Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst

Cronin, Steve P.; Mamun, Abdullah Al; Toda, Megan J.; Mashuta, Mark S.; Losovyj, Yaroslav; Kozlowski, Pawel M.; Buchanan, Robert M.; Grapperhaus, Craig A.

doi:10.1021/acs.inorgchem.9b01912

Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst

Journal Article · Tue Sep 10 00:00:00 EDT 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b01912· OSTI ID:1800549

^[1]; ^[2]; ^[2]; Mashuta, Mark S. ^[2]; Losovyj, Yaroslav ^[3]; ^[2]; Buchanan, Robert M. ^[2]; ^[2]

Univ. of Louisville, KY (United States); OSTI
Univ. of Louisville, KY (United States)
Indiana Univ., Bloomington, IN (United States)

The zinc(II) complex of diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazonepyridine), ZnL¹ (1), was prepared and evaluated as a precatalyst for the hydrogen evolution reaction (HER) under homogeneous conditions in acetonitrile. Complex 1 is protonated on the noncoordinating nitrogen of the hydrazonepyridine moiety to yield the active catalyst Zn(HL¹)OAc (2) upon addition of acetic acid. Addition of methyl iodide to 1 yields the corresponding methylated derivative ZnL²I (3). In solution, partial dissociation of the coordinated iodide yields the cationic derivative 3'. Complexes 1–3 were characterized by ¹H NMR, FT-IR, and UV–visible spectroscopies. The solid-state structures of 2 and 3 were determined by single crystal X-ray diffraction. HER studies conducted in acetonitrile with acetic acid as the proton source yield a turnover frequency (TOF) of 7700 s^–1 for solutions of 1 at an overpotential of 1.27 V and a TOF of 6700 s^–1 for solutions of 3 at an overpotential of 0.56 V. For both complexes, the required potential for catalysis, E_cat/2, is larger than the thermodynamic reduction potential, E_1/2, indicative of a kinetic barrier attributed to intramolecular proton rearrangement. The effect is larger for solutions of 1 (+440 mV) than for solutions of 3 (+160 mV). Controlled potential coulometry studies were used to determine faradaic efficiencies of 71 and 89% for solutions of 1 and 3, respectively. For both catalysts, extensive cycling of potential under catalytic conditions results in the deposition of a film on the glassy carbon electrode surface that is active as an HER catalyst. Analysis of the film of 3 by X-ray photoelectron spectroscopy indicates the complex remains intact upon deposition. A proposed ligand-centered HER mechanism with 1 as a precatalyst to 2 is supported computationally using density functional theory (DFT). All catalytic intermediates in the mechanism were structurally and energetically characterized with the DFT/B3LYP/6-311g(d,p) in solution phase using a polarizable continuum model (PCM). Finally, the thermodynamic feasibility of the mechanism is supported by calculation of equilibrium constants or reduction potentials for each proposed step.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); USDOE

Grant/Contract Number:: FG02-08CH11538

OSTI ID:: 1800549

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 19 Vol. 58; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (33)

Electrocatalytic Hydrogen Production by an Aluminum(III) Complex: Ligand-Based Proton and Electron Transfer Thompson, Emily J.; Berben, Louise A. Angewandte Chemie International Edition, Vol. 54, Issue 40 https://doi.org/10.1002/anie.201503935	journal	August 2015
A Thiosemicarbazone-Nickel(II) Complex as Efficient Electrocatalyst for Hydrogen Evolution Straistari, Tatiana; Fize, Jennifer; Shova, Sergiu ChemCatChem, Vol. 9, Issue 12 https://doi.org/10.1002/cctc.201600967	journal	November 2016
Influence of the Metal Ion on the Electrocatalytic Hydrogen Production by a Thiosemicarbazone Palladium Complex: Influence of the Metal Ion on the Electrocatalytic Hydrogen Production by a Thiosemicarbazone Palladium Complex Straistari, Tatiana; Hardré, Renaud; Massin, Julien European Journal of Inorganic Chemistry, Vol. 2018, Issue 20-21 https://doi.org/10.1002/ejic.201800120	journal	May 2018
Complexes of group 12 metals containing a hybrid thiosemicarbazone-pyridylhydrazone ligand Calatayud, David G.; López-Torres, Elena; Dilworth, Jonathan R. Inorganica Chimica Acta, Vol. 381 https://doi.org/10.1016/j.ica.2011.10.023	journal	February 2012
Metal-Assisted Ligand-Centered Electrocatalytic Hydrogen Evolution upon Reduction of a Bis(thiosemicarbazonato)Cu(II) Complex Haddad, Andrew Z.; Cronin, Steve P.; Mashuta, Mark S. Inorganic Chemistry, Vol. 56, Issue 18 https://doi.org/10.1021/acs.inorgchem.7b01608	journal	August 2017
Ligand-Assisted Metal-Centered Electrocatalytic Hydrogen Evolution upon Reduction of a Bis(thiosemicarbazonato)Ni(II) Complex Jain, Rahul; Mamun, Abdullah Al; Buchanan, Robert M. Inorganic Chemistry, Vol. 57, Issue 21 https://doi.org/10.1021/acs.inorgchem.8b02110	journal	October 2018
Effect of Stacking Interactions on the Translation of Structurally Related Bis(thiosemicarbazonato)nickel(II) HER Catalysts to Modified Electrode Surfaces Gupta, Alexander J.; Vishnosky, Nicholas S.; Hietsoi, Oleksandr Inorganic Chemistry, Vol. 58, Issue 18 https://doi.org/10.1021/acs.inorgchem.9b01209	journal	September 2019
Voltammetric Determination of the Iodide/Iodine Formal Potential and Triiodide Stability Constant in Conventional and Ionic Liquid Media Bentley, Cameron L.; Bond, Alan M.; Hollenkamp, Anthony F. The Journal of Physical Chemistry C, Vol. 119, Issue 39 https://doi.org/10.1021/acs.jpcc.5b07484	journal	September 2015
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
Copper Complexes of Thiosemicarbazone−Pyridylhydrazine (THYNIC) Hybrid Ligands: A New Versatile Potential Bifunctional Chelator for Copper Radiopharmaceuticals Cowley, Andrew R.; Dilworth, Jonathan R.; Donnelly, Paul S. Inorganic Chemistry, Vol. 45, Issue 2 https://doi.org/10.1021/ic0514492	journal	January 2006
H ₂ Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation Fourmond, Vincent; Jacques, Pierre-André; Fontecave, Marc Inorganic Chemistry, Vol. 49, Issue 22 https://doi.org/10.1021/ic101187v	journal	November 2010
Electrochemical Reduction of Brønsted Acids by Glassy Carbon in Acetonitrile—Implications for Electrocatalytic Hydrogen Evolution McCarthy, Brian D.; Martin, Daniel J.; Rountree, Eric S. Inorganic Chemistry, Vol. 53, Issue 16 https://doi.org/10.1021/ic500770k	journal	July 2014
6-311G(MC)(d,p): a second-row analogue of the 6-311G(d,p) basis set: calculated heats of formation for second-row hydrides Wong, Ming Wah; Gill, Peter M. W.; Nobes, Ross H. The Journal of Physical Chemistry, Vol. 92, Issue 17 https://doi.org/10.1021/j100328a015	journal	August 1988
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis Costentin, Cyrille; Drouet, Samuel; Robert, Marc Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242 https://doi.org/10.1021/ja303560c	journal	June 2012
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
Turning on the Protonation-First Pathway for Electrocatalytic CO ₂ Reduction by Manganese Bipyridyl Tricarbonyl Complexes Ngo, Ken T.; McKinnon, Meaghan; Mahanti, Bani Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b08776	journal	February 2017
Anion-Redox Mechanism of MoO(S ₂ ) ₂ (2,2′-bipyridine) for Electrocatalytic Hydrogen Production Garrett, Benjamin R.; Polen, Shane M.; Pimplikar, Maneesha Journal of the American Chemical Society, Vol. 139, Issue 12 https://doi.org/10.1021/jacs.7b01350	journal	March 2017
Powering the planet with solar fuel Gray, Harry B. Nature Chemistry, Vol. 1, Issue 1 https://doi.org/10.1038/nchem.141	journal	April 2009
Electrochemical and spectroscopic methods for evaluating molecular electrocatalysts Lee, Katherine J.; Elgrishi, Noémie; Kandemir, Banu Nature Reviews Chemistry, Vol. 1, Issue 5 https://doi.org/10.1038/s41570-017-0039	journal	May 2017
Homogeneous catalysis: An electrochemical and spectroscopic look at renewable energy Graziono, Gabriella Nature Reviews Chemistry, Vol. 2, Issue 4 https://doi.org/10.1038/s41570-018-0130	journal	March 2018
Computational electrochemistry: prediction of liquid-phase reduction potentials Marenich, Aleksandr V.; Ho, Junming; Coote, Michelle L. Phys. Chem. Chem. Phys., Vol. 16, Issue 29 https://doi.org/10.1039/C4CP01572J	journal	January 2014
A nickel complex of a conjugated bis-dithiocarbazate Schiff base for the photocatalytic production of hydrogen Wise, Catherine F.; Liu, Dan; Mayer, Kathryn J. Dalton Transactions, Vol. 44, Issue 32 https://doi.org/10.1039/C5DT02042E	journal	January 2015
Hydrogen evolution catalysis by molybdenum sulfides (MoS _x ): are thiomolybdate clusters like [Mo ₃ S ₁₃ ] ²⁻ suitable active site models? Grutza, Marie-Luise; Rajagopal, Ashwene; Streb, Carsten Sustainable Energy & Fuels, Vol. 2, Issue 9 https://doi.org/10.1039/C8SE00155C	journal	January 2018
Proton-coupled electron transfer kinetics for the hydrogen evolution reaction of hangman porphyrins Roubelakis, Manolis M.; Bediako, D. Kwabena; Dogutan, Dilek K. Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee21123h	journal	January 2012
Continuous surface charge polarizable continuum models of solvation. I. General formalism Scalmani, Giovanni; Frisch, Michael J. The Journal of Chemical Physics, Vol. 132, Issue 11 https://doi.org/10.1063/1.3359469	journal	March 2010
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
Interplay of hemilability and redox activity in models of hydrogenase active sites Ding, Shengda; Ghosh, Pokhraj; Darensbourg, Marcetta Y. Proceedings of the National Academy of Sciences, Vol. 114, Issue 46 https://doi.org/10.1073/pnas.1710475114	journal	October 2017
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
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
A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s^-1 for H₂ Production Helm, M. L.; Stewart, M. P.; Bullock, R. M. Science, Vol. 333, Issue 6044, p. 863-866 https://doi.org/10.1126/science.1205864	journal	August 2011
A Molecular MoS2 Edge Site Mimic for Catalytic Hydrogen Generation Karunadasa, H. I.; Montalvo, E.; Sun, Y. Science, Vol. 335, Issue 6069 https://doi.org/10.1126/science.1215868	journal	February 2012

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