Electrocatalytic Reduction of Dinitrogen to Ammonia with Water as Proton and Electron Donor Catalyzed by a Combination of a Tri-ironoxotungstate and an Alkali Metal Cation.

The electrification of ammonia synthesis is a key target for its decentralization and lowering impact on atmospheric CO2 concentrations. The lithium metal electrochemical reduction of nitrogen to ammonia using alcohols as proton/electron donors is an important advance, but requires rather negative potentials, and anhydrous conditions. Organometallic electrocatalysts using redox mediators have also been reported. Water as a proton and electron donor has not been demonstrated in these reactions. Here a N2 to NH3 electrocatalytic reduction using an inorganic molecular catalyst, a tri-iron substituted polyoxotungstate, {SiFe3W9}, is presented. The catalyst requires the presence of Li+ or Na+ cations as promoters through their binding to {SiFe3W9}. Experimental NMR, CV and UV-vis measurements, and MD simulations and DFT calculations show that the alkali metal cation enables the decrease of the redox potential of {SiFe3W9} allowing the activation of N2. Controlled potential electrolysis with highly purified 14N2 and 15N2 ruled out formation of NH3 from contaminants. Importantly, using Na+ cations and polyethylene glycol as solvent, the anodic oxidation of water can be used as a proton and electron donor for the formation of NH3. In an undivided cell electrolyzer under 1 bar N2, rates of NH3 formation of 1.15 nmol sec-1 cm-2, faradaic efficiencies of ∼25%, 5.1 equiv of NH3 per equivalent of {SiFe3W9} in 10 h, and a TOF of 64 s-1 were obtained. The future development of suitable high surface area cathodes and well solubilized N2 and the use of H2O as the reducing agent are important keys to the future deployment of an electrocatalytic ammonia synthesis.

Hybrid Molecular Magnets with Lanthanide- and Countercation-Mediated Interfacial Electron Transfer between Phthalocyanine and Polyoxovanadate.

A series of {V12}-nuclearity polyoxovanadate cages covalently functionalized with one or sandwiched by two phthalocyaninato (Pc) lanthanide (Ln) moieties via V-O-Ln bonds were prepared and fully characterized for paramagnetic Ln = SmIII-ErIII and diamagnetic Ln = LuIII, including YIII. The LnPc-functionalized {V12O32} cages with fully oxidized vanadium centers in the ground state were isolated as (nBu4N)3[HV12O32Cl(LnPc)] and (nBu4N)2[HV12O32Cl(LnPc)2] compounds. As corroborated by a combined experimental (EPR, DC and AC SQUID, laser photolysis transient absorption spectroscopy, and electrochemistry) and computational (DFT, MD, and model Hamiltonian approach) methods, the compounds feature intra- and intermolecular electron transfer that is responsible for a partial reduction at V(3d) centers from VV to VIV in the solid state and at high sample concentrations. The effects are generally Ln dependent and are clearly demonstrated for the (nBu4N)3[HV12O32Cl(LnPc)] representative with Ln = LuIII or DyIII. Intramolecular charge transfer takes place for Ln = LuIII and occurs from a Pc ligand via the Ln center to the {V12O32} core of the same molecule, whereas for Ln = DyIII, only intermolecular charge transfer is allowed, which is realized from Pc in one molecule to the {V12O32} core of another molecule usually via the nBu4N+ countercation. For all Ln but DyIII, two of these phenomena may be present in different proportions. Besides, it is demonstrated that (nBu4N)3[HV12O32Cl(DyPc)] is a field-induced single molecule magnet with a maximal relaxation time of the order 10-3 s. The obtained results open up the way to further exploration and fine-tuning of these three modular molecular nanocomposites regarding tailoring and control of their Ln-dependent charge-separated states (induced by intramolecular transfer) and relaxation dynamics as well as of electron hopping between molecules. This should enable us to realize ultra-sensitive polyoxometalate powered quasi-superconductors, sensors, and data storage/processing materials for quantum technologies and neuromorphic computing.

Molecular Transition Metal Oxide Electrocatalysts for the Reversible Carbon Dioxide-Carbon Monoxide Transformation.

Carbon monoxide dehydrogenase (CODH) enzymes are active for the reversible CO oxidation-CO2 reduction reaction and are of interest in the context of CO2 abatement and carbon-neutral solar fuels. Bioinspired by the active-site composition of the CODHs, polyoxometalates triply substituted with first-row transition metals were modularly synthesized. The polyanions, in short, {SiM3 W9 } and {SiM'2 M''W9 }, M, M', M''=CuII , NiII , FeIII are shown to be electrocatalysts for reversible CO oxidation-CO2 reduction. A catalytic Tafel plot showed that {SiCu3 W9 } was the most reactive for CO2 reduction, and electrolysis reactions yielded significant amounts of CO with 98 % faradaic efficiency. In contrast, Fe-Ni compounds such as {SiFeNi2 W9 } preferably catalyzed the oxidation of CO to CO2 similar to what is observed for the [NiFe]-CODH enzyme. Compositional control of the heterometal complexes, now and in the future, leads to control of reactivity and selectivity for CO2 electrocatalytic reduction.

Tuning Photoinduced Electron Transfer in POM-Bodipy Hybrids by Controlling the Environment: Experiment and Theory.

The optical and electrochemical properties of a series of polyoxometalate (POM) oxoclusters decorated with two bodipy (boron-dipyrromethene) light-harvesting units were examined. Evaluated here in this polyanionic donor-acceptor system is the effect of the solvent and associated counterions on the intramolecular photoinduced electron transfer. The results show that both solvents and counterions have a major impact upon the energy of the charge-transfer state by modifying the solvation shell around the POMs. This modification leads to a significantly shorter charge separation time in the case of smaller counterion and slower charge recombination in a less polar solvent. These results were rationalized in terms of Marcus theory and show that solvent and counterion both affect the driving force for photoinduced electron transfer and the reorganization energy. This was corroborated with theoretical investigations combining DFT and molecular dynamics simulations.