Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS)2 Complex

Jain, Rahul; Mashuta, Mark S.; Buchanan, Robert M.; Grapperhaus, Craig A.

doi:10.1002/ejic.201700590

Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation with a Ni(PS)₂Complex

Journal Article · Mon Aug 21 00:00:00 EDT 2017 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.201700590· OSTI ID:1533163

Jain, Rahul ^[1]; Mashuta, Mark S. ^[2]; ^[2]; ^[2]

Univ. of Louisville, KY (United States); DOE/OSTI
Univ. of Louisville, KY (United States)

Tetra-coordinate Ni^II and Zn^II 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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Louisville, KY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: FG02-08CH11538

OSTI ID:: 1533163

Alternate ID(s):: OSTI ID: 1377932

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 31 Vol. 2017; ISSN 1434-1948

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

Size- and Shape-Dependent Activity of Metal Nanoparticles as Hydrogen-Evolution Catalysts: Mechanistic Insights into Photocatalytic Hydrogen Evolution Kotani, Hiroaki; Hanazaki, Ryo; Ohkubo, Kei Chemistry - A European Journal, Vol. 17, Issue 9 https://doi.org/10.1002/chem.201002399	journal	January 2011
Synthesis of neutral iridium(III) and rhodium(III) complexes with the proligands Pri2P(C6H4SH-2) [priPSH]; PhP(C6H4SH-2)2 [phPS2H2] and PhP(C2H4SH)2 [ePS2H2]. The X-ray crystal structures of [Ir(priPS)3] and [Rh(H)(phPS2)(CO)(PPh3)] Morales-Morales, David; Rodrı́guez-Morales, Sergio; Dilworth, Jonathan R. Inorganica Chimica Acta, Vol. 332, Issue 1 https://doi.org/10.1016/S0020-1693(02)00695-3	journal	April 2002
Sacrificial electron donor reagents for solar fuel production Pellegrin, Yann; Odobel, Fabrice Comptes Rendus Chimie, Vol. 20, Issue 3 https://doi.org/10.1016/j.crci.2015.11.026	journal	March 2017
Synthesis and electrocatalytic function for hydrogen generation of cobalt and nickel complexes supported by phenylenediamine ligand Zhang, Yun-Xiao; Tang, Ling-Zhi; Deng, Yuan-Fu Inorganic Chemistry Communications, Vol. 72 https://doi.org/10.1016/j.inoche.2016.08.022	journal	October 2016
Synthesis and electrochemical properties of a water soluble nickel(II) complex supported by N-phenylpyridin-2-ylmethanimine ligand Xue, Dan; Peng, Qiu-Xia; Zhan, Shu-Zhong Inorganic Chemistry Communications, Vol. 82 https://doi.org/10.1016/j.inoche.2017.04.018	journal	August 2017
Hydrogenase Enzymes and Their Synthetic Models: The Role of Metal Hydrides Schilter, David; Camara, James M.; Huynh, Mioy T. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00180	journal	June 2016
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 Zhang, Wuyu; Haddad, Andrew Z.; Garabato, Brady D. Inorganic Chemistry, Vol. 56, Issue 4 https://doi.org/10.1021/acs.inorgchem.6b02829	journal	February 2017
Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water Das, Amit; Han, Zhiji; Brennessel, William W. ACS Catalysis, Vol. 5, Issue 3 https://doi.org/10.1021/acscatal.5b00045	journal	January 2015
Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels Morris, Amanda J.; Meyer, Gerald J.; Fujita, Etsuko Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar9001679	journal	December 2009
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y. Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr100246c	journal	November 2010
Determining the Overpotential for a Molecular Electrocatalyst Appel, Aaron M.; Helm, Monte L. ACS Catalysis, Vol. 4, Issue 2 https://doi.org/10.1021/cs401013v	journal	December 2013
Metal-Stabilized Thiyl Radicals as Scaffolds for Reversible Alkene Addition via C–S Bond Formation/Cleavage Ouch, Kagna; Mashuta, Mark S.; Grapperhaus, Craig A. Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic200416y	journal	October 2011
Metal Complexes (M = Zn, Sn, and Pb) of 2-Phosphinobenzenethiolates: Insights into Ligand Folding and Hemilability Barry, Brian M.; Stein, Benjamin W.; Larsen, Christopher A. Inorganic Chemistry, Vol. 52, Issue 17 https://doi.org/10.1021/ic400990n	journal	August 2013
Development of Molecular Electrocatalysts for Energy Storage DuBois, Daniel L. Inorganic Chemistry, Vol. 53, Issue 8 https://doi.org/10.1021/ic4026969	journal	February 2014
o-Lithiothiophenol equivalents. Generation, reactions and applications in synthesis of hindered thiolate ligands Block, Eric; Eswarakrishnan, Venkatachalam; Gernon, Michael Journal of the American Chemical Society, Vol. 111, Issue 2 https://doi.org/10.1021/ja00184a039	journal	January 1989
2-Phosphino- and 2-phosphinylbenzenethiols: new ligand types Block, Eric; Ofori-Okai, Gabriel; Zubieta, Jon Journal of the American Chemical Society, Vol. 111, Issue 6 https://doi.org/10.1021/ja00188a071	journal	March 1989
Rapid and Reversible Reactions of [NiFe]-Hydrogenases with Sulfide Vincent, Kylie A.; Belsey, Natalie A.; Lubitz, Wolfgang Journal of the American Chemical Society, Vol. 128, Issue 23 https://doi.org/10.1021/ja061732f	journal	June 2006
Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N -Heterocyclic Carbene–Isoquinoline Complex Thoi, V. Sara; Kornienko, Nikolay; Margarit, Charles G. Journal of the American Chemical Society, Vol. 135, Issue 38 https://doi.org/10.1021/ja4074003	journal	September 2013
Hydrogen Production under Aerobic Conditions by Membrane-Bound Hydrogenases from Ralstonia Species Goldet, Gabrielle; Wait, Annemarie F.; Cracknell, James A. Journal of the American Chemical Society, Vol. 130, Issue 33 https://doi.org/10.1021/ja8027668	journal	August 2008
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 Kim, Jang Sub; Reibenspies, Joseph H.; Darensbourg, Marcetta Y. Journal of the American Chemical Society, Vol. 118, Issue 17 https://doi.org/10.1021/ja953686h	journal	January 1996
Proposed Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation at a Noninnocent Mononuclear Metal–Thiolate Haddad, Andrew Z.; Kumar, Davinder; Ouch Sampson, Kagna Journal of the American Chemical Society, Vol. 137, Issue 29 https://doi.org/10.1021/jacs.5b05561	journal	July 2015
Beyond Metal-Hydrides: Non-Transition-Metal and Metal-Free Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation Haddad, Andrew Z.; Garabato, Brady D.; Kozlowski, Pawel M. Journal of the American Chemical Society, Vol. 138, Issue 25 https://doi.org/10.1021/jacs.6b04441	journal	June 2016
Homogeneous Oxidation of Trialkylamines by Metal Complexes and Its Impact on Electrogenerated Chemiluminescence in the Trialkylamine/Ru(bpy)₃²⁺ System Kanoufi, Frédéric; Zu, Yanbing; Bard, Allen J. 105, Vol. 1, Issue 210-216 https://doi.org/10.1021/jp002880	journal	December 2000
Homogeneous Oxidation of Trialkylamines by Metal Complexes and Its Impact on Electrogenerated Chemiluminescence in the Trialkylamine/Ru(bpy)₃²⁺ System Kanoufi, Frédéric; Zu, Yanbing; Bard, Allen J. The Journal of Physical Chemistry B, Vol. 105, Issue 1 https://doi.org/10.1021/jp002880+	journal	December 2000
Electrochemical Oxidation of Aliphatic Amines and Their Attachment to Carbon and Metal Surfaces Adenier, Alain; Chehimi, Mohamed M.; Gallardo, Iluminada Langmuir, Vol. 20, Issue 19 https://doi.org/10.1021/la049194c	journal	September 2004
Earth-abundant hydrogen evolution electrocatalysts McKone, James R.; Marinescu, Smaranda C.; Brunschwig, Bruce S. Chem. Sci., Vol. 5, Issue 3 https://doi.org/10.1039/C3SC51711J	journal	January 2014
Electrochemical hydrogenation of a homogeneous nickel complex to form a surface adsorbed hydrogen-evolving species Martin, Daniel J.; McCarthy, Brian D.; Donley, Carrie L. Chemical Communications, Vol. 51, Issue 25 https://doi.org/10.1039/C4CC08662G	journal	January 2015
Metal-free electrocatalytic hydrogen oxidation using frustrated Lewis pairs and carbon-based Lewis acids Lawrence, Elliot J.; Clark, Ewan R.; Curless, Liam D. Chemical Science, Vol. 7, Issue 4 https://doi.org/10.1039/C5SC04564A	journal	January 2016
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/ Jones, Anne K.; Sillery, Emma; Albracht, Simon P. J. Chemical Communications, Issue 8 https://doi.org/10.1039/b201337a	journal	March 2002
From The Cover: Electrocatalytic hydrogen oxidation by an enzyme at high carbon monoxide or oxygen levels Vincent, K. A.; Cracknell, J. A.; Lenz, O. Proceedings of the National Academy of Sciences, Vol. 102, Issue 47, p. 16951-16954 https://doi.org/10.1073/pnas.0504499102	journal	October 2005
Molecular mechanisms of cobalt-catalyzed hydrogen evolution Marinescu, S. C.; Winkler, J. R.; Gray, H. B. Proceedings of the National Academy of Sciences, Vol. 109, Issue 38 https://doi.org/10.1073/pnas.1213442109	journal	September 2012
ORTEP -3 for Windows - a version of ORTEP -III with a Graphical User Interface (GUI) Farrugia, L. J. Journal of Applied Crystallography, Vol. 30, Issue 5 https://doi.org/10.1107/S0021889897003117	journal	October 1997
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007

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Recent advances in the mechanisms of the hydrogen evolution reaction by non-innocent sulfur-coordinating metal complexes Drosou, Maria; Kamatsos, Fotios; Mitsopoulou, Christiana A. Inorganic Chemistry Frontiers, Vol. 7, Issue 1 https://doi.org/10.1039/c9qi01113g	journal	January 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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