DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A cobalt mimochrome for photochemical hydrogen evolution from neutral water

Journal Article · · Journal of Inorganic Biochemistry
 [1];  [2];  [2];  [2];  [3];  [3];  [2]
  1. Univ. of Rochester, NY (United States); OSTI
  2. Univ. of Rochester, NY (United States)
  3. Univ. of Naples Federico II (Italy)

Here, a system for visible light-driven hydrogen production from water is reported. This system makes use of a synthetic mini-enzyme known as a mimochrome (CoMC6*a) consisting of a cobalt deuteroporphyrin and two attached peptides as a catalyst, [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) as a photosensitizer, and ascorbic acid as a sacrificial electron donor. The system achieves turnover numbers (TONs) up to 10,000 with respect to catalyst and optimal activity at pH 7. Comparison with related systems shows that CoMC6*a maintains the advantages of biomolecular catalysts, while exceeding other cobalt porphyrins in terms of total TON and longevity of catalysis. Herein, we lay groundwork for future study, where the synthetic nature of CoMC6*a will provide a unique opportunity to tailor proton reduction chemistry and expand to new reactivity.

Research Organization:
Univ. of Rochester, NY (United States)
Sponsoring Organization:
National Institutes of Health (NIH); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0002106
OSTI ID:
1977310
Journal Information:
Journal of Inorganic Biochemistry, Journal Name: Journal of Inorganic Biochemistry Journal Issue: C Vol. 230; ISSN 0162-0134
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (91)

Photocatalysis: Basic Principles, Diverse Forms of Implementations and Emerging Scientific Opportunities journal August 2017
Splitting Water with Cobalt journal July 2011
From Solar Energy to Fuels: Recent Advances in Light-Driven C 1 Chemistry journal September 2019
Light‐driven catalysis with engineered enzymes and biomimetic systems journal July 2020
Mimochrome, a metalloporphyrin‐based catalytic Swiss knife† journal July 2020
Enhancement of Peroxidase Activity in Artificial Mimochrome VI Catalysts through Rational Design journal July 2018
Artificial Hydrogenases Based on Cobaloximes and Heme Oxygenase journal October 2016
Hydrogen Photoevolution from a Green-Absorbing Iridium(III)-Cobalt­(III) Dyad journal March 2016
Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues journal October 1982
Cobalt complexes as artificial hydrogenases for the reductive side of water splitting journal August 2013
Reengineering cyt b562 for hydrogen production: A facile route to artificial hydrogenases journal May 2016
Stabilization of enzymes via immobilization: Multipoint covalent attachment and other stabilization strategies journal November 2021
Recent developments in hydrogen evolving molecular cobalt(II)–polypyridyl catalysts journal December 2015
Molecular catalysts of Co, Ni, Fe, and Mo for hydrogen generation in artificial photosynthetic systems journal October 2018
First-row transition metal polypyridine complexes that catalyze proton to hydrogen reduction journal January 2020
Sacrificial electron donor reagents for solar fuel production journal March 2017
Recent progress in homogeneous light-driven hydrogen evolution using first-row transition metal catalysts journal March 2021
Hydrogen the fuel for 21st century journal September 2009
Photochemical hydrogen evolution from cobalt microperoxidase-11 journal April 2021
Analysis of the Photodecomposition Products of Ru(bpy) 3 2+ in Various Buffers and upon Zeolite Encapsulation journal November 2000
Tuning Mechanism through Buffer Dependence of Hydrogen Evolution Catalyzed by a Cobalt Mini-enzyme journal March 2020
Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems journal November 2016
Triplet Photosensitizers Showing Strong Absorption of Visible Light and Long-Lived Triplet Excited States and Application in Photocatalysis: A Mini Review journal August 2021
Theoretical Study of the Full Photosolvolysis Mechanism of [Ru(bpy) 3 ] 2+ : Providing a General Mechanistic Roadmap for the Photochemistry of [Ru(N^N) 3 ] 2+ -Type Complexes toward Both Cis and Trans Photoproducts journal August 2020
Photocatalytic Hydrogen Production Using a Red-Absorbing Ir(III)–Co(III) Dyad journal May 2017
Nanocrystals for Triplet Sensitization: Molecular Behavior from Quantum-Confined Materials journal February 2018
Molecular Cobalt Catalysts for H 2 Generation with Redox Activity and Proton Relays in the Second Coordination Sphere journal December 2018
Photochemical Hydrogen Evolution from Neutral Water with a Cobalt Metallopeptide Catalyst journal November 2019
Highly Selective Indole Oxidation Catalyzed by a Mn-Containing Artificial Mini-Enzyme journal July 2021
Rate and Stability of Photocatalytic Water Oxidation using [Ru(bpy) 3 ] 2+ as Photosensitizer journal July 2016
Insights into Decomposition Pathways and Fate of Ru(bpy)32+ during Photocatalytic Water Oxidation with S2O82– as Sacrificial Electron Acceptor journal November 2016
Elucidating the Key Role of pH on Light-Driven Hydrogen Evolution by a Molecular Cobalt Catalyst journal January 2017
Homogeneous, Heterogeneous, and Biological Catalysts for Electrochemical N 2 Reduction toward NH 3 under Ambient Conditions journal April 2019
A Place in the Sun for Artificial Photosynthesis? journal May 2016
Engineered Enzymes and Bioinspired Catalysts for Energy Conversion journal August 2019
Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen journal March 1995
Hydrogen Evolution Catalyzed by Cobaloximes journal December 2009
Hydrogenases journal March 2014
Cobalt(I) porphyrin catalysts of hydrogen production from water journal July 1985
3d Element Complexes of Pentadentate Bipyridine-Pyridine-Based Ligand Scaffolds: Structures and Photocatalytic Activities journal April 2013
Electronic Effects on a Mononuclear Co Complex with a Pentadentate Ligand for Catalytic H 2 Evolution journal September 2014
Cobaloxime-Based Artificial Hydrogenases journal July 2014
Complexities of ascorbate as a reducing agent journal December 1981
Mechanism of Photocatalytic Hydrogen Generation by a Polypyridyl-Based Cobalt Catalyst in Aqueous Solution journal December 2014
Visible Light-Driven Hydrogen Production from Aqueous Protons Catalyzed by Molecular Cobaloxime Catalysts journal June 2009
Thermal and light-induced reduction of the ruthenium complex cation Ru(bpy)33+ in aqueous solution journal August 1984
Homogeneous catalysis of the photoreduction of water by visible light. 2. Mediation by a tris(2,2'-bipyridine)ruthenium(II)-cobalt(II) bipyridine system journal April 1981
Estimation of excited-state redox potentials by electron-transfer quenching. Application of electron-transfer theory to excited-state redox processes journal August 1979
Discovery and High-Throughput Screening of Heteroleptic Iridium Complexes for Photoinduced Hydrogen Production journal May 2005
Original Design of an Oxygen-Tolerant [NiFe] Hydrogenase: Major Effect of a Valine-to-Cysteine Mutation near the Active Site journal February 2011
Hydrogen Generation by Hangman Metalloporphyrins journal June 2011
A Cobalt–Dithiolene Complex for the Photocatalytic and Electrocatalytic Reduction of Protons journal October 2011
Substituent Effects on Cobalt Diglyoxime Catalysts for Hydrogen Evolution journal November 2011
Understanding and Tuning the Catalytic Bias of Hydrogenase journal May 2012
Versatile Photocatalytic Systems for H 2 Generation in Water Based on an Efficient DuBois-Type Nickel Catalyst journal December 2013
Suppression of Proton Mobility by Hydrophobic Hydration journal November 2009
Photocatalytic Water Oxidation in a Buffered Tris(2,2‘-bipyridyl)ruthenium Complex-Colloidal IrO 2 System journal June 2000
Size-Dependent Valence and Conduction Band-Edge Energies of Semiconductor Nanocrystals journal June 2011
Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment journal January 2021
Current understanding and challenges of solar-driven hydrogen generation using polymeric photocatalysts journal September 2019
Molecular artificial photosynthesis journal January 2014
Towards a comprehensive understanding of visible-light photogeneration of hydrogen from water using cobalt( ii ) polypyridyl catalysts journal January 2014
Earth-abundant hydrogen evolution electrocatalysts journal January 2014
Protein secondary-shell interactions enhance the photoinduced hydrogen production of cobalt protoporphyrin IX journal January 2014
Development and understanding of cobaloxime activity through electrochemical molecular catalyst screening journal January 2014
Photoinduced hydrogen evolution by a pentapyridine cobalt complex: elucidating some mechanistic aspects journal January 2014
Aqueous light driven hydrogen production by a Ru–ferredoxin–Co biohybrid journal January 2015
Photochemical hydrogen production and cobaloximes: the influence of the cobalt axial N-ligand on the system stability journal January 2016
Photocatalytic hydrogen evolution with ruthenium polypyridine sensitizers: unveiling the key factors to improve efficiencies journal January 2016
Photoinduced hydrogen evolution with new tetradentate cobalt( ii ) complexes based on the TPMA ligand journal January 2016
Photochemical upconversion is suppressed by high concentrations of molecular sensitizers journal January 2018
Artificial photosynthesis: opportunities and challenges of molecular catalysts journal January 2019
Hydrogen evolution from water catalyzed by cobalt-mimochrome VI*a, a synthetic mini-protein journal January 2018
The odyssey of cobaloximes for catalytic H 2 production and their recent revival with enzyme-inspired design journal January 2020
Light-driven hydrogen production catalysed by transition metal complexes in homogeneous systems journal January 2009
Proton reduction to hydrogen in biological and chemical systems journal January 2012
Molecular systems for light driven hydrogen production journal January 2012
Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting: Recent progress and future challenges journal January 2012
Proton-coupled electron transfer kinetics for the hydrogen evolution reaction of hangman porphyrins journal January 2012
Efficient photocatalytic hydrogen generation from water by a cationic cobalt(ii) porphyrin journal January 2014
Triplet photosensitizers: from molecular design to applications journal January 2013
Catalytic proton reduction with transition metal complexes of the redox-active ligand bpy2PYMe journal January 2013
Better than platinum? Fuel cells energized by enzymes journal November 2005
Cobalt and nickel diimine-dioxime complexes as molecular electrocatalysts for hydrogen evolution with low overvoltages journal November 2009
Cobalt-dithiolene complexes for the photocatalytic and electrocatalytic reduction of protons in aqueous solutions journal June 2012
De novo biosynthesis of a nonnatural cobalt porphyrin cofactor in E. coli and incorporation into hemoproteins journal April 2021
Recent advances in visible-light-driven organic reactions journal April 2017
The Photochemistry of the Future journal September 1912
Direct observation of triplet energy transfer from semiconductor nanocrystals journal January 2016
Direct evaluation of self-quenching behavior of fluorophores at high concentrations using an evanescent field journal February 2021
Light-Driven CO2 Reduction by Co-Cytochrome b562 journal April 2021