Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS)2 Complex
Abstract
Tetra-coordinate NiII and ZnII complexes employing the PS chelates 2-(diphenylphosphanyl)benzenethiol (HL1) and 2-(diisopropylphosphanyl)benzenethiol (HL2) have been synthesized and characterized by spectroscopic, structural, and electrochemical methods. All complexes were screened for electrocatalytic activity for hydrogen evolution with acetic acid and hydrochloric acid and hydrogen oxidation in the presence of triethylamine. The nickel complex Ni(L1)2 (1) was found to reduce protons from external acids to generate hydrogen with a turnover frequency of 140 s–1 at an overpotential of 1.1 V and cleave dihydrogen using redox active base triethylamine (Et3N) with a turnover frequency of 23 s–1 at an overpotential of 0.33 V. Ni(L2)2 (3) was also found to be an active catalyst for dihydrogen oxidation, but inefficient for proton reduction due to inaccessible Ni (II/I) reduction in the potential window. Zn(L1)2 (2) and Zn(L2)2 (4) complexes were found to be inadequate for their electrocatalytic behaviour towards both the reactions.
- Publication Date:
- Research Org.:
- Univ. of Louisville, KY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1533163
- Alternate Identifier(s):
- OSTI ID: 1377932
- Grant/Contract Number:
- FG02-08CH11538
- Resource Type:
- Accepted Manuscript
- Journal Name:
- European Journal of Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 2017; Journal Issue: 31; Journal ID: ISSN 1434-1948
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Hydrogen; Electrocatalysis; Redox chemistry; Ligand design
Citation Formats
Jain, Rahul, Mashuta, Mark S., Buchanan, Robert M., and Grapperhaus, Craig A. Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS)2 Complex. United States: N. p., 2017.
Web. doi:10.1002/ejic.201700590.
Jain, Rahul, Mashuta, Mark S., Buchanan, Robert M., & Grapperhaus, Craig A. Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS)2 Complex. United States. https://doi.org/10.1002/ejic.201700590
Jain, Rahul, Mashuta, Mark S., Buchanan, Robert M., and Grapperhaus, Craig A. Mon .
"Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS)2 Complex". United States. https://doi.org/10.1002/ejic.201700590. https://www.osti.gov/servlets/purl/1533163.
@article{osti_1533163,
title = {Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS)2 Complex},
author = {Jain, Rahul and Mashuta, Mark S. and Buchanan, Robert M. and Grapperhaus, Craig A.},
abstractNote = {Tetra-coordinate NiII and ZnII complexes employing the PS chelates 2-(diphenylphosphanyl)benzenethiol (HL1) and 2-(diisopropylphosphanyl)benzenethiol (HL2) have been synthesized and characterized by spectroscopic, structural, and electrochemical methods. All complexes were screened for electrocatalytic activity for hydrogen evolution with acetic acid and hydrochloric acid and hydrogen oxidation in the presence of triethylamine. The nickel complex Ni(L1)2 (1) was found to reduce protons from external acids to generate hydrogen with a turnover frequency of 140 s–1 at an overpotential of 1.1 V and cleave dihydrogen using redox active base triethylamine (Et3N) with a turnover frequency of 23 s–1 at an overpotential of 0.33 V. Ni(L2)2 (3) was also found to be an active catalyst for dihydrogen oxidation, but inefficient for proton reduction due to inaccessible Ni (II/I) reduction in the potential window. Zn(L1)2 (2) and Zn(L2)2 (4) complexes were found to be inadequate for their electrocatalytic behaviour towards both the reactions.},
doi = {10.1002/ejic.201700590},
journal = {European Journal of Inorganic Chemistry},
number = 31,
volume = 2017,
place = {United States},
year = {Mon Aug 21 00:00:00 EDT 2017},
month = {Mon Aug 21 00:00:00 EDT 2017}
}
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Works referenced in this record:
Proposed Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation at a Noninnocent Mononuclear Metal–Thiolate
journal, July 2015
- Haddad, Andrew Z.; Kumar, Davinder; Ouch Sampson, Kagna
- Journal of the American Chemical Society, Vol. 137, Issue 29
Synthesis and electrocatalytic function for hydrogen generation of cobalt and nickel complexes supported by phenylenediamine ligand
journal, October 2016
- Zhang, Yun-Xiao; Tang, Ling-Zhi; Deng, Yuan-Fu
- Inorganic Chemistry Communications, Vol. 72
Metal-Stabilized Thiyl Radicals as Scaffolds for Reversible Alkene Addition via C–S Bond Formation/Cleavage
journal, October 2011
- Ouch, Kagna; Mashuta, Mark S.; Grapperhaus, Craig A.
- Inorganic Chemistry, Vol. 50, Issue 20
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Direct comparison of the electrocatalytic oxidation of hydrogen by an enzyme and a platinum catalystElectronic supplementary information (ESI) available: Levich plots at 1% and 10% hydrogen, and a comparison of the effect of carbon monoxide on oxidation currents obtained at platinum and enzyme-modified electrodes. See http://www.rsc.org/suppdata/cc/b2/b201337a/
journal, March 2002
- Jones, Anne K.; Sillery, Emma; Albracht, Simon P. J.
- Chemical Communications, Issue 8
Determining the Overpotential for a Molecular Electrocatalyst
journal, December 2013
- Appel, Aaron M.; Helm, Monte L.
- ACS Catalysis, Vol. 4, Issue 2
Molecular mechanisms of cobalt-catalyzed hydrogen evolution
journal, September 2012
- Marinescu, S. C.; Winkler, J. R.; Gray, H. B.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 38
Homogeneous Oxidation of Trialkylamines by Metal Complexes and Its Impact on Electrogenerated Chemiluminescence in the Trialkylamine/Ru(bpy)32+ System
journal, December 2000
- Kanoufi, Frédéric; Zu, Yanbing; Bard, Allen J.
- The Journal of Physical Chemistry B, Vol. 105, Issue 1
Rapid and Reversible Reactions of [NiFe]-Hydrogenases with Sulfide
journal, June 2006
- Vincent, Kylie A.; Belsey, Natalie A.; Lubitz, Wolfgang
- Journal of the American Chemical Society, Vol. 128, Issue 23
o-Lithiothiophenol equivalents. Generation, reactions and applications in synthesis of hindered thiolate ligands
journal, January 1989
- Block, Eric; Eswarakrishnan, Venkatachalam; Gernon, Michael
- Journal of the American Chemical Society, Vol. 111, Issue 2
2-Phosphino- and 2-phosphinylbenzenethiols: new ligand types
journal, March 1989
- Block, Eric; Ofori-Okai, Gabriel; Zubieta, Jon
- Journal of the American Chemical Society, Vol. 111, Issue 6
Synthesis of neutral iridium(III) and rhodium(III) complexes with the proligands Pri2P(C6H4SH-2) [priPSH]; PhP(C6H4SH-2)2 [phPS2H2] and PhP(C2H4SH)2 [ePS2H2]. The X-ray crystal structures of [Ir(priPS)3] and [Rh(H)(phPS2)(CO)(PPh3)]
journal, April 2002
- Morales-Morales, David; Rodrı́guez-Morales, Sergio; Dilworth, Jonathan R.
- Inorganica Chimica Acta, Vol. 332, Issue 1
Beyond Metal-Hydrides: Non-Transition-Metal and Metal-Free Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation
journal, June 2016
- Haddad, Andrew Z.; Garabato, Brady D.; Kozlowski, Pawel M.
- Journal of the American Chemical Society, Vol. 138, Issue 25
Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water
journal, January 2015
- Das, Amit; Han, Zhiji; Brennessel, William W.
- ACS Catalysis, Vol. 5, Issue 3
Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides
journal, June 2016
- Schilter, David; Camara, James M.; Huynh, Mioy T.
- Chemical Reviews, Vol. 116, Issue 15
From The Cover: Electrocatalytic hydrogen oxidation by an enzyme at high carbon monoxide or oxygen levels
journal, October 2005
- Vincent, K. A.; Cracknell, J. A.; Lenz, O.
- Proceedings of the National Academy of Sciences, Vol. 102, Issue 47, p. 16951-16954
Characteristics of Nickel(0), Nickel(I), and Nickel(II) in Phosphino Thioether Complexes: Molecular Structure and S -Dealkylation of (Ph 2 P( o -C 6 H 4 )SCH 3 ) 2 Ni 0
journal, January 1996
- Kim, Jang Sub; Reibenspies, Joseph H.; Darensbourg, Marcetta Y.
- Journal of the American Chemical Society, Vol. 118, Issue 17
Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N -Heterocyclic Carbene–Isoquinoline Complex
journal, September 2013
- Thoi, V. Sara; Kornienko, Nikolay; Margarit, Charles G.
- Journal of the American Chemical Society, Vol. 135, Issue 38
Size- and Shape-Dependent Activity of Metal Nanoparticles as Hydrogen-Evolution Catalysts: Mechanistic Insights into Photocatalytic Hydrogen Evolution
journal, January 2011
- Kotani, Hiroaki; Hanazaki, Ryo; Ohkubo, Kei
- Chemistry - A European Journal, Vol. 17, Issue 9
Translation of Ligand-Centered Hydrogen Evolution Reaction Activity and Mechanism of a Rhenium-Thiolate from Solution to Modified Electrodes: A Combined Experimental and Density Functional Theory Study
journal, February 2017
- Zhang, Wuyu; Haddad, Andrew Z.; Garabato, Brady D.
- Inorganic Chemistry, Vol. 56, Issue 4
Synthesis and electrochemical properties of a water soluble nickel(II) complex supported by N-phenylpyridin-2-ylmethanimine ligand
journal, August 2017
- Xue, Dan; Peng, Qiu-Xia; Zhan, Shu-Zhong
- Inorganic Chemistry Communications, Vol. 82
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010
- Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y.
- Chemical Reviews, Vol. 110, Issue 11
Earth-abundant hydrogen evolution electrocatalysts
journal, January 2014
- McKone, James R.; Marinescu, Smaranda C.; Brunschwig, Bruce S.
- Chem. Sci., Vol. 5, Issue 3
Metal-free electrocatalytic hydrogen oxidation using frustrated Lewis pairs and carbon-based Lewis acids
journal, January 2016
- Lawrence, Elliot J.; Clark, Ewan R.; Curless, Liam D.
- Chemical Science, Vol. 7, Issue 4
Sacrificial electron donor reagents for solar fuel production
journal, March 2017
- Pellegrin, Yann; Odobel, Fabrice
- Comptes Rendus Chimie, Vol. 20, Issue 3
Metal Complexes (M = Zn, Sn, and Pb) of 2-Phosphinobenzenethiolates: Insights into Ligand Folding and Hemilability
journal, August 2013
- Barry, Brian M.; Stein, Benjamin W.; Larsen, Christopher A.
- Inorganic Chemistry, Vol. 52, Issue 17
ORTEP -3 for Windows - a version of ORTEP -III with a Graphical User Interface (GUI)
journal, October 1997
- Farrugia, L. J.
- Journal of Applied Crystallography, Vol. 30, Issue 5
Electrochemical Oxidation of Aliphatic Amines and Their Attachment to Carbon and Metal Surfaces
journal, September 2004
- Adenier, Alain; Chehimi, Mohamed M.; Gallardo, Iluminada
- Langmuir, Vol. 20, Issue 19
Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels
journal, December 2009
- Morris, Amanda J.; Meyer, Gerald J.; Fujita, Etsuko
- Accounts of Chemical Research, Vol. 42, Issue 12
Hydrogen Production under Aerobic Conditions by Membrane-Bound Hydrogenases from Ralstonia Species
journal, August 2008
- Goldet, Gabrielle; Wait, Annemarie F.; Cracknell, James A.
- Journal of the American Chemical Society, Vol. 130, Issue 33
Development of Molecular Electrocatalysts for Energy Storage
journal, February 2014
- DuBois, Daniel L.
- Inorganic Chemistry, Vol. 53, Issue 8
Works referencing / citing this record:
Recent advances in the mechanisms of the hydrogen evolution reaction by non-innocent sulfur-coordinating metal complexes
journal, January 2020
- Drosou, Maria; Kamatsos, Fotios; Mitsopoulou, Christiana A.
- Inorganic Chemistry Frontiers, Vol. 7, Issue 1