Formation and Reactivity of a Mn(O)(μ-O)Ce Species: A Closest Mimic of Photosystem II.

Understanding the basic structure of the oxygen-evolving complex (OEC) in photosystem II (PS-II) and the water oxidation mechanism can aid in the discovery of more efficient and sustainable catalysts for water oxidation. In this context, we present evidence of the formation of a [(TPA)Mn(O)(μ-O)Ce(NO)] () complex (TPA = tris(pyridyl-2-methyl)amine) by adding aqueous ceric ammonium nitrate to an acetonitrile solution of the [(TPA)Mn] () complex. This unique intermediate () was analyzed by using various spectroscopic techniques and electrospray ionization mass spectrometry.

Axial ligand-induced high electrocatalytic hydrogen evolution activity of molecular cobaloximes in homo- and heterogeneous medium.

Three new molecular cobaloxime complexes with the general formula [ClCo(dpgH)L] (1-3), where L1 = -(4-pyridylmethyl)-1,8-naphthalimide, L2 = 4-bromo--(4-pyridylmethyl)-1,8-naphthalimide, L3 = 4-piperidin--(4-pyridylmethyl)-1,8-naphthalimide, have been synthesized and characterized by UV-Vis, multinuclear NMR, FT-IR and PXRD spectroscopic techniques. The crystal structures of all complexes have also been reported. The electrocatalytic activity of complexes is investigated under two catalysis conditions: (i) homogeneous conditions in acetonitrile using acetic acid (AcOH) as a proton source and (ii) heterogeneous conditions upon immobilization onto the surface of activated carbon cloth (CC).

Exploring suitability of solid 3D substrates for designing self-supported electrocatalysts for water splitting.

The choice of solid 3D substrates to design electrocatalysts significantly impacts the efficiency and effectiveness of self-supported electrocatalysts used in water splitting. These substrates are pivotal in significantly boosting the performance by providing structural support, facilitating electron transport, and increasing the active surface area. This improvement leads to higher catalytic performance and better stability, ultimately optimizing the electrocatalytic process.

Nitrate-coordinated FeNi(OH) for hydrazine oxidation assisted seawater splitting at the industrial-level current density.

In this study, we developed a nitrate-coordinated iron-nickel hydroxide [N-FeNi(OH)] catalyst for hydrazine oxidation-assisted seawater splitting. Replacement of O evolution by hydrazine oxidation in a two-electrode setup resulted in a cell voltage of 1.20 V at 100 mA cm.

Metal-organic frameworks (MOFs) for hybrid water electrolysis: structure-property-performance correlation.

Hybrid water electrolysis (HWE) is a promising pathway for the simultaneous production of high-value chemicals and clean H fuel. Unlike conventional electrochemical water splitting, which relies on the oxygen evolution reaction (OER), HWE involves the anodic oxidation reaction (AOR). The AORs facilitate the conversion of organic or inorganic compounds at the anode into valuable chemicals, while the cathode carries out the hydrogen evolution reaction (HER) to produce H.

Nitrogen substitution induced lattice contraction in nickel nanoparticles for electrochemical hydrogen evolution from simulated seawater.

Herein, we demonstrate a facile method for the introduction of nitrogen in the lattices of nickel nanoparticles to form NiN ( = 0.13, 0.20, 0.

Ruthenium Azobis(benzothiazole): Electronic Structure and Impact of Substituents on the Electrocatalytic Single-Site Water Oxidation Process.

The present article deals with the structurally and spectroelectrochemically characterized newer class of ruthenium-azoheteroarenes [Ru(Ph-trpy)(Cl)(L)]ClO, []ClO-[]ClO (Ph-trpy: 4'-phenyl-2,2':6',2″-terpyridine; L1: 2,2-azobis(benzothiazole) ([]ClO); L2: 2,2'-azobis(6-methylbenzothiazole) ([]ClO); L3: 2,2'-azobis(6-chlorobenzothiazole) ([]ClO)). A collective consideration of experimental (i.e.

Chlorocobaloxime containing -(4-pyridylmethyl)-1,8-naphthalamide peripheral ligands: synthesis, characterization and enhanced electrochemical hydrogen evolution in alkaline medium.

Two new discrete cobaloxime based complexes with the general formula [ClCo(dioxime)L] (1 and 2), L1 = -(4-pyridylmethyl)-1,8-naphthalamide, L2 = 4-bromo--(4-pyridylmethyl)-1,8-naphthalamide have been synthesized and characterized by various spectroscopic techniques such as FT-IR, H, C{H} NMR and PXRD. The molecular structures of both complexes have also been determined using single crystal X-ray crystallography. The solid state molecular structures revealed distorted octahedral geometry around the Co(III) central metal ion with two dioximes in the equatorial plane and axial positions are occupied by chloro and pyridine nitrogen of -(4-pyridylmethyl)-1,8-naphthalamide ligands.

Homoleptic Ni(II) dithiocarbamate complexes as pre-catalysts for the electrocatalytic oxygen evolution reaction.

Four new functionalized Ni(II) dithiocarbamate complexes of the formula (1-4) (L = -methylthiophene--3-pyridylmethyl dithiocarbamate, L = -methylthiophene--4-pyridylmethyl dithiocarbamate, L = -benzyl--3-pyridylmethyl dithiocarbamate, and L = -benzyl--4-pyridylmethyl dithiocarbamate) have been synthesized and characterized by IR, UV-vis, and H and C{H} NMR spectroscopic techniques. The solid-state structure of complex 1 has also been determined by single crystal X-ray crystallography. Single crystal X-ray analysis revealed a monomeric centrosymmetric structure for complex 1 in which two dithiocarbamate ligands are bonded to the Ni(II) metal ion in a S^S chelating mode resulting in a square planar geometry around the nickel center.

Ruthenium-Benzothiadiazole Building Block Derived Dynamic Heterometallic Ru-Ag Coordination Polymer and Its Enhanced Water-Splitting Feature.

This article deals with the development of the unprecedented redox-mediated heterometallic coordination polymer {[Ru(acac)(μ-bis-η-,η-NBTD)Ag(ClO)]ClO} () via the oxidation of the monomeric building block -[Ru(acac)(η-N-BTD)] () by AgClO (BTD = exodentate 2,1,3-benzothiadiazole, acac = acetylacetonate). Monomeric -[Ru(acac)(η-N-BTD)] () and [Ru(acac)(η--BTD)(CHCN)] () were simultaneously obtained from the electron-deficient BTD heterocycle and the electron-rich metal precursor Ru(acac)(CHCN) in refluxing CHCN. Molecular identities of - were authenticated by their single-crystal X-ray structures as well as by solution spectral features.

Tuning the properties of CoFe-layered double hydroxide by vanadium substitution for improved water splitting activity.

Here, we demonstrate the enhanced water splitting activity of CoFe-LDH by vanadium substitution. Volcano plots are obtained for intrinsic water oxidation and hydrogen evolution with increasing vanadium substitution, and the best catalyst V0.3-CoFe-LDH achieved 10 mA cm-2 current density for H2 and O2 evolution merely at 98 mV and 240 mV overpotential, respectively.

Electrochemical transformation of Prussian blue analogues into ultrathin layered double hydroxide nanosheets for water splitting.

Herein, we demonstrate a template directed route for the synthesis of self-supported cobalt-iron based Prussian blue analogues (PBAs). The PBAs are electrochemically transformed into layered double hydroxides to produce excellent water oxidation and hydrogen evolution activity, while the overall water splitting is attained at a cell voltage of 1.58 V to reach 20 mA cm-2 current density.

Designing Self-Supported Metal-Organic Framework Derived Catalysts for Electrochemical Water Splitting.

To achieve efficient water splitting, it is essential to develop catalysts with high electrochemical performance, enhanced durability and tunable properties. Most of the transition metal-based catalysts employed for the water splitting have been fabricated on the solid-electrode support by using binder, which decreases the activity and durability of the catalyst system. In this respect, self-supported metal organic framework (MOF) derived catalysts have been introduced with enhanced catalytic activity and mechanical stability for the electrochemical water splitting.