As a common mineral phase on Earth and Martian regolith, natural rutile was reported as a potential candidate for use as a Fenton catalyst in this study. The influences of Fe and V in various chemical states on the generation of reactive oxygen species (ROSs) and the catalytic activity of rutile were examined. A series of rutile samples with various surface and bulk states of Fe and V were obtained initially by hydrogen annealing of natural rutile at ~773–1173 K. X-ray diffraction, electron paramagnetic resonance spectra, and X-ray photoelectron spectroscopy demonstrated that the atomic fractions of Fe(III) and V(V) decreased sharply with increasing temperature, along with the accumulation of surface Fe(II) and bulk V(III). All as-prepared materials showed enhanced Fenton degradation efficiency on methylene blue (MB) compared with P25-TiO2, and the treated samples exhibited up to 3.5-fold improvement in efficiency at pH 3 compared to the untreated sample. The improved efficiency was attributed mainly to Fenton catalysis involving Fe(II) and V(III). The dissolved Fe2+ played a crucial role in the homogeneous Fenton reaction, while the bound V(III) favored adsorption primarily and may have facilitated heterogeneous Fenton reaction and the regeneration of Fe2+. The pH regulated the reaction mechanism among homogeneous (pH = 3) and heterogeneous (pH = 3.7) Fenton catalysis and physical adsorption (pH = 5, 6). The aim of the present study was to improve the understanding of the potential role of natural rutile with advanced oxidation functions in Earth systems and even on Mars, which also provide an inspiration for screening natural rutile and any other similar, Earth-abundant, low-cost minerals for environmental application.

The synthesis of copper citrate complex supported on acid-activated vermiculite was investigated with a view to preparing an efficient, mild, robust and recyclable catalyst for the Biginelli reaction. The new catalyst was characterized by X-ray fluorescence (XRF), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), and scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). Copper citrate supported over activated vermiculite (AAVrm-Cu2) showed good catalytic activity in the synthesis of 3,4-dihydropyrimidinones. The catalyst can be separated easily from the reaction mixture by filtration and retains its catalytic activity for up to five cycles of reaction with no apparent decrease in yield.

Understanding how catalysts work during chemical reactions is crucial when developing efficient catalytic materials. The dynamic processes involved are extremely sensitive to changes in pressure, gas environment and temperature. Hence, there is a need for spatially resolved operando techniques to investigate catalysts under working conditions and over time. The use of dedicated operando techniques with added detection of catalytic conversion presents a unique opportunity to study the mechanisms underlying the catalytic reactions systematically. Herein, we report on the detailed setup and technical capabilities of a modular, homebuilt gas feed system directly coupled to a quadrupole mass spectrometer, which allows for operando transmission electron microscopy (TEM) studies of heterogeneous catalysts. The setup is compatible with conventional, commercially available gas cell TEM holders, making it widely accessible and reproducible by the community. In addition, the operando functionality of the setup was tested using CO oxidation over Pt nanoparticles.

A new closed cell is presented for in situ X-ray ptychography which allows studies under gas flow and at elevated temperature. In order to gain complementary information by transmission and scanning electron microscopy, the cell makes use of a Protochips E-chipTM which contains a small, thin electron transparent window and allows heating. Two gold-based systems, 50 nm gold particles and nanoporous gold as a relevant catalyst sample, were used for studying the feasibility of the cell. Measurements showing a resolution around 40 nm have been achieved under a flow of synthetic air and during heating up to temperatures of 933 K. An elevated temperature exhibited little influence on image quality and resolution. With this study, the potential of in situ hard X-ray ptychography for investigating annealing processes of real catalyst samples is demonstrated. Furthermore, the possibility to use the same sample holder for ex situ electron microscopy before and after the in situ study underlines the unique possibilities available with this combination of electron microscopy and X-ray microscopy on the same sample.

A simple and efficient method for in situ preparation of highly stable polyimide (PI)-supported silver nanoparticles (AgNPs) was proposed. This process achieves excellent dispersion and high stability of AgNPs in the PI matrix. The formation of AgNPs in PI and the morphology evolution of PI/Ag nanocomposites were characterized by x-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy (FT-IR), and x-ray photoelectron spectra studies. The catalytic properties of these PI-supported AgNPs were investigated by monitoring the reduction of 4-nitrophenol by excess NaBH4 in water. The catalytic reaction was observed to have a pseudo first-order rate constant of 0.567 min−1 (9.45 × 10−3 s−1), which is comparable to other heterogeneous silver catalysts reported in the literature. Notably, the PI-supported AgNPs retained their relatively high catalytic activity over seven recycles with almost no leaching of catalytic species in the reaction solution. Moreover, the catalytic activity of the catalyst is still quite appreciable even after a six-month shelf-storage under room temperature.

A tomographic heating holder for transmission electron microscopy that can be used to study supported catalysts at temperatures of up to ~1,500°C is described. The specimen is placed in direct thermal contact with a tungsten filament that is oriented perpendicular to the axis of the holder without using a support film, allowing tomographic image acquisition at high specimen tilt angles with minimum optical shadowing. We use the holder to illustrate the evolution of the active phases of Pt nanoparticles on carbon black and PtPd nanoparticles on γ-alumina with temperature. Particle size distributions and changes in active surface area are quantified from tilt series of images acquired after subjecting the specimens to increasing temperatures. The porosity of the alumina support and the sintering mechanisms of the catalysts are shown to depend on distance from the heating filament.