RESUMEN
Production of green hydrogen (H2) is a sustainable process able to address the current energy crisis without contributing to long-term greenhouse gas emissions. Many Ag-based catalysts have shown promise for light-driven H2 generation, however, pure Ag-in its bulk or nanostructured forms-suffers from slow electron transfer kinetics and unfavorable AgâH bond strength. It is demonstrated that the complexation of Ag with various chalcogenides can be used as a tool to optimize these parameters and reach improved photocatalytic performance. In this work, metal-organic-chalcogenolate assemblies (MOCHAs) are introduced as effective catalysts for light-driven hydrogen evolution reaction (HER) and investigate their performance and structural stability by examining a series of AgXPh (X = S, Se, and Te) compounds. Two catalyst-support sensitization strategies are explored: by designing MOCHA/TiO2 composites and by employing a common Ru-based photosensitizer. It is demonstrated that the heterogeneous approach yields stable HER performance but involves a catalyst transformation at the initial stage of the photocatalytic process. In contrast to this, the visible-light-driven MOCHA-dye dyad shows similar HER activity while also ensuring the structural integrity of the MOCHAs. The work shows the potential of MOCHAs in constructing photosystems for catalytic H2 production and provides a direct comparison between known AgXPh compounds.
RESUMEN
Silicon oxycarbides (SiOCs) impregnated with tetrabutylammonium halides (TBAX) were investigated as an alternative to silica-based supported ionic liquid phases for the production of bio-based cyclic carbonates derived from limonene and linseed oil. The support materials and the supported ionic liquid phases (SILPs) were characterized via Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen adsorption, X-ray photoelectron spectroscopy, microscopy, and solvent adsorption. The silicon oxycarbide supports were pyrolyzed at 300-900 °C prior to being coated with different tetrabutylammonium halides and further used as heterogeneous catalysts for the formation of cyclic carbonates in batch mode. Excellent selectivities of 97-100% and yields of 53-62% were obtained with tetrabutylammonium chloride supported on the silicon oxycarbides. For comparison, the catalytic performance of commonly employed silica-supported ionic liquids was investigated under the same conditions. The silica-supported species triggered the formation of a diol as a byproduct, leading to a lower selectivity of 87% and a lower yield of 48%. Ultimately, macroporous monolithic SiOC-SILPs with suitable permeability characteristics (k1 = 10-11 m2) were produced via photopolymerization-assisted solidification templating and applied for the selective and continuous production of limonene carbonate with supercritical carbon dioxide as the reagent and sole solvent. Constant product output over 48 h without concurrent catalyst leaching was achieved.
RESUMEN
Today, many essential industrial processes depend on syngas. Due to a high energy demand and overall cost as well as a dependence on natural gas as its precursor, alternative routes to produce this valuable mixture of hydrogen and carbon monoxide are urgently needed. Electrochemical syngas production via two competing processes, namely carbon dioxide (CO2) reduction and hydrogen (H2) evolution, is a promising method. Often, noble metal catalysts such as gold or silver are used, but those metals are costly and have limited availability. Here, we show that metal-organic chalcogenolate assemblies (MOCHAs) combine several properties of successful electrocatalysts. We report a scalable microwave-assisted synthesis method for highly crystalline MOCHAs ([AgXPh] ∞: X = Se, S) with high yields. The morphology, crystallinity, chemical and structural stability are thoroughly studied. We investigate tuneable syngas production via electrocatalytic CO2 reduction and find the MOCHAs show a maximum Faraday efficiency (FE) of 55 and 45% for the production of carbon monoxide and hydrogen, respectively.
RESUMEN
In this report, we present results on the electrocatalytic activity of conducting polymers [polyaniline (PANI) and polypyrrole (PPy)] toward the electrochemical oxygen reduction reaction (ORR) to hydrogen peroxide (H2O2). The electropolymerization of the polymers and electrolysis conditions were optimized for H2O2 production. On flat glassy carbon (GC) electrodes, the faradaic efficiency (FE) for H2O2 production was significantly improved by the polymers. Rotating disc electrode (RDE) studies revealed that this is mainly a result of blocking further H2O2 to the water reduction pathway by the polymers. PPy on carbon paper (CP) significantly increased the molar production of H2O2 by over 250% at an average FE of above 95% compared to bare CP with a FE of 25%. Thus, the polymers are acting as catalysts on the electrode for the ORR, although their catalytic mechanisms differ from other electrocatalysts.
