A Monodisperse, End‐Capped Ru(bda) Oligomer with Outstanding Performance in Heterogeneous Electrochemical Water Oxidation

Water oxidation catalysis is a key step for sustainable fuel production by water splitting into hydrogen and oxygen. The synthesis of a novel coordination oligomer based on four Ru(bda) (bda = 2,2′‐bipyridine‐6,6′‐dicarboxylate) centers, three 4,4′‐bipyridine (4,4′‐bpy) linkers, and two 4‐picoline (4‐pic) end caps is reported. The monodispersity of this tetranuclear compound is characterized by NMR techniques. Heterogeneous electrochemical water oxidation after immobilization on multi‐walled carbon nanotubes (MWCNTs) shows catalytic performance unprecedented for this compound class, with a turnover frequency (TOF) of 133 s−1 and a turnover number (TON) of 4.89 × 106, at a current density of 43.8 mA cm−2 and a potential of 1.45 V versus normal hydrogen electrode (NHE).

[1]  G. Meyer,et al.  General Kinetic Model for pH Dependence of Proton-Coupled Electron Transfer: Application to an Electrochemical Water Oxidation System. , 2023, Journal of the American Chemical Society.

[2]  F. Würthner,et al.  Self‐assembled Ru(bda) Coordination Oligomers as Efficient Catalysts for Visible Light‐Driven Water Oxidation in Pure Water , 2022, Angewandte Chemie.

[3]  F. Würthner,et al.  Enzyme-like water preorganization in a synthetic molecular cleft for homogeneous water oxidation catalysis , 2022, Nature Catalysis.

[4]  A. Cadranel,et al.  The Excited‐State Creutz–Taube Ion , 2022, Angewandte Chemie.

[5]  Junwang Tang,et al.  Polymer Photoelectrodes for Solar Fuel Production: Progress and Challenges , 2022, Chemical reviews.

[6]  M. Natali,et al.  Beyond Water Oxidation: Hybrid, Molecular-Based Photoanodes for the Production of Value-Added Organics , 2022, Frontiers in Chemistry.

[7]  F. Puntoriero,et al.  Recent progresses in molecular-based artificial photosynthesis , 2022, Current Opinion in Green and Sustainable Chemistry.

[8]  Lei Wang,et al.  Boosting Electrochemical Oxygen Reduction Performance of Iron Phthalocyanine through Axial Coordination Sphere Interaction. , 2021, ChemSusChem.

[9]  E. Fazio,et al.  Photoinduced Water Oxidation in Chitosan Nanostructures Containing Covalently Linked RuII Chromophores and Encapsulated Iridium Oxide Nanoparticles , 2021, Chemistry.

[10]  F. Würthner,et al.  Surface-Promoted Evolution of Ru-bda Coordination Oligomers Boosts the Efficiency of Water Oxidation Molecular Anodes , 2021, Journal of the American Chemical Society.

[11]  F. Würthner,et al.  Structure‐Activity Relationship for Di‐ up to Tetranuclear Macrocyclic Ruthenium Catalysts in Homogeneous Water Oxidation , 2021, Chemistry.

[12]  E. Alessio,et al.  Models of molecular photocatalysts for water oxidation: Strategies for conjugating the Ru(bda) fragment (bda = 2,2′-bipyridine-6,6′-dicarboxylate) to porphyrin photosensitizers , 2021 .

[13]  G. Dolanc,et al.  Can Green Hydrogen Production Be Economically Viable under Current Market Conditions , 2020, Energies.

[14]  F. Würthner,et al.  Efficient Electrochemical Water Oxidation by a Trinuclear Ru(bda) Macrocycle Immobilized on Multi‐Walled Carbon Nanotube Electrodes , 2020, Advanced Energy Materials.

[15]  M. Lanza,et al.  Water oxidation electrocatalysis using ruthenium coordination oligomers adsorbed on multiwalled carbon nanotubes , 2020, Nature Chemistry.

[16]  Carolina Gimbert-Suriñach,et al.  A Ru-bda Complex with a Dangling Carboxylate Group: Synthesis and Electrochemical Properties. , 2020, Inorganic chemistry.

[17]  I. Ciofini,et al.  Increasing the Cytotoxicity of Ru(II) Polypyridyl Complexes by tuning the Electronic Structure of Dioxo Ligands. , 2019, Journal of the American Chemical Society.

[18]  Carolina Gimbert-Suriñach,et al.  The development of molecular water oxidation catalysts , 2019, Nature Reviews Chemistry.

[19]  G. Meyer,et al.  Molecular Photoelectrode for Water Oxidation Inspired by Photosystem II. , 2019, Journal of the American Chemical Society.

[20]  Licheng Sun,et al.  Ru-bda: Unique Molecular Water-Oxidation Catalysts with Distortion Induced Open Site and Negatively Charged Ligands. , 2019, Journal of the American Chemical Society.

[21]  Carolina Gimbert-Suriñach,et al.  Seven Coordinated Molecular Ruthenium-Water Oxidation Catalysts: A Coordination Chemistry Journey. , 2019, Chemical reviews.

[22]  Javier J. Concepcion,et al.  O-O Radical Coupling: From Detailed Mechanistic Understanding to Enhanced Water Oxidation Catalysis. , 2018, Inorganic chemistry.

[23]  M. Nilsson,et al.  Improving the Interpretation of Small Molecule Diffusion Coefficients. , 2018, Analytical chemistry.

[24]  J. Reek,et al.  Rational Design Rules for Molecular Water Oxidation Catalysts based on Scaling Relationships. , 2017, Chemistry.

[25]  Jie Zhu,et al.  Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film. , 2017, ChemSusChem.

[26]  Yan Xie,et al.  Light-Driven Water Splitting by a Covalently Linked Ruthenium-Based Chromophore–Catalyst Assembly , 2017 .

[27]  F. Würthner,et al.  Trinuclear Ruthenium Macrocycles: Toward Supramolecular Water Oxidation Catalysis in Pure Water , 2017 .

[28]  A. Llobet,et al.  Foot of the Wave Analysis for Mechanistic Elucidation and Benchmarking Applications in Molecular Water Oxidation Catalysis. , 2016, ChemSusChem.

[29]  A. Llobet,et al.  A Million Turnover Molecular Anode for Catalytic Water Oxidation. , 2016, Angewandte Chemie.

[30]  Nathan H. Williamson,et al.  The lognormal and gamma distribution models for estimating molecular weight distributions of polymers using PGSE NMR. , 2016, Journal of magnetic resonance.

[31]  Peter D. Frischmann,et al.  A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II. , 2016, Nature chemistry.

[32]  V. Batista,et al.  Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex. , 2015, Journal of the American Chemical Society.

[33]  J. Hodak,et al.  Four chromophores in one building block: synthesis, structure and characterization of trans-[Ru(MQ)4Cl2]4+ and trans-[Ru(4,4’-bpy)4Cl2] (MQ+ = N-methyl-4,4’-bipyridinium, bpy = bipyridine) , 2015 .

[34]  L. Cavallo,et al.  Supramolecular water oxidation with Ru-bda-based catalysts. , 2014, Chemistry.

[35]  J. Savéant,et al.  Multielectron, Multistep Molecular Catalysis of Electrochemical Reactions: Benchmarking of Homogeneous Catalysts , 2014 .

[36]  Licheng Sun,et al.  Highly efficient and robust molecular ruthenium catalysts for water oxidation , 2012, Proceedings of the National Academy of Sciences.

[37]  Antoni Llobet,et al.  A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II. , 2012, Nature chemistry.

[38]  A. Cadranel,et al.  Efficient energy transfer via the cyanide bridge in dinuclear complexes containing Ru(II) polypyridine moieties. , 2012, Dalton transactions.

[39]  Maurizio Prato,et al.  Shaping the beating heart of artificial photosynthesis: oxygenic metal oxide nano-clusters , 2012 .

[40]  Biaobiao Zhang,et al.  Highly efficient oxidation of water by a molecular catalyst immobilized on carbon nanotubes. , 2011, Angewandte Chemie.

[41]  P. D. Tran,et al.  Noncovalent modification of carbon nanotubes with pyrene-functionalized nickel complexes: carbon monoxide tolerant catalysts for hydrogen evolution and uptake. , 2011, Angewandte Chemie.

[42]  E. Fujita,et al.  Molecular approaches to the photocatalytic reduction of carbon dioxide for solar fuels. , 2009, Accounts of chemical research.

[43]  Licheng Sun,et al.  Isolated seven-coordinate Ru(IV) dimer complex with [HOHOH](-) bridging ligand as an intermediate for catalytic water oxidation. , 2009, Journal of the American Chemical Society.

[44]  Haisheng Chen,et al.  Progress in electrical energy storage system: A critical review , 2009 .

[45]  P. Balaram,et al.  A model for the interaction of trifluoroethanol with peptides and proteins. , 2009, International journal of peptide and protein research.

[46]  Javier J. Concepcion,et al.  One site is enough. Catalytic water oxidation by [Ru(tpy)(bpm)(OH2)]2+ and [Ru(tpy)(bpz)(OH2)]2+. , 2008, Journal of the American Chemical Society.

[47]  W. Kaim,et al.  Towards new organometallic wires: tetraruthenium complexes bridged by phenylenevinylene and vinylpyridine ligands. , 2007, Chemistry.

[48]  G. Meyer.  Molecular approaches to solar energy conversion with coordination compounds anchored to semiconductor surfaces. , 2005, Inorganic chemistry.

[49]  R. Thummel,et al.  A new family of Ru complexes for water oxidation. , 2005, Journal of the American Chemical Society.

[50]  Yoram Cohen,et al.  Diffusion NMR spectroscopy in supramolecular and combinatorial chemistry: an old parameter--new insights. , 2005, Angewandte Chemie.

[51]  Antoni Llobet,et al.  A new Ru complex capable of catalytically oxidizing water to molecular dioxygen. , 2004, Journal of the American Chemical Society.

[52]  José García de la Torre,et al.  Comparison of theories for the translational and rotational diffusion coefficients of rod‐like macromolecules. Application to short DNA fragments , 1984 .

[53]  Susan W. Gersten,et al.  Catalytic oxidation of water by an oxo-bridged ruthenium dimer , 1982 .