H2 Evolution at an Electrochemical “Underpotential” with an Iridium-Based Molecular Photoelectrocatalyst

Stratakes, Bethany M.; Miller, Alexander J. M.

doi:10.1021/acscatal.0c02265

H₂ Evolution at an Electrochemical “Underpotential” with an Iridium-Based Molecular Photoelectrocatalyst

Journal Article · Wed Jul 15 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c02265· OSTI ID:1782419

Stratakes, Bethany M. ^[1]; ^[2]

Univ. of North Carolina, Chapel Hill, NC (United States); University of North Carolina at Chapel Hill
Univ. of North Carolina, Chapel Hill, NC (United States)

Molecular platforms capable of both photochemical H₂ evolution and electrochemical catalyst regeneration hold promise for the efficient generation of solar fuels. Systems studied to date require a significant electrochemical overpotential (η), so no photon energy is being chemically stored. A detailed study of the parameters that govern the electrochemical overpotential of molecular photoelectrocatalysts is presented. By understanding how tuning the solvent, catalyst structure, and acid pK_a affect the kinetics and thermodynamics of the potential- and light-driven H₂ evolution reaction, conditions were identified wherein the solvento complex [Cp*Ir(bpy)(NCCH₃)][PF₆]₂ (Cp* is pentamethylcyclopentadienyl; bpy is 2,2'-bipyridine) mediates photoelectrocatalytic H₂ formation at an electrochemical “underpotential” (η < 0) driven by visible light. Under 460 nm illumination and in the presence of the weak organic acid H-PhTMG⁺ (2-phenyl-1,1,3,3- tetramethylguanidinium), the catalyst facilitates H₂ evolution with Faradaic efficiencies up to 90% and overpotentials as low as –90 mV. As a result, mechanistic studies enabled the construction of graphical “maps” that can guide the choice of catalyst and conditions to minimize overpotential, applicable to both photoelectrocatalysts and dark electrocatalysts.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of North Carolina, Chapel Hill, NC (United States)

Sponsoring Organization:: National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001011; SC0014255

OSTI ID:: 1782419

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 16 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling Rivier, Lucie; Peljo, Pekka; Vannay, Laurent A. C. Angewandte Chemie International Edition, Vol. 56, Issue 9 https://doi.org/10.1002/anie.201610240	journal	January 2017
Mechanistic Study on the Photogeneration of Hydrogen by Decamethylruthenocene Rivier, Lucie; Peljo, Pekka; Maye, Sunny Chemistry – A European Journal, Vol. 25, Issue 55 https://doi.org/10.1002/chem.201902353	journal	September 2019
Nachweis innermolekularer Beweglichkeit durch NMR-Spektroskopie, XVIII1) Vergleich der Inversionsgeschwindigkeiten am doppelt gebundenen Stickstoff bei Guanidinen und Imidazolidiniminen Kessler, Horst; Leibfritz, Dieter Justus Liebigs Annalen der Chemie, Vol. 737, Issue 1 https://doi.org/10.1002/jlac.19707370106	journal	August 1970
Electrochemical generation of a metal-hydride complex [(C5Me5)Ir(L) H]+ (L = 2,2′-bipyridine). The electrochemical behaviour. Caix, C.; Chardon-Noblat, S.; Deronzier, A. Journal of Electroanalytical Chemistry, Vol. 362, Issue 1-2 https://doi.org/10.1016/0022-0728(93)80035-G	journal	December 1993
Electrochemical formation of cationic iridium(III)-hydrido complexes in solution and in polymeric films: their chemical, electrochemical and electrocatalytic activity in the hydrogen generation process Caix, Chrystelle; Chardon-Noblat, Sylvie; Deronzier, Alain Journal of Electroanalytical Chemistry, Vol. 403, Issue 1-2 https://doi.org/10.1016/0022-0728(95)04324-1	journal	February 1996
Electronic structure of catalytic intermediates for production of H2: (C5Me5)Ir(bpy) and its conjugated acid Ladwig, Monika; Kaim, Wolfgang Journal of Organometallic Chemistry, Vol. 439, Issue 1 https://doi.org/10.1016/0022-328X(92)80055-3	journal	October 1992
Electrocatalytic reduction of CO2 into formate with [(η5Me5C5)M(L)Cl]+ complexes (L = 2,2′-bipyridine ligands; M  Rh(III) and Ir(III)) Caix, Chrystelle; Chardon-Noblat, Sylvie; Deronzier, Alain Journal of Electroanalytical Chemistry, Vol. 434, Issue 1-2 https://doi.org/10.1016/S0022-0728(97)00058-2	journal	August 1997
(Pentamethylcyclopentadienyl)(polypyridyl) rhodium and iridium complexes as electrocatalysts for the reduction of protons to dihydrogen and the hydrogenation of organics Caix, Chrystelle; Chardon-Noblat, Sylvie; Deronzier, Alain Journal of Organometallic Chemistry, Vol. 540, Issue 1-2 https://doi.org/10.1016/S0022-328X(97)00096-X	journal	August 1997
Nachweis innermolekularer beweglichkeit durch NMR-spektroskopie XVI Kessler, H.; Leibfritz, D. Tetrahedron, Vol. 25, Issue 20 https://doi.org/10.1016/S0040-4020(01)83258-0	journal	January 1969
Molecular catalysis of electrochemical reactions Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel Current Opinion in Electrochemistry, Vol. 2, Issue 1 https://doi.org/10.1016/j.coelec.2017.02.006	journal	April 2017
A simple and efficient one-step protocol for the preparation of alkyl-substituted ammonium tetrafluoroborate and hexafluorophosphate salts Saba, Shahrokh; Hernandez, Renee; Choy, Christine Chin Journal of Fluorine Chemistry, Vol. 153 https://doi.org/10.1016/j.jfluchem.2013.05.007	journal	September 2013
Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems. Nicholson, R. S.; Shain, Irving Analytical Chemistry, Vol. 36, Issue 4, p. 706-723 https://doi.org/10.1021/ac60210a007	journal	April 1964
Generalized Numerical Method for Stationary Electrode Polarography. Application to Reactions Involving Second-Order Homogeneous Chemical Complications. Booman, G. L.; Pence, D. T. Analytical Chemistry, Vol. 37, Issue 11 https://doi.org/10.1021/ac60230a020	journal	October 1965
Thermodynamic Hydricity of Transition Metal Hydrides Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00168	journal	June 2016
Solvent-Dependent Thermochemistry of an Iridium/Ruthenium H ₂ Evolution Catalyst Brereton, Kelsey R.; Pitman, Catherine L.; Cundari, Thomas R. Inorganic Chemistry, Vol. 55, Issue 22 https://doi.org/10.1021/acs.inorgchem.6b02223	journal	November 2016
Decoding Proton-Coupled Electron Transfer with Potential–p K _a Diagrams McCarthy, Brian D.; Dempsey, Jillian L. Inorganic Chemistry, Vol. 56, Issue 3 https://doi.org/10.1021/acs.inorgchem.6b02325	journal	January 2017
Highly Active Ruthenium CNC Pincer Photocatalysts for Visible-Light-Driven Carbon Dioxide Reduction Das, Sanjit; Rodrigues, Roberta R.; Lamb, Robert W. Inorganic Chemistry, Vol. 58, Issue 12 https://doi.org/10.1021/acs.inorgchem.9b00791	journal	May 2019
Aqueous Hydricity from Calculations of Reduction Potential and Acidity in Water Brereton, Kelsey R.; Bellows, Sarina M.; Fallah, Hengameh The Journal of Physical Chemistry B, Vol. 120, Issue 50 https://doi.org/10.1021/acs.jpcb.6b09864	journal	December 2016
Dissection of Electronic Substituent Effects in Multielectron–Multistep Molecular Catalysis. Electrochemical CO ₂ -to-CO Conversion Catalyzed by Iron Porphyrins Azcarate, Iban; Costentin, Cyrille; Robert, Marc The Journal of Physical Chemistry C, Vol. 120, Issue 51 https://doi.org/10.1021/acs.jpcc.6b09947	journal	December 2016
Photochemical Production of Ethane from an Iridium Methyl Complex Pitman, Catherine L.; Miller, Alexander J. M. Organometallics, Vol. 36, Issue 10 https://doi.org/10.1021/acs.organomet.7b00175	journal	May 2017
Thermodynamic Hydricity across Solvents: Subtle Electronic Effects and Striking Ligation Effects in Iridium Hydrides Brereton, Kelsey R.; Jadrich, Caleb N.; Stratakes, Bethany M. Organometallics, Vol. 38, Issue 16 https://doi.org/10.1021/acs.organomet.9b00278	journal	July 2019
Breaking the Correlation between Energy Costs and Kinetic Barriers in Hydrogen Evolution via a Cobalt Pyridine-Diimine-Dioxime Catalyst Huo, Pengfei; Uyeda, Christopher; Goodpaster, Jason D. ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b01387	journal	August 2016
A Mononuclear Tungsten Photocatalyst for H ₂ Production Huckaba, Aron J.; Shirley, Hunter; Lamb, Robert W. ACS Catalysis, Vol. 8, Issue 6 https://doi.org/10.1021/acscatal.7b04242	journal	April 2018
Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H ₂ Production Klug, Christina M.; Cardenas, Allan Jay P.; Bullock, R. Morris ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.7b04379	journal	March 2018
Utilization of Thermodynamic Scaling Relationships in Hydricity To Develop Nickel Hydrogen Evolution Reaction Electrocatalysts with Weak Acids and Low Overpotentials Ostericher, Andrew L.; Waldie, Kate M.; Kubiak, Clifford P. ACS Catalysis, Vol. 8, Issue 10 https://doi.org/10.1021/acscatal.8b02922	journal	September 2018
Homogenous Electrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential in Acidic Organic Solutions Pegis, Michael L.; McKeown, Bradley A.; Kumar, Neeraj ACS Central Science, Vol. 2, Issue 11 https://doi.org/10.1021/acscentsci.6b00261	journal	October 2016
Brønsted Acid Scaling Relationships Enable Control Over Product Selectivity from O 2 Reduction with a Mononuclear Cobalt Porphyrin Catalyst Wang, Yu-Heng; Schneider, Patrick E.; Goldsmith, Zachary K. ACS Central Science, Vol. 5, Issue 6 https://doi.org/10.1021/acscentsci.9b00194	journal	June 2019
Molecular Photoelectrocatalysts for Light-Driven Hydrogen Production Brereton, Kelsey R.; Bonn, Annabell G.; Miller, Alexander J. M. ACS Energy Letters, Vol. 3, Issue 5 https://doi.org/10.1021/acsenergylett.8b00255	journal	April 2018
Hydrogen Production by Molecular Photocatalysis Esswein, Arthur J.; Nocera, Daniel G. Chemical Reviews, Vol. 107, Issue 10 https://doi.org/10.1021/cr050193e	journal	October 2007
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
Molecular Photoelectrocatalysts for Visible Light-Driven Hydrogen Evolution from Neutral Water Pitman, Catherine L.; Miller, Alexander J. M. ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500441f	journal	July 2014
.pi.-Arene Aqua Complexes of Cobalt, Rhodium, Iridium, and Ruthenium: Preparation, Structure, and Kinetics of Water Exchange and Water Substitution Dadci, Lynda; Elias, Horst; Frey, Urban Inorganic Chemistry, Vol. 34, Issue 1 https://doi.org/10.1021/ic00105a048	journal	January 1995
Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile Roberts, John A. S.; Bullock, R. Morris Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic302461q	journal	June 2012
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
Theory of Catalytic Polarographic Currents Delahay, Paul; Stiehl, George L. Journal of the American Chemical Society, Vol. 74, Issue 14 https://doi.org/10.1021/ja01134a014	journal	July 1952
Unsensitized Photochemical Hydrogen Production Catalyzed by Diiron Hydrides Wang, Wenguang; Rauchfuss, Thomas B.; Bertini, Luca Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja211778j	journal	February 2012
Photoswitchable Hydride Transfer from Iridium to 1-Methylnicotinamide Rationalized by Thermochemical Cycles Barrett, Seth M.; Pitman, Catherine L.; Walden, Andrew G. Journal of the American Chemical Society, Vol. 136, Issue 42 https://doi.org/10.1021/ja508762g	journal	October 2014
Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium Pitman, Catherine L.; Brereton, Kelsey R.; Miller, Alexander J. M. Journal of the American Chemical Society, Vol. 138, Issue 7 https://doi.org/10.1021/jacs.5b12363	journal	February 2016
Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism Chambers, Matthew B.; Kurtz, Daniel A.; Pitman, Catherine L. Journal of the American Chemical Society, Vol. 138, Issue 41 https://doi.org/10.1021/jacs.6b08701	journal	October 2016
Homogeneous Molecular Catalysis of Electrochemical Reactions: Catalyst Benchmarking and Optimization Strategies Costentin, Cyrille; Savéant, Jean-Michel Journal of the American Chemical Society, Vol. 139, Issue 24 https://doi.org/10.1021/jacs.7b02879	journal	June 2017
Extension of the Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile to a Full Span of 28 p K _a Units: Unification of Different Basicity Scales Kaljurand, Ivari; Kütt, Agnes; Sooväli, Lilli The Journal of Organic Chemistry, Vol. 70, Issue 3 https://doi.org/10.1021/jo048252w	journal	February 2005
Analytical study of a series of substituted (2,2'-bipyridyl)(pentamethylcyclopentadienyl)rhodium and -iridium complexes with regard to their effectiveness as redox catalysts for the indirect electrochemical and chemical reduction of NAD(P)+ Steckhan, Eberhard.; Herrmann, Sabine.; Ruppert, Romain. Organometallics, Vol. 10, Issue 5 https://doi.org/10.1021/om00051a056	journal	May 1991
Free-Energy Relationships between the Proton and Hydride Donor Abilities of [HNi(diphosphine) ₂ ] ⁺ Complexes and the Half-Wave Potentials of Their Conjugate Bases Berning, Douglas E.; Miedaner, Alex; Curtis, Calvin J. Organometallics, Vol. 20, Issue 9 https://doi.org/10.1021/om0100582	journal	April 2001
Single-chromophore single-molecule photocatalyst for the production of dihydrogen using low-energy light Whittemore, T. J.; Xue, C.; Huang, J. Nature Chemistry, Vol. 12, Issue 2 https://doi.org/10.1038/s41557-019-0397-4	journal	January 2020
Heterogeneous photocatalyst materials for water splitting Kudo, Akihiko; Miseki, Yugo Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B800489G	journal	January 2009
Catalysis of the electrochemical reduction of carbon dioxide Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel Chem. Soc. Rev., Vol. 42, Issue 6 https://doi.org/10.1039/C2CS35360A	journal	January 2013
Efficient photochemical reduction of CO ₂ to CO by visible light irradiation of systems containing Re(bipy)(CO) ₃ X or Ru(bipy) ₃ ²⁺ –Co ²⁺ combinations as homogeneous catalysts Hawecker, Jeannot; Lehn, Jean-Marie; Ziessel, Raymond J. Chem. Soc., Chem. Commun., Issue 9 https://doi.org/10.1039/C39830000536	journal	January 1983
Development and understanding of cobaloxime activity through electrochemical molecular catalyst screening Wakerley, David W.; Reisner, Erwin Phys. Chem. Chem. Phys., Vol. 16, Issue 12 https://doi.org/10.1039/C4CP00453A	journal	January 2014
Non-sensitized selective photochemical reduction of CO ₂ to CO under visible light with an iron molecular catalyst Rao, Heng; Bonin, Julien; Robert, Marc Chemical Communications, Vol. 53, Issue 19 https://doi.org/10.1039/C6CC09967J	journal	January 2017
Homoconjugated hydrogen bonds with amidine and guanidine bases Osmometric, potentiometric and FTIR studies Galezowski, Wlodzimierz; Jarczewski, Arnold; Stanczyk, Malgorzata Journal of the Chemical Society, Faraday Transactions, Vol. 93, Issue 15 https://doi.org/10.1039/a700668c	journal	January 1997
Molecular systems for light driven hydrogen production Eckenhoff, William T.; Eisenberg, Richard Dalton Transactions, Vol. 41, Issue 42 https://doi.org/10.1039/c2dt30823a	journal	January 2012
Basicity of substituted 2-phenyl-1,1,3,3- tetramethylguanidines and other bases in acetonitrile solvent Leffek, Kenneth T.; Pruszynski, Przemyslaw; Thanapaalasingham, Kohila Canadian Journal of Chemistry, Vol. 67, Issue 4 https://doi.org/10.1139/v89-089	journal	April 1989
Recommendations on reporting electrode potentials in nonaqueous solvents (Recommendations 1983) Gritzner, G.; Kuta, J. Pure and Applied Chemistry, Vol. 56, Issue 4 https://doi.org/10.1351/pac198456040461	journal	January 1984

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H2 Evolution at an Electrochemical “Underpotential” with an Iridium-Based Molecular Photoelectrocatalyst

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H₂ Evolution at an Electrochemical “Underpotential” with an Iridium-Based Molecular Photoelectrocatalyst