Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the 'green' synthesis of non-racemic chiral molecules.

The structure of IrO2 during the oxygen evolution reaction (OER) was studied by operando X-ray absorption spectroscopy (XAS) at the Ir L3-edge to gain insight into the processes that occur during the electrocatalytic reaction at the anode during water electrolysis. For this purpose, calcined and uncalcined IrO2 nanoparticles were tested in an operando spectroelectrochemical cell. In situ XAS under different applied potentials uncovered strong structural changes when changing the potential. Modulation excitation spectroscopy combined with XAS enhanced the information on the dynamic changes significantly. Principal component analysis (PCA) of the resulting spectra as well as FEFF9 calculations uncovered that both the Ir L3-edge energy and the white line intensity changed due to the formation of oxygen vacancies and lower oxidation state of iridium at higher potentials, respectively. The deconvoluted spectra and their components lead to two different OER modes. It was observed that at higher OER potentials, the well-known OER mechanisms need to be modified, which is also associated with the stabilization of the catalyst, as confirmed by in situ inductively coupled plasma mass spectrometry (ICP-MS). At these elevated OER potentials above 1.5 V, stronger Ir–Ir interactions were observed. They were more dominant in the calcined IrO2 samples than in the uncalcined ones. The stronger Ir–Ir interaction upon vacancy formation is also supported by theoretical studies. We propose that this may be a crucial factor in the increased dissolution stability of the IrO2 catalyst after calcination. The results presented here provide additional insights into the OER in acid media and demonstrate a powerful technique for quantifying the differences in mechanisms on different OER electrocatalysts. Furthermore, insights into the OER at a fundamental level are provided, which will contribute to further understanding of the reaction mechanisms in water electrolysis.

The increasing scarcity of iridium (Ir) and its rutile-type oxide (IrO 2 ), the current state-of-the-art oxygen evolution reaction (OER) catalysts, is driving the transition toward the use of mixed Ir oxides with a highly active yet inexpensive metal (Ir x M 1−x O 2 ). Ruthenium (Ru) has been commonly employed due to its high OER activity although its electrochemical stability in Ir-Ru mixed oxide nanoparticles (Ir x Ru 1−x O 2 NPs), especially at high relative contents, is rarely evaluated for long-term application as water electrolyzers. In this work, we bridge the knowledge gap by performing a thorough study on the composition-and phase-dependent stability of welldefined Ir x Ru 1−x O 2 NPs prepared by flame spray pyrolysis under dynamic operating conditions. As-prepared NPs (Ir x Ru 1−x O y ) present an amorphous coral-like structure with a hydrous Ir-Ru oxide phase, which upon post-synthetic thermal treatment fully converts to a rutile-type structure followed by a selective Ir enrichment at the NP topmost surface. It was demonstrated that Ir incorporation into a RuO 2 matrix drastically reduced Ru dissolution by ca. 10-fold at the expense of worsening Ir inherent stability, regardless of the oxide phase present. Hydrous Ir x Ru 1−x O y NPs, however, were shown to be 1000-fold less stable than rutile-type Ir x Ru 1−x O 2 , where the severe Ru leaching yielded a fast convergence toward the activity of monometallic hydrous IrO y . For rutiletype Ir x Ru 1−x O 2 , the sequential start-up/shut-down OER protocol employed revealed a steady-state dissolution for both Ir and Ru, as well as the key role of surface Ru species in OER activity: minimal Ru surface losses (<1 at. %) yielded OER activities for tested Ir 0.2 Ru 0.8 O 2 equivalent to those of untested Ir 0.8 Ru 0.2 O 2 . Ir enrichment at the NP topmost surface, which mitigates selective subsurface Ru dissolution, is identified as the origin of the NP stabilization. These results suggest Ru-rich Ir x Ru 1−x O 2 NPs to be viable electrocatalysts for long-term water electrolysis, with significant repercussions in cost reduction.