Two Novel Schiff Base Manganese Complexes as Bifunctional Electrocatalysts for CO₂ Reduction and Water Oxidation

One mononuclear Mn(III) complex [MnIIIL(H2O)(MeCN)](ClO4) (1) and one hetero-binuclear complex [(CuIILMnII(H2O)3)(CuIIL)2](ClO4)2·CH3OH (2) have been synthesized with the Schiff base ligand (H2L = N,N′-bis(3-methoxysalicylidene)-1,2-phenylenediamine). Single crystal X-ray structural analysis manifests that the Mn(III) ion in 1 has an octahedral coordination structure, whereas the Mn(II) ion in 2 possesses a trigonal bipyramidal configuration and the Cu(II) ion in 2 is four-coordinated with a square-planar geometry. Electrochimerical catalytic investigation demonstrates that the two complexes can electrochemically catalyze water oxidation and CO2 reduction simultaneously. The coordination environments of the Mn(III), Mn(II), and Cu(II) ions in 1 and 2 were provided by the Schiff base ligand (L) and labile solvent molecules. The coordinately unsaturated environment of the Cu(II) center in 2 can perfectly facilitate the catalytic performance of 2. Complexes 1 and 2 display that the over potentials for water oxidation are 728 mV and 216 mV, faradaic efficiencies (FEs) are 88% and 92%, respectively, as well as the turnover frequency (TOF) values for the catalytic reduction of CO2 to CO are 0.38 s−1 at −1.65 V and 15.97 s−1 at −1.60 V, respectively. Complex 2 shows much better catalytic performance for both water oxidation and CO2 reduction than that of complex 1, which could be owing to a structural reason which is attributed to the synergistic catalytic action of the neighboring Mn(III) and Cu(II) active sites in 2. Complexes 1 and 2 are the first two compounds coordinated with Schiff base ligand for both water oxidation and CO2 reduction. The finding in this work can offer significant inspiration for the future development of electrocatalysis in this area

Two Novel Schiff Base Manganese Complexes as Bifunctional Electrocatalysts for CO2 Reduction and Water Oxidation

One mononuclear Mn(III) complex [MnIIIL(H2O)(MeCN)](ClO4) (1) and one hetero-binuclear complex [(CuIILMnII(H2O)3)(CuIIL)2](ClO4)2·CH3OH (2) have been synthesized with the Schiff base ligand (H2L = N,N′-bis(3-methoxysalicylidene)-1,2-phenylenediamine). Single crystal X-ray structural analysis manifests that the Mn(III) ion in 1 has an octahedral coordination structure, whereas the Mn(II) ion in 2 possesses a trigonal bipyramidal configuration and the Cu(II) ion in 2 is four-coordinated with a square-planar geometry. Electrochimerical catalytic investigation demonstrates that the two complexes can electrochemically catalyze water oxidation and CO2 reduction simultaneously. The coordination environments of the Mn(III), Mn(II), and Cu(II) ions in 1 and 2 were provided by the Schiff base ligand (L) and labile solvent molecules. The coordinately unsaturated environment of the Cu(II) center in 2 can perfectly facilitate the catalytic performance of 2. Complexes 1 and 2 display that the over potentials for water oxidation are 728 mV and 216 mV, faradaic efficiencies (FEs) are 88% and 92%, respectively, as well as the turnover frequency (TOF) values for the catalytic reduction of CO2 to CO are 0.38 s−1 at −1.65 V and 15.97 s−1 at −1.60 V, respectively. Complex 2 shows much better catalytic performance for both water oxidation and CO2 reduction than that of complex 1, which could be owing to a structural reason which is attributed to the synergistic catalytic action of the neighboring Mn(III) and Cu(II) active sites in 2. Complexes 1 and 2 are the first two compounds coordinated with Schiff base ligand for both water oxidation and CO2 reduction. The finding in this work can offer significant inspiration for the future development of electrocatalysis in this area

Microwave Speech Recognizer Empowered by a Programmable Metasurface

International audienceSpeech recognition becomes increasingly important in the modern society, especially for human–machine interactions, but its deployment is still severely thwarted by the struggle of machines to recognize voiced commands in challenging real‐life settings: oftentimes, ambient noise drowns the acoustic sound signals, and walls, face masks or other obstacles hide the mouth motion from optical sensors. To address these formidable challenges, an experimental prototype of a microwave speech recognizer empowered by programmable metasurface is presented here that can remotely recognize human voice commands and speaker identities even in noisy environments and if the speaker's mouth is hidden behind a wall or face mask. The programmable metasurface is the pivotal hardware ingredient of the system because its large aperture and huge number of degrees of freedom allows the system to perform a complex sequence of sensing tasks, orchestrated by artificial‐intelligence tools. Relying solely on microwave data, the system avoids visual privacy infringements. The developed microwave speech recognizer can enable privacy‐respecting voice‐commanded human–machine interactions is experimentally demonstrated in many important but to‐date inaccessible application scenarios. The presented strategy will unlock new possibilities and have expectations for future smart homes, ambient‐assisted health monitoring, as well as intelligent surveillance and security

Microwave Speech Recognizer Empowered by a Programmable Metasurface

We present an experimental prototype of a microwave speech recognizer empowered by a programmable metasurface that can recognize voice commands and speaker identities remotely even in noisy environments and if the speaker’s mouth is hidden behind a wall or face mask. Thereby, we enable voice-commanded human machine interactions in many important but to-date inaccessible application scenarios, including smart health careand factory scenarios. The programmable metasurface is the pivotal hardware ingredient of our system because its large aperture and huge number of degrees of freedom allows our system to perform a complex sequence of tasks, orchestrated by artificial-intelligence tools. First, the speaker’s mouth is localized by imaging the scene and identifying the region of interest. Second, microwaves are efficiently focused on the speaker’s mouth toencode information about the vocalized speech in reflected microwave biosignals. The efficient focusing on the speaker’s mouth is the origin of our system’s robustness to various types of parasitic motion. Third, a dedicated neural network directly retrieves the sought-after speech information from the measured microwave biosignals. Relying solely on microwave data, our system avoids visual privacy infringements. We expect that thepresented strategy will unlock new possibilities for future smart homes, ambient-assisted health monitoring and care, smart factories, as well as intelligent surveillance and security

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