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Identification and quantification of functional groups in activated carbons by means of a multi-technique approach.

The adsorption of H2 and CO over Pt/Al2O3 was studied in gas and in liquid phase by FT-IR and ATR-IR spectroscopies under otherwise similar conditions. The solvent competes with hydrogen and CO for terrace and kink metal sites.

This work is focused on the determination of the most likely border morphologies in the H-terminated graphenic domains that constitute activated carbons, focusing on four different carbons and six supported-metal catalysts. Among the available characterization techniques, Inelastic Neutron Scattering spectroscopy provides detailed vibrational spectra containing the fingerprint of the terminal C-H groups of carbon materials. From the experimental spectra, we observed clear differences among carbons having different origin, and a systematic decrease in the integrated area upon metal deposition that linearly scales with the nanoparticles dispersion. Density Functional Theory simulations are fundamental to assign the experimental bands to specific species. Thus, an extended simulation work on both regular and defective aromatic models was carried out, providing the inelastic neutron scattering fingerprint of a large number of different C-H terminations. By fitting the experimental spectra with a linear combination of the simulated spectra, it was possible to quantify the concentration of each terminal C-H geometry in the samples, and to identify the species most affected by the metal nanoparticles deposition. Specific benzene rings exposing a single C-H group appear to have a decisive role in the interaction with the metal nanoparticles and their deposition procedure.

The formation of palladium hydride and carbide phases in palladium-based catalysts is a critical process that changes the catalytic performance and selectivity of the catalysts in important industrial reactions, such as the selective hydrogenation of alkynes or alkadienes. We present a comprehensive study of a 5 wt% carbon supported Pd nanoparticle (NP) catalyst in various environments by using in situ and operando X-ray absorption spectroscopy and diffraction, to determine the structure and evolution of palladium hydride and carbide phases, and their distribution throughout the NPs. We demonstrate how the simultaneous analysis of extended X-ray absorption fine structure (EXAFS) spectra and X-ray powder diffraction (XRPD) patterns allows discrimination between the inner “core” and outer “shell” regions of the NP during hydride phase formation at different temperatures and under different hydrogen pressures, indicating that the amount of hydrogen in the shell region of the NP is lower than that in the core. For palladium carbide, advanced analysis of X-ray absorption near-edge structure (XANES) spectra allows the detection of Pd–C bonds with carbon-containing molecules adsorbed at the surface of the NPs. In addition, H/Pd and C/Pd stoichiometries of PdHx and PdCy phases were obtained by using theoretical modelling and fitting of XANES spectra. Finally, the collection of operando time-resolved XRPD patterns (with a time resolution of 5 s) allowed the detection, during the ethylene hydrogenation reaction, of periodic oscillations in the NPs core lattice parameter, which were in phase with the MS signal of ethane (product) and in antiphase with the MS signal of H2 (reactant), highlighting an interesting direct structure–reactivity relationship. The presented studies show how a careful combination of X-ray absorption and diffraction can differentiate the structure of the core, shell and surface of the palladium NPs under working conditions and prove their relevant roles in catalysis.

We looked for the active hydrogen species in a highly dispersed and very homogeneous 5 wt% Pt/C industrial catalyst (Pt particle mean diameter of 2.0 ± 0.5 nm) for hydrogenation reactions, by coupling H2 adsorption measurements with Inelastic Neutron Scattering (INS). Taking advantage of the enormous progress undergone by INS instruments, we succeeded in collecting INS spectra of unprecedented quality that allowed us to: (1) demonstrate that the Pt nanoparticles are mainly located at the regular edges of the sp2 graphitic domains on the activated carbon; (2) validate that most of the H2 physisorbed on the carbon is side-on adsorbed; (3) detect for the first time H2 molecules adsorbed on hydride-covered Pt nanoparticles; (4) observe Pt-hydrides (on the Pt/C catalyst with the lowest Pt loading among those investigated by INS so far) and (5) provide evidence for the occurrence of spillover of atomic hydrogen from the Pt surface to unsaturated reactive sites located at the irregular borders of the sp2 domains on the activated carbon.

The behavior of a Pd(OAc)2/P4VP catalyst submitted to different pretreatments (prereduced, preoxidized, and untreated) during the aerobic oxidation of 2-propanol to acetone in the gas phase has been investigated. Synchronous, time-resolved, SAXS/XAS/MS techniques coupled with operando DRIFT spectroscopy (which gave information on the destiny of the acetate ligands) and ex situ HR-TEM (to detect the formation of Pd nanoparticles and to obtain their size distribution) were employed to accomplish a dynamical picture of the changes occurring to the Pd phase under transient reaction conditions. In addition, the catalytic performances were qualitatively explored by means of a CATLAB microreactor, with the final aim to establish structure–activity relationships. Our approach clearly demonstrates that highly isolated Pd2+ cationic species, either atomically dispersed or in the form of ultrasmall Pd2+–oxo clusters, are efficient and very stable active sites for the gas-phase aerobic oxidation of 2-propanol to acet...