Highlights

Carbon supports are ubiquitous components of heterogeneous catalysts for acetylene hydrochlorination to vinyl chloride, from commercial mercury-based systems to more sustainable metal single-atom alternatives. Their potential co-catalytic role has long been postulated but never unequivocally demonstrated. Herein, combining operando X-ray absorption spectroscopy with other spectroscopic and kinetic analyses, we evidence the bifunctionality of carbons and metal sites (Pt, Au, Ru) in the acetylene hydrochlorination catalytic cycle.

Zirconium-containing metal-organic framework (MOF) with UiO-66 topology is an extremely versatile material, which finds applications beyond gas separation and catalysis.  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.

Using operando time-resolved X-ray absorption spectroscopy, we investigated the origin of volcano-shaped ethanol oxidative dehydrogenation activity trend of VOx/CeO2 catalysts as a function of VOx surface coverage. Vanadium and cerium synergistically change their oxidation states during the catalytic cycle. The catalytic activity correlates with the concentration of reversible Ce4+/3+species.

The ability to study in situ the formation and consumption of Pd hydrides (PdH) in liquid environments is a significant challenge hampering a deeper understanding of catalyzed liquid-phase hydrogenation reactions. Here, using quick scanning X-ray absorption spectroscopy (QEXAFS), we present a detailed kinetic study of Pd hydride formation and reactivity on Pd/Al₂O₃ in 2-propanol solvent. 

Operando/in situ spectro-electrochemical studies often require high loadings and thick catalyst layers (CLs) leading to large ion- and mass-transport limitations. In this study we investigate PdH-formation in two Pd-catalysts with similar surface areas but drastically different morphologies. Our results unveil that the CL-thickness largely determines the PdH formation trends calling for the minimization of the CL-thickness in such experiments.

Operando X-ray absorption spectroscopy revealed a linear correlation between the amount of oxidic Fe²⁺ and the ambient temperature activity of Pt−FeO_x preferential carbon monoxide oxidation catalysts. The hydrogen prereduction temperature and pressure determines the amount of active Fe²⁺ sites for alumina- and silica-supported Pt−Fe catalysts. Catalyst deactivation is linked with the oxidation of these sites.

The development of next-generation perovskite-based optoelectronic devices relies critically on the understanding of the interaction between charge carriers and the polar lattice in out-of-equilibrium conditions. While it has become increasingly evident for CsPbBr₃ perovskites that the Pb–Br framework flexibility plays a key role in their light-activated functionality, the corresponding local structural rearrangement has not yet been unambiguously identified. In this work the photoinduced lattice changes were investigated using combination of time-resolved and temperature-dependent studies at Br K and Pb L₃ X-ray absorption edges and ab initio simulations.

Operando time-resolved V and Ti K-edge X-ray absorption near-edge spectroscopy, coupled with a transient experimental strategy, quantitatively showed that the formation of acetaldehyde over 5% V₂O₅/15% TiO₂/SiO₂ is kinetically coupled to the formation of a V⁴⁺ intermediate, while the formation of V³⁺ is delayed and 10–70 times slower. The low-coordinated nature of various redox states of VO_x species (V⁵⁺, V⁴⁺, and V³⁺) in the 5% V₂O₅/15% TiO₂/SiO₂ catalyst is confirmed using the extensive database of V K-edge XANES spectra of standards and specially synthesized molecular crystals.

Cu diimine complexes present a noble metal free alternative to classical Ru, Re, Ir and Pt based photosensitizers in solution photochemistry, photoelectrochemical or dye-sensitized solar cells. Optimization of these dyes requires an understanding of factors governing the key photochemical properties: excited state lifetime and emission quantum yield. Using pump-probe XAS and DFT calculations we have explored the involvement of exciplex formation in the deactivation of the photoexcited state.