Cobaloxime complex salts : synthesis, patterning on carbon nanomembranes and heterogeneous hydrogen evolution studies

Cobaloximes are promising, earth-abundant catalysts for the light-driven hydrogen evolution reaction. Typically, these cobalt(III) complexes are prepared in situ or employed in their neutral form, e.g. [Co(dmgH 2 )(py)Cl], even though related complex salts have been reported previously and could in principle offer improved catalytic activity as well as more efficient immobilization on solid support. Here we report an interdisciplinary investigation into complex salts [Co(dmgH) 2 (py) 2 ] + [Co(dmgBPh 2 ) 2 Cl 2 ] - , TBA + [Co(dmgBPh 2 ) 2 Cl 2 ] - and [Co(dmgH) 2 (py) 2 ] + BArF - . We describe their strategic syntheses from commercially available complex [Co(dmgH) 2 (py)Cl] and demonstrate that these double and single complex salts are potent catalysts for the light-driven hydrogen evolution reaction. We also show that scanning electrochemical cell microscopy can be used to deposit arrays of catalysts [Co(dmgH) 2 (py) 2 ] + [Co(dmgBPh 2 ) 2 Cl 2 ] - and [Co(dmgH) 2 (py)Cl] on supported and free-standing amino-terminated ~ 1 nm thick carbon nanomembranes (CNMs). Photocatalytic H 2 evolution at such arrays was quantified with Pd microsensors using scanning electrochemical microscopy, thus providing a new approach for catalytic evaluation and opening up novel routes for the creation and analysis of “designer catalyst arrays”, nano-printed in a desired pattern on a solid support

Carbene based photochemical molecular assemblies for solar driven hydrogen generation

Novel photocatalysts based on ruthenium complexes with NHC (N-heterocyclic carbene)-type bridging ligands have been prepared and structurally and photophysically characterised. The identity of the NHC-unit of the bridging ligand was established unambiguously by means of X-ray structural analysis of a heterodinuclear ruthenium–silver complex. The photophysical data indicate ultrafast intersystem crossing into an emissive and a non-emissive triplet excited state after excitation of the ruthenium centre. Exceptionally high luminescence quantum yields of up to 39% and long lifetimes of up to 2 μs are some of the triplet excited state characteristics. Preliminary studies into the visible light driven photocatalytic hydrogen formation show no induction phase and constant turnover frequencies that are independent on the concentration of the photocatalyst. In conclusion this supports the notion of a stable assembly under photocatalytic conditions

Search for intermediate-mass black hole binaries in the third observing run of Advanced LIGO and Advanced Virgo

International audienceIntermediate-mass black holes (IMBHs) span the approximate mass range 100−105 M⊙, between black holes (BHs) that formed by stellar collapse and the supermassive BHs at the centers of galaxies. Mergers of IMBH binaries are the most energetic gravitational-wave sources accessible by the terrestrial detector network. Searches of the first two observing runs of Advanced LIGO and Advanced Virgo did not yield any significant IMBH binary signals. In the third observing run (O3), the increased network sensitivity enabled the detection of GW190521, a signal consistent with a binary merger of mass ∼150 M⊙ providing direct evidence of IMBH formation. Here, we report on a dedicated search of O3 data for further IMBH binary mergers, combining both modeled (matched filter) and model-independent search methods. We find some marginal candidates, but none are sufficiently significant to indicate detection of further IMBH mergers. We quantify the sensitivity of the individual search methods and of the combined search using a suite of IMBH binary signals obtained via numerical relativity, including the effects of spins misaligned with the binary orbital axis, and present the resulting upper limits on astrophysical merger rates. Our most stringent limit is for equal mass and aligned spin BH binary of total mass 200 M⊙ and effective aligned spin 0.8 at 0.056 Gpc−3 yr−1 (90% confidence), a factor of 3.5 more constraining than previous LIGO-Virgo limits. We also update the estimated rate of mergers similar to GW190521 to 0.08 Gpc−3 yr−1.Key words: gravitational waves / stars: black holes / black hole physicsCorresponding author: W. Del Pozzo, e-mail: [email protected]† Deceased, August 2020