the linkages in these oligomers eventually results in the formation and accumulation of monomeric glucose. The solid-acid catalyst accelerated the isomerization of glucose to fructose, which then rapidly reacted under hydrothermal conditions to form degradation products, which included HMF, LA, formic acid, and acetic acid. The formation of these species could be suppressed by decreasing the residence time of glucose in the reactor, reaction temperature, and contact with the metal reactor. The hydrolysis of regenerated cellulose proceeded faster and under milder conditions than microcrystalline cellulose, which resulted in increased glucose yield and selectivity.

The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant βO4 linkages and, to a lesser extent, the 55’ carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10–15 % depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin.

Coke formation during the methanol-to-olefin (MTO) conversion has been studied at the single-particle level with in situ UV/Vis and confocal fluorescence microscopy. For this purpose, large H-ZSM-5 crystals differing in their Si/Al molar ratio have been investigated. During MTO, performed at 623 and 773 K, three major UV/Vis bands assigned to different carbonaceous deposits and their precursors are observed. The absorption at 420 nm, assigned to methyl-substituted aromatic compounds, initiates the buildup of the optically active coke species. With time-on-stream, these carbonaceous compounds expand in size, resulting in the gradual development of a second absorption band at around 500 nm. An additional broad absorption band in the 600 nm region indicates the enhanced formation of extended carbonaceous compounds that form as the reaction temperature is raised. Overall, the rate of coke formation decreases with decreasing aluminum content. Analysis of the reaction kinetics indicates that an increased Brønsted acid site density facilitates the formation of larger coke species and enhances their formation rate. The use of multiple excitation wavelengths in confocal fluorescence microscopy enables the localization of coke compounds with different molecular dimensions in an individual H-ZSM-5 crystal. It demonstrates that small coke species evenly spread throughout the entire H-ZSM-5 crystal, whereas extended coke deposits primarily form near the crystal edges and surfaces. Polarization-dependent UV/Vis spectroscopy measurements illustrate that extended coke species are predominantly formed in the straight channels of H-ZSM-5. In addition, at higher temperatures, fast deactivation leads to the formation of large aromatic compounds within channel intersections and at the external zeolite surface, where the lack of spatial restrictions allows the formation of graphite-like coke.

A combination of atomic force microscopy (AFM), high-resolution scanning electron microscopy (HR-SEM), focused-ion-beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotron-based IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM-5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol-to-olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM-5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM-5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 5–50 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Brønsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity.

Liquid-chromatography electrospray-ionisation mass spectrometry (LC-ESI-MS) studies on reaction mixtures of the telomerization of 1,3-butadiene with biomass-based polyols revealed that the TOMPP (TOMPP=tris(2-methoxyphenyl)phosphine) ligand is converted towards the corresponding (2,7-octadienyl)phosphonium species during catalysis. The extent of ligand alkylation is substrate dependent and was identified as the primary cause of deactivation for carbohydrate substrates with anomeric hydroxyl groups. Coordination studies of the phosphonium cation with [Pd(dba)₂] (dba=dibenzylideneacetone) gave insight into the alkylation mechanism and showed that the formation of the phosphonium cation is fully reversible. The reaction yields the key cationic intermediate [Pd(1,2,3,7,8-η⁵-octa-2,7-dien-1-yl)(TOMPP)]⁺, which, in the presence of the iodide anion, results in the formation of [Pd(1,2,3-η³-octa-2,7-dien-1-yl)(I)(TOMPP)]. Both complexes were fully characterized by various techniques including single crystal X-ray crystallography. Based on these results, an extension to the Pd/TOMPP-catalyzed telomerization mechanism was formulated to include the 2,7-octadienylphosphonium cation as a ligand reservoir. Catalytic tests show that the use of [Pd(dba)₂] as precatalyst improves the telomerization of glucose and xylose.

Large zeolite crystals have been used as model systems for the investigation of diffusion and catalytic reactivity phenomena in microporous host materials for at least two decades. However, their potential in assisting the detection of elusive reactive intermediates appears to have been underestimated. Herein, we show that a complementary use of vibrational and optical spectroscopy in combination with theoretical calculations allows for the unambiguous identification of transient carbocationic species generated upon the acid-catalyzed oligomerization of styrene derivatives within zeolite H-ZSM-5. Thanks to the mediated diffusion of the reactant in the large H-ZSM-5 crystals and minimal external surface the reaction intermediates can be accumulated within zeolite micropores in sufficient concentrations to allow their detection by synchrotron-based IR microspectroscopy. The UV/Vis and IR spectra display strong polarization dependence of on the molecular alignment of the dimeric styrene carbocations imposed by the zeolite channels and cages that can be rationalized in terms of the electronic and vibrational transitions of the intrazeolite carbocations. Based on these findings, a molecular-level picture of the macroscopic arrangement of the reaction intermediates confined within microporous zeolite matrices can be devised.

X-ray absorption, UV/Vis, and fluorescence microspectroscopy have been used to characterize the catalytic conversion of thiophene derivatives within the micropores of an individual H-ZSM-5 zeolite crystal. Space-resolved information into the Si/Al ratios and sulfur content was provided by X-ray absorption microspectroscopy. X-ray absorption near-edge spectroscopy spectral information and modeling indicated the presence of a sulfur atom, in close proximity of two oxygen atoms, that is, at approximately 2.5 Å. Space-resolved spectroscopic measurements provided experimental evidence for the formation of conjugated carbocationic reaction intermediates by opening of the thiophene ring. The molecular alignment of reaction products within the straight pores of the individual H-ZSM-5 zeolite crystals was observed with polarized light UV/Vis microspectroscopy. In addition, confocal fluorescence microscopy revealed the 3D distribution of different reaction products and demonstrated the influence of the H-ZSM-5 crystal’s intergrowth structure and its related molecular diffusion barriers.

The present status of in-situ scanning transmission X-ray microscopy (STXM) is reviewed, with an emphasis on the abilities of the STXM technique in comparison with electron microscopy. The experimental aspects and interpretation of X-ray absorption spectroscopy (XAS) are briefly introduced and the experimental boundary conditions that determine the potential applications for in-situ XAS and in-situ STXM studies are discussed. Nanoscale chemical imaging of catalysts under working conditions is outlined using cobalt and iron Fischer–Tropsch catalysts as showcases. In the discussion, we critically compare STXM-XAS and STEM-EELS (scanning transmission electron microscopy–electron energy loss spectroscopy) measurements and indicate some future directions of in-situ nanoscale imaging of catalytic solids and related nanomaterials.

Alkaline earth metal oxides (MO) are catalytically active in the etherification of glycerol. Density Functional Theory (DFT) calculations have been used to examine the reactivity of glycerol with MO surfaces with M=Mg, Ca, Sr or Ba. More specifically, the optimum glycerol adsorption mode and the strength of glycerol interaction with regular MO (001) surfaces and a stepped CaO surface have been investigated and involves the interaction with acid–base surface sites. The basicity of lattice oxygen atoms is correlated with the adsorption energy: BaO (−3.02 eV) > SrO (−2.85 eV) > CaO (−2.05 eV) > MgO (−1.35 eV). The interactions have an exothermic character, that is, the more basic the alkaline earth metal oxide, the more exothermic is the adsorption process and the higher the dissociation extent. Thus, the dissociation of glycerol increases in the order: MgO (not dissociated) < CaO (partially dissociated < SrO (partially dissociated) < BaO (completely dissociated). The presence of defects is found to play a key role in the mechanism: glycerol interaction with a stepped CaO surface presents the highest adsorption energy (−3.78 eV), and the molecule is found to dissociate at the step. The calculated structural parameters are found to be in good agreement with experimental data on catalyst reactivity. Moreover, the earlier postulated reaction mechanism, which also involves the additional involvement of Lewis acid sites proved to be feasible for CaO and SrO regular surfaces, and for the stepped CaO surface. It was found that for these oxides one of the most favored adsorption modes involves a non-dissociative adsorption of one hydroxyl group of glycerol, which as a result becomes a better leaving group. Therefore, theoretical evidence was found for the possible direct involvement of Lewis acid sites in the catalytic etherification of bio-derived alcohols, such as glycerol, as it is anticipated that these observations can be extended to sugar alcohols as well.

A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with all studied catalyst materials, however, the selectivity for hydrogen increased from 15 % to 51 % when going from the unpromoted to a BaO-promoted catalyst. The formation of the undesired byproducts CO, methane, and dimethyl ether was considerably reduced as well. The observed trend in catalyst performance follows the trend in increasing basicity of the studied promoter elements, indicating a chemical effect of the promoter material. Superior catalytic performance, in terms of H₂ and CO selectivity, was obtained with a Au/La₂O₃ catalyst. At 300 °C the hydrogen selectivity reached 80 % with only 2 % CO formation, and the catalyst displayed a stable performance over at least 24 h on-stream. Furthermore, the formation of CO was found to be independent of the oxygen concentration in the feed. The commercial lanthanum oxide used in this study had a low specific surface area, which led to the formation of relative large gold particles. Therefore, the catalytic activity could be enhanced by decreasing the gold particle size through deposition on lanthanum oxide supported on high-surface-area alumina.

Formation of coke in large H-ZSM-5 and H-SAPO-34 crystals during the methanol-to-olefin (MTO) reaction has been studied in a space- and time-resolved manner. This has been made possible by applying a high-temperature in-situ cell in combination with micro-spectroscopic techniques. The buildup of optically active carbonaceous species allows detection with UV/Vis microscopy, while a confocal fluorescence microscope in an upright configuration visualises the formation of coke molecules and their precursors inside the catalyst grains. In H-ZSM-5, coke is initially formed at the triangular crystal edges, in which straight channel openings reach directly the external crystal surface. At reaction temperatures ranging from 530 to 745 K, two absorption bands at around 415 and 550 nm were detected due to coke or its precursors. Confocal fluorescence microscopy reveals fluorescent carbonaceous species that initially form in the near-surface area and gradually diffuse inwards the crystal in which internal intergrowth boundaries hinder a facile penetration for the more bulky aromatic compounds. In the case of H-SAPO-34 crystals, an absorption band at around 400 nm arises during the reaction. This band grows in intensity with time and then decreases if the reaction is carried out between 530 and 575 K, whereas at higher temperatures its intensity remains steady with time on stream. Formation of the fluorescent species during the course of the reaction is limited to the near-surface region of the H-SAPO-34 crystals, thereby creating diffusion limitations for the coke front moving towards the middle of the crystal during the MTO reaction. The two applied micro-spectroscopic techniques introduced allow us to distinguish between graphite-like coke deposited on the external crystal surface and aromatic species formed inside the zeolite channels. The use of the methods can be extended to a wide variety of catalytic reactions and materials in which carbonaceous deposits are formed.

Glycerol is an attractive renewable building block for the synthesis of di- and triglycerols, which have numerous applications in the cosmetic and pharmaceutical industries. In this work, the selective etherification of glycerol to di- and triglycerol was studied in the presence of alkaline earth metal oxides and the data are compared with those obtained with Na₂CO₃ as a homogeneous catalyst. It was found that glycerol conversion increased with increasing catalyst basicity; that is, the conversion increases in the order: MgO<CaO<SrO<BaO. The best selectivity values for (di- + tri-) glycerol (>90 % at 60 % conversion) are obtained over CaO, SrO, and BaO. For these catalysts no substantial acrolein formation was observed. Furthermore, at the start of the reaction mainly linear diglycerol was produced, whereas at higher conversion degrees branched diglycerol started to form. In another series of experiments different types of CaO materials were prepared. It was found that these CaO-based materials not only differed in their surface area and number of basic sites, but also in their Lewis acid strength. Within this series the CaO material possessing the strongest Lewis acid sites had the highest catalytic activity, comparable to that of BaO, pointing towards the important role of Lewis acidity for this etherification reaction. Based on these observations a plausible alternative reaction scheme for glycerol etherification is presented, which considers the facilitation of the hydroxyl leaving process. Finally, the stability of the catalytic solids under study was investigated and it was found that colloidal CaO particles of about 50–100 nm can be spontaneously generated during reaction. Catalytic testing of these CaO colloids, after isolation from the reaction medium, revealed a very high etherification activity. Understanding the nature of these Ca-based colloids opens new opportunities for investigating supported colloidal particle catalysts to take advantage of both their hetero- and homogeneous nature.

An indirect magnetic resonance imaging (MRI) method has been developed to determine in a noninvasive manner the distribution of paramagnetic Co²⁺ complexes inside Co/Al₂O₃ catalyst extrudates after impregnation with Co²⁺/citrate solutions of different pH and citrate concentrations. UV/Vis/NIR microspectroscopic measurements were carried out simultaneously to obtain complementary information on the nature of the Co²⁺ complexes. In this way, it could be confirmed that the actual distribution of Co²⁺ inside the extrudates could be derived from the MRI images. By combining these space- and time-resolved techniques, information was obtained on both the strength and the mode of interaction between [Co(H₂O)₆]²⁺ and different Co²⁺ citrate complexes with the Al₂O₃ support. Complexation of Co²⁺ by citrate was found to lead to a stronger interaction of Co with the support surface and formation of an eggshell distribution of Co²⁺ complexes after impregnation. By addition of free citrate and by changing the pH of the impregnation solution, it was possible to obtain the rather uncommon egg-yolk and egg-white distributions of Co²⁺ inside the extrudates after impregnation. In other words, by carefully altering the chemical composition and pH of the impregnation solution, the macrodistribution of Co²⁺ complexes inside catalyst extrudates could be fine-tuned from eggshell over egg white and egg yolk to uniform.

Glycerol is considered a potential renewable building block for the synthesis of existing as well as new chemicals. A promising route is the telomerization of 1,3-butadiene with glycerol leading to C₈ chain ethers of glycerol with applications in, for example, surfactant chemistry. Recently, we reported a new set of palladium-based homogeneous catalytic systems for the telomerization of 1,3-butadiene with glycerol and found that palladium complexes bearing methoxy-functionalized triphenylphosphine ligands are highly active catalysts capable of converting crude glycerol without any significant loss of activity. Herein, we present a detailed account of these investigations by reporting on the influence of the butadiene/glycerol ratio, temperature, and reaction time on product selectivity and activity allowing further optimization of catalyst performance. Maximum activity and yield were reached for high 1,3-butadiene/glycerol ratios at a temperature of 90 °C, whereas the selectivity for mono- and diethers of glycerol could be optimized by combining high reaction temperatures and short reaction times with low butadiene/glycerol ratios. Variation of the Pd^II metal precursors and the metal/ligand ratio showed that palladium precursors with halogen ligands gave unsatisfying results, in contrast to precursors with weakly coordinated ligands such as [Pd(OAc)₂] and [Pd(acac)₂]. [Pd(dba)₂], the only Pd⁰ precursor tested, gave the best results in terms of activity, which illustrates the importance of the ability to form a Pd⁰ species in the catalytic cycle. Finally, base addition resulted in a shortening of the reaction time and most likely facilitates the formation of a Pd⁰ species. Based on these results, we were able to realize the first attempts towards a rational ligand design aimed at a high selectivity for mono- and diether formation.