A biomimetic photoelectrochemical device from a molecular heterometallic sodium–manganese water splitting catalyst

Abstract

A photoelectrochemical device for water splitting has been fabricated from a new water stable molecular [Na 2 Mn 4 ] complex that acts as an in situ precursor towards NaMn 2 O x nanoparticles under catalytic conditions when immobilized within a conductive PEDOT : PSS/Nafion composite film for optimal electron transport. The optimized photoanode architecture of ITO/TiO 2 /Ru/60% PEDOT : PSS/Na 2 Mn 4 /Nafion resulted in a water oxidation onset potential of 1.35 V (vs. RHE) and achieved a maximum current density of 1.31 mA cm −2 (initial) and 0.80 mA cm −2 (stabilized) at 1.8 V (vs. RHE) at pH 6.5. † Electronic supplementary information (ESI) available: The detailed synthesis procedure for the [Na 2 Mn 4 ] complex is provided. The single crystal X-ray refinement data, PEDOT : PSS/Na 2 Mn 4 /Nafion solution preparation and UV-Vis spectrum, time-of-flight secondary-ion-mass-spectroscopy data, field emission scanning electron microscope images of the 60% PEDOT : PSS/Na 2 Mn 4 /Nafion device, electron paramagnetic resonance measurements, and control experiment are also included. CCDC 949196. For ESI and crystallographic data in CIF or other electronic format see

New Avenues to Chemical Space for Energy Materials by the Molecular Precursor Approach

“…It illustrates how the choice of discrete precursors fine-tunes the structure and composition of the resulting solid catalytic materials. [94,96] In extension to obtained oxide materials, the group of Savéant observed the formation of Co nanoparticles from the electrophoretic decomposition of the Co[(diphenylglyoxime) 3 (BF) 2 ]BF 4 complex at reducing potentials. The synthesized nanoparticles showed remarkable activity toward HER in water at pH 7 at low overpotential.…”

Two Trinuclear CuII Complexes: Effect of Phosphonate Ligand on the Magnetic Property and Electrocatalytic Reactivity for Water Oxidation

“…as water oxidation catalyst has attracted much more attention. [12][13][14][15] Among these non-precious metal complexes, owing to the multiplex coordination geometries and redox or electron transfer reactions of Cu II ion, someC u II complexes have been provedt oh aveh igh activity in electrocatalytic water oxidation. [16,17] However,m any of thesereported mononuclear Cu II water oxidation catalysts (WOC)n eed to get high oxidation state for the four electrons transfer catalytic process, which lead to low stability or high overpotentials of these catalysts.…”

“…However, as the precious metals limit the large‐scale application of the catalysts, exploring inexpensive and earth‐abundant metal complexes such as Cu, Co, Ni, Mn, Fe etc. as water oxidation catalyst has attracted much more attention . Among these non‐precious metal complexes, owing to the multiplex coordination geometries and redox or electron transfer reactions of Cu II ion, some Cu II complexes have been proved to have high activity in electrocatalytic water oxidation .…”