Herein we describe the first homogeneous non-noble metal catalyst for the hydrogenation of CO to methanol. The catalyst is formed in situ from [Co(acac) ], Triphos, and HNTf and enables the reaction to be performed at 100 °C without a decrease in activity. Kinetic studies suggest an inner-sphere mechanism, and in situ NMR and MS experiments reveal the formation of the active catalyst through slow removal of the acetylacetonate ligands.
The production of primary benzylic and aliphatic amines, which represent essential feedstocks and key intermediates for valuable chemicals, life science molecules and materials, is of central importance. Here, we report the synthesis of this class of amines starting from carbonyl compounds and ammonia by Ru-catalyzed reductive amination using H2. Key to success for this synthesis is the use of a simple RuCl2(PPh3)3 catalyst that empowers the synthesis of >90 various linear and branched benzylic, heterocyclic, and aliphatic amines under industrially viable and scalable conditions. Applying this catalyst, −NH2 moiety has been introduced in functionalized and structurally diverse compounds, steroid derivatives and pharmaceuticals. Noteworthy, the synthetic utility of this Ru-catalyzed amination protocol has been demonstrated by upscaling the reactions up to 10 gram-scale syntheses. Furthermore, in situ NMR studies were performed for the identification of active catalytic species. Based on these studies a mechanism for Ru-catalyzed reductive amination is proposed.
A highly porous copper-loaded titanium dioxide material has been developed to catalyze reduction of CO 2 to CO using light as the energy source. In this system, activity for CO production could be enhanced by addition of oxygen, which stabilizes the catalytically active Cu(I) oxidation state. The oxidation half-reaction has also been investigated, and the titanium dioxide itself was found to be the electron source.
Recently, chemoselective
methods for the hydrogenation of fluorinated,
silylated, and borylated arenes have been developed providing direct
access to previously unattainable, valuable products. Herein, a comprehensive
study on the employed rhodium-cyclic (alkyl)(amino)carbene (CAAC)
catalyst precursor is disclosed. Mechanistic experiments, kinetic
studies, and surface-spectroscopic methods revealed supported rhodium(0)
nanoparticles (NP) as the active catalytic species. Further studies
suggest that CAAC-derived modifiers play a key role in determining
the chemoselectivity of the hydrogenation of fluorinated arenes, thus
offering an avenue for further tuning of the catalytic properties.
Cost‐effective production of green hydrogen is a major challenge for global adoption of a hydrogen economy. Technologies such as photoelectrochemical (PEC) or photocatalytic (PC) water splitting and photovoltaic + electrolysis (PV+E) allow for sustainable hydrogen production from sunlight and water, but are not yet competitive with fossil fuel‐derived hydrogen. Herein, open‐source software for techno‐economic analysis (pyH2A) along with a Monte Carlo‐based methodology for modelling of technological progress are developed. Together, these tools allow for the study of required technological improvement to reach a competitive target cost. They are applied to PEC, PC, and PV+E to identify required progress for each and derive actionable research targets. For PEC, it is found that cell lifetime improvements (>2 years) and operation under high solar concentration (>50‐fold) are crucial, necessitating systems with high space‐time yields. In the case of PC, solar‐to‐hydrogen efficiency has to reach at least 6%, and lowering catalyst concentration (<0.2 g L−1) by improving absorption properties is identified as a promising path to low‐cost hydrogen. PV+E requires ≈two or threefold capital cost reductions for photovoltaic and electrolyzer components. It is hoped that these insights can inform materials research efforts to improve these technologies in the most impactful ways.
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