Nanoscale Anatomy of Iron-Silica Self-Organized Membranes: Implications for Prebiotic Chemistry.

Iron-silica self-organized membranes, so-called chemical gardens, behave as fuel cells and catalyze the formation of amino/carboxylic acids and RNA nucleobases from organics that were available on early Earth. Despite their relevance for prebiotic chemistry, little is known about their structure and mineralogy at the nanoscale. Studied here are focused ion beam milled sections of iron-silica membranes, grown from synthetic and natural, alkaline, serpentinization-derived fluids thought to be widespread on early Earth. Electron microscopy shows they comprise amorphous silica and iron nanoparticles of large surface areas and inter/intraparticle porosities. Their construction resembles that of a heterogeneous catalyst, but they can also exhibit a bilayer structure. Surface-area measurements suggest that membranes grown from natural waters have even higher catalytic potential. Considering their geochemically plausible precipitation in the early hydrothermal systems where abiotic organics were produced, iron-silica membranes might have assisted the generation and organization of the first biologically relevant organics.

Efficient Alkyne Semihydrogenation Catalysis Enabled by Synergistic Chemical and Thermal Modifications of a PdIn MOF.

Recently, there has been a growing interest in using MOF templating to synthesize heterogeneous catalysts based on metal nanoparticles on carbonaceous supports. Unlike the common approach of direct pyrolysis of PdIn-MOFs at high temperatures, this work proposes a reductive chemical treatment under mild conditions before pyrolysis (resulting in PdIn-QT). The resulting material (PdIn-QT) underwent comprehensive characterization via state-of-the-art aberration-corrected electron microscopy, N2 physisorption, X-ray absorption spectroscopy, Raman, X-ray photoelectron spectroscopy, and X-ray diffraction. These analyses have proven the existence of PdIn bimetallic nanoparticles supported on N-doped carbon. In situ DRIFT spectroscopy reveals the advantageous role of indium (In) in regulating Pd activity in alkyne semihydrogenation. Notably, incorporating a soft nucleation step before pyrolysis enhances surface area, porosity, and nitrogen content compared to direct MOF pyrolysis. The optimized material exhibits outstanding catalytic performance with 96% phenylacetylene conversion and 96% selectivity to phenylethylene in the fifth cycle under mild conditions (5 mmol phenylacetylene, 7 mg cat, 5 mL EtOH, R.T., 1 H2 bar).

Textural, Microstructural and Chemical Characterization of Ferritic Stainless Steel Affected by the Gold Dust Defect.

The "gold dust defect" (GDD) appears at the surface of ferritic stainless steels (FSS) and degrades their appearance. Previous research showed that this defect might be related to intergranular corrosion and that the addition of aluminium improves surface quality. However, the nature and origin of this defect are not properly understood yet. In this study, we performed detailed electron backscatter diffraction analyses and advanced monochromated electron energy-loss spectroscopy experiments combined with machine-learning analyses in order to extract a wealth of information on the GDD. Our results show that the GDD leads to strong textural, chemical, and microstructural heterogeneities. In particular, the surface of affected samples presents an α-fibre texture which is characteristic of poorly recrystallised FSS. It is associated with a specific microstructure in which elongated grains are separated from the matrix by cracks. The edges of the cracks are rich in chromium oxides and MnCr2O4 spinel. In addition, the surface of the affected samples presents a heterogeneous passive layer, in contrast with the surface of unaffected samples, which shows a thicker and continuous passive layer. The quality of the passive layer is improved with the addition of aluminium, explaining the better resistance to the GDD.