Covalent Attachment of the Water‐insoluble Ni(P Cy 2 N Phe 2 ) 2 Electrocatalyst to Electrodes Showing Reversible Catalysis in Aqueous Solution

Rodríguez‐Maciá, Patricia; Priyadarshani, Nilusha; Dutta, Arnab; Weidenthaler, Claudia; Lubitz, Wolfgang; Shaw, Wendy J.; Rüdiger, Olaf

doi:10.1002/elan.201600306

Title: Covalent Attachment of the Water‐insoluble Ni(P ^Cy ₂ N ^Phe ₂ ) ₂ Electrocatalyst to Electrodes Showing Reversible Catalysis in Aqueous Solution

Journal Article · Thu Oct 06 00:00:00 EDT 2016 · Electroanalysis

DOI:https://doi.org/10.1002/elan.201600306· OSTI ID:1401000

Rodríguez‐Maciá, Patricia ^[1]; Priyadarshani, Nilusha ^[2]; Dutta, Arnab ^[3]; Weidenthaler, Claudia ^[4]; Lubitz, Wolfgang ^[1]; Shaw, Wendy J. ^[2]; Rüdiger, Olaf ^[1]

Max Planck Institute für Chemische Energiekonversion Stiftstr. 34–36 45470 Mülheim an der Ruhr Germany
Pacific Northwest National Laboratory 902 Battelle Blvd. Richland WA 99354 USA
Pacific Northwest National Laboratory 902 Battelle Blvd. Richland WA 99354 USA, Chemistry Department IIT Gandhinagar Ahmedabad 382424 India
Max-Planck-Institut für Kohlenforschung Kaiser-Wilhelm-Platz 1 45470 Mülheim an der Ruhr Germany

Abstract Hydrogenases are a diverse group of metalloenzymes which catalyze the reversible conversion between molecular hydrogen and protons at high rates. The catalytic activity of these enzymes does not require overpotential because their active site has been evolutionarily optimized to operate fast and efficiently. These enzymes have inspired the development of molecular catalysts, which have dramatically improved in efficiency in recent years, to the point that some synthetic catalysts even outperform hydrogenases under certain conditions. In this work, we use a reversible noble‐metal‐free homogeneous catalyst, the [Ni(P ^Cy ₂ N ^Phe ₂ ) ₂ ] ²⁺ complex, and we covalently immobilize it on a functionalized highly oriented pyrolytic graphite “edge” (HOPG _e ) electrode surface. This catalyst is not water soluble, but once it is surface‐confined on the electrode, it maintains its catalytic properties in aqueous solutions, showing reversibility for H ₂ oxidation/reduction. Immobilization of the [Ni(P ^Cy ₂ N ^Phe ₂ ) ₂ ] ²⁺ complex onto a multi‐walled carbon nanotubes coated electrode leads to even higher catalytic current densities and enhanced stability.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

OSTI ID:: 1401000

Journal Information:: Electroanalysis, Journal Name: Electroanalysis Vol. 28 Journal Issue: 10; ISSN 1040-0397

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

Citation Metrics:

Cited by: 12 works

Citation information provided by
Web of Science

References (29)

Chemical approaches to artificial photosynthesis Concepcion, J. J.; House, R. L.; Papanikolas, J. M. Proceedings of the National Academy of Sciences, Vol. 109, Issue 39 https://doi.org/10.1073/pnas.1212254109	journal	September 2012
A Hydrogen-Evolving Ni(P ₂ N ₂ ) ₂ Electrocatalyst Covalently Attached to a Glassy Carbon Electrode: Preparation, Characterization, and Catalysis. Comparisons with the Homogeneous Analogue Das, Atanu K.; Engelhard, Mark H.; Bullock, R. Morris Inorganic Chemistry, Vol. 53, Issue 13 https://doi.org/10.1021/ic500701a	journal	June 2014
Dynamic electrochemical investigations of hydrogen oxidation and production by enzymes and implications for future technology Armstrong, Fraser A.; Belsey, Natalie A.; Cracknell, James A. Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B801144N	journal	January 2009
Versatile Photocatalytic Systems for H ₂ Generation in Water Based on an Efficient DuBois-Type Nickel Catalyst Gross, Manuela A.; Reynal, Anna; Durrant, James R. Journal of the American Chemical Society, Vol. 136, Issue 1 https://doi.org/10.1021/ja410592d	journal	December 2013
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Self-assembling hydrogel scaffolds for photocatalytic hydrogen production Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C. Nature Chemistry, Vol. 6, Issue 11 https://doi.org/10.1038/nchem.2075	journal	October 2014
Biomimetic assembly and activation of [FeFe]-hydrogenases Berggren, G.; Adamska, A.; Lambertz, C. Nature, Vol. 499, Issue 7456 https://doi.org/10.1038/nature12239	journal	June 2013
Minimal Proton Channel Enables H ₂ Oxidation and Production with a Water-Soluble Nickel-Based Catalyst Dutta, Arnab; Lense, Sheri; Hou, Jianbo Journal of the American Chemical Society, Vol. 135, Issue 49 https://doi.org/10.1021/ja407826d	journal	November 2013
Reduction of oxygen catalyzed by nickel diphosphine complexes with positioned pendant amines Yang, Jenny Y.; Bullock, R. Morris; Dougherty, William G. Dalton Transactions, Vol. 39, Issue 12 https://doi.org/10.1039/b921245k	journal	January 2010
Photocatalytic Hydrogen Production using Polymeric Carbon Nitride with a Hydrogenase and a Bioinspired Synthetic Ni Catalyst Caputo, Christine A.; Gross, Manuela A.; Lau, Vincent W. Angewandte Chemie, Vol. 126, Issue 43 https://doi.org/10.1002/ange.201406811	journal	September 2014
Arginine-Containing Ligands Enhance H ₂ Oxidation Catalyst Performance Dutta, Arnab; Roberts, John A. S.; Shaw, Wendy J. Angewandte Chemie International Edition, Vol. 53, Issue 25 https://doi.org/10.1002/anie.201402304	journal	May 2014
Proton reduction by molecular catalysts in water under demanding atmospheres Wakerley, David W.; Gross, Manuela A.; Reisner, Erwin Chem. Commun., Vol. 50, Issue 100 https://doi.org/10.1039/C4CC06159D	journal	January 2014
Catalytic Turnover of [FeFe]-Hydrogenase Based on Single-Molecule Imaging Madden, Christopher; Vaughn, Michael D.; Díez-Pérez, Ismael Journal of the American Chemical Society, Vol. 134, Issue 3 https://doi.org/10.1021/ja207461t	journal	October 2011
Molecular Electrocatalysts for the Oxidation of Hydrogen and the Production of Hydrogen - The Role of Pendant Amines as Proton Relays DuBois, Daniel L.; Bullock, R. Morris European Journal of Inorganic Chemistry, Vol. 2011, Issue 7 https://doi.org/10.1002/ejic.201001081	journal	January 2011
The roles of the first and second coordination spheres in the design of molecular catalysts for H ₂ production and oxidation Rakowski DuBois, M.; DuBois, Daniel L. Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B801197B	journal	January 2009
Direct Comparison of the Performance of a Bio-inspired Synthetic Nickel Catalyst and a [NiFe]-Hydrogenase, Both Covalently Attached to Electrodes Rodriguez-Maciá, Patricia; Dutta, Arnab; Lubitz, Wolfgang Angewandte Chemie International Edition, Vol. 54, Issue 42 https://doi.org/10.1002/anie.201502364	journal	July 2015
Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation Franz, James A.; O’Hagan, Molly; Ho, Ming-Hsun Organometallics, Vol. 32, Issue 23 https://doi.org/10.1021/om400695w	journal	November 2013
Moving Protons with Pendant Amines: Proton Mobility in a Nickel Catalyst for Oxidation of Hydrogen O’Hagan, Molly; Shaw, Wendy J.; Raugei, Simone Journal of the American Chemical Society, Vol. 133, Issue 36, p. 14301-14312 https://doi.org/10.1021/ja201838x	journal	September 2011
Hydrogenase-Coated Carbon Nanotubes for Efficient H ₂ Oxidation Alonso-Lomillo, M. Asunción; Rüdiger, Olaf; Maroto-Valiente, Angel Nano Letters, Vol. 7, Issue 6 https://doi.org/10.1021/nl070519u	journal	June 2007
Hydrogen Oxidation and Production Using Nickel-Based Molecular Catalysts with Positioned Proton Relays Wilson, Aaron D.; Newell, Rachel H.; McNevin, Michael J. Journal of the American Chemical Society, Vol. 128, Issue 1 https://doi.org/10.1021/ja056442y	journal	January 2006
From Hydrogenases to Noble Metal-Free Catalytic Nanomaterials for H2 Production and Uptake Le Goff, A.; Artero, V.; Jousselme, B. Science, Vol. 326, Issue 5958 https://doi.org/10.1126/science.1179773	journal	December 2009
Amide bond formation: beyond the myth of coupling reagents Valeur, Eric; Bradley, Mark Chem. Soc. Rev., Vol. 38, Issue 2 https://doi.org/10.1039/B701677H	journal	January 2009
A noble metal-free proton-exchange membrane fuel cell based on bio-inspired molecular catalysts Tran, P. D.; Morozan, A.; Archambault, S. Chemical Science, Vol. 6, Issue 3 https://doi.org/10.1039/C4SC03774J	journal	January 2015
Amino acid modified Ni catalyst exhibits reversible H ₂ oxidation/production over a broad pH range at elevated temperatures Dutta, Arnab; DuBois, Daniel L.; Roberts, John A. S. Proceedings of the National Academy of Sciences, Vol. 111, Issue 46 https://doi.org/10.1073/pnas.1416381111	journal	November 2014
Efficient solar-to-fuels production from a hybrid microbial–water-splitting catalyst system Torella, Joseph P.; Gagliardi, Christopher J.; Chen, Janice S. Proceedings of the National Academy of Sciences, Vol. 112, Issue 8 https://doi.org/10.1073/pnas.1424872112	journal	February 2015
Bio-inspired noble metal-free nanomaterials approaching platinum performances for H ₂ evolution and uptake Huan, Tran N.; Jane, Reuben T.; Benayad, Anass Energy & Environmental Science, Vol. 9, Issue 3 https://doi.org/10.1039/C5EE02739J	journal	January 2016
Further characterization of the [Fe]-hydrogenase from Desulfovibrio desulfuricans ATCC 7757 Hatchikian, E. Claude; Forget, Nicole; Fernandez, Victor M. European Journal of Biochemistry, Vol. 209, Issue 1 https://doi.org/10.1111/j.1432-1033.1992.tb17297.x	journal	October 1992
Hydrogenases Lubitz, Wolfgang; Ogata, Hideaki; Rüdiger, Olaf Chemical Reviews, Vol. 114, Issue 8 https://doi.org/10.1021/cr4005814	journal	March 2014
14N HYSCORE investigation of the H-cluster of [FeFe] hydrogenase: evidence for a nitrogen in the dithiol bridge Silakov, Alexey; Wenk, Brian; Reijerse, Eduard Physical Chemistry Chemical Physics, Vol. 11, Issue 31 https://doi.org/10.1039/b905841a	journal	January 2009

Similar Records

Covalent Attachment of the Water-insoluble Ni(P ^Cy ₂ N ^Phe ₂ ) ₂ Electrocatalyst to Electrodes Showing Reversible Catalysis in Aqueous Solution

Journal Article · Sat Oct 01 00:00:00 EDT 2016 · Electroanalysis · OSTI ID:1401000

Rodríguez-Maciá, Patricia; Priyadarshani, Nilusha; Dutta, Arnab; +4 more

Achieving Reversible H₂/H⁺ Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study

Journal Article · Tue Jul 26 00:00:00 EDT 2016 · ACS Catalysis · OSTI ID:1401000

Priyadarshani, Nilusha; Dutta, Arnab; Ginovska, Bojana; +4 more

The role of solvent and the outer coordination sphere on H₂ oxidation using [Ni(P^Cy₂N^Pyz₂)₂]²⁺

Journal Article · Fri May 01 00:00:00 EDT 2015 · European Journal of Inorganic Chemistry (Online) · OSTI ID:1401000

Dutta, Arnab; Lense, Sheri J.; Roberts, John A.; +2 more

Title: Covalent Attachment of the Water‐insoluble Ni(P Cy 2 N Phe 2 ) 2 Electrocatalyst to Electrodes Showing Reversible Catalysis in Aqueous Solution

Citation Formats

References (29)

Similar Records

Related Subjects

Title: Covalent Attachment of the Water‐insoluble Ni(P ^Cy ₂ N ^Phe ₂ ) ₂ Electrocatalyst to Electrodes Showing Reversible Catalysis in Aqueous Solution