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Title: Interfacial Deposition of Ru(II) Bipyridine-Dicarboxylate Complexes by Ligand Substitution for Applications in Water Oxidation Catalysis

Abstract

Water oxidation is a critical step in artificial photosynthesis and provides the protons and electrons used in reduction reactions to make solar fuels. Significant advances have been made in the area of molecular water oxidation catalysts with a notable breakthrough in the development of Ru(II) complexes that use a planar “bda” ligand (bda is 2,2'-bipyridine-6,6'-dicarboxylate). These Ru(II)(bda) complexes show lower overpotentials for driving water oxidation making them ideal for light-driven applications with a suitable chromophore. Nevertheless, synthesis of heterogeneous Ru(II)(bda) complexes remains challenging. We discuss here a new “bottom-up” synthetic method for immobilizing these catalysts at the surface of a photoanode for use in a dye-sensitized photoelectrosynthesis cell (DSPEC). The procedure provides a basis for rapidly screening the role of ligand variations at the catalyst in order to understand the impact on device performance. The best results of a water-oxidation DSPEC photoanode based on this procedure reached 1.4 mA/cm2 at pH 7 in 0.1 M [PO4H2]-/[PO4H]2- solution with minimal loss in catalytic behavior over 30 min, and produced an incident photon to current efficiency (IPCE) of 24.8% at 440 nm.

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
  2. Florida Intl Univ., Miami, FL (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1470086
Grant/Contract Number:  
SC0001011
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 2; Related Information: UNC partners with University of North Carolina (lead); Duke University; University of Florida; Georgia Institute of Technology; University; North Carolina Central University; Research Triangle Institute; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); photosynthesis (natural and artificial); hydrogen and fuel cells; electrodes - solar; charge transport; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Wang, Degao, Marquard, Seth L., Troian-Gautier, Ludovic, Sheridan, Matthew V., Sherman, Benjamin D., Wang, Ying, Eberhart, Michael S., Farnum, Byron H., Dares, Christopher J., and Meyer, Thomas J.. Interfacial Deposition of Ru(II) Bipyridine-Dicarboxylate Complexes by Ligand Substitution for Applications in Water Oxidation Catalysis. United States: N. p., 2018. Web. doi:10.1021/jacs.7b10809.
Wang, Degao, Marquard, Seth L., Troian-Gautier, Ludovic, Sheridan, Matthew V., Sherman, Benjamin D., Wang, Ying, Eberhart, Michael S., Farnum, Byron H., Dares, Christopher J., & Meyer, Thomas J.. Interfacial Deposition of Ru(II) Bipyridine-Dicarboxylate Complexes by Ligand Substitution for Applications in Water Oxidation Catalysis. United States. https://doi.org/10.1021/jacs.7b10809
Wang, Degao, Marquard, Seth L., Troian-Gautier, Ludovic, Sheridan, Matthew V., Sherman, Benjamin D., Wang, Ying, Eberhart, Michael S., Farnum, Byron H., Dares, Christopher J., and Meyer, Thomas J.. Tue . "Interfacial Deposition of Ru(II) Bipyridine-Dicarboxylate Complexes by Ligand Substitution for Applications in Water Oxidation Catalysis". United States. https://doi.org/10.1021/jacs.7b10809. https://www.osti.gov/servlets/purl/1470086.
@article{osti_1470086,
title = {Interfacial Deposition of Ru(II) Bipyridine-Dicarboxylate Complexes by Ligand Substitution for Applications in Water Oxidation Catalysis},
author = {Wang, Degao and Marquard, Seth L. and Troian-Gautier, Ludovic and Sheridan, Matthew V. and Sherman, Benjamin D. and Wang, Ying and Eberhart, Michael S. and Farnum, Byron H. and Dares, Christopher J. and Meyer, Thomas J.},
abstractNote = {Water oxidation is a critical step in artificial photosynthesis and provides the protons and electrons used in reduction reactions to make solar fuels. Significant advances have been made in the area of molecular water oxidation catalysts with a notable breakthrough in the development of Ru(II) complexes that use a planar “bda” ligand (bda is 2,2'-bipyridine-6,6'-dicarboxylate). These Ru(II)(bda) complexes show lower overpotentials for driving water oxidation making them ideal for light-driven applications with a suitable chromophore. Nevertheless, synthesis of heterogeneous Ru(II)(bda) complexes remains challenging. We discuss here a new “bottom-up” synthetic method for immobilizing these catalysts at the surface of a photoanode for use in a dye-sensitized photoelectrosynthesis cell (DSPEC). The procedure provides a basis for rapidly screening the role of ligand variations at the catalyst in order to understand the impact on device performance. The best results of a water-oxidation DSPEC photoanode based on this procedure reached 1.4 mA/cm2 at pH 7 in 0.1 M [PO4H2]-/[PO4H]2- solution with minimal loss in catalytic behavior over 30 min, and produced an incident photon to current efficiency (IPCE) of 24.8% at 440 nm.},
doi = {10.1021/jacs.7b10809},
journal = {Journal of the American Chemical Society},
number = 2,
volume = 140,
place = {United States},
year = {Tue Jan 02 00:00:00 EST 2018},
month = {Tue Jan 02 00:00:00 EST 2018}
}

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Works referenced in this record:

Photoassisted Overall Water Splitting in a Visible Light-Absorbing Dye-Sensitized Photoelectrochemical Cell
journal, January 2009

  • Youngblood, W. Justin; Lee, Seung-Hyun Anna; Kobayashi, Yoji
  • Journal of the American Chemical Society, Vol. 131, Issue 3, p. 926-927
  • DOI: 10.1021/ja809108y

Chemical approaches to artificial photosynthesis
journal, May 1989


Visible light-driven water oxidation—from molecular catalysts to photoelectrochemical cells
journal, January 2011

  • Duan, Lele; Tong, Lianpeng; Xu, Yunhua
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c1ee01276b

A visible light water-splitting cell with a photoanode formed by codeposition of a high-potential porphyrin and an iridium water-oxidation catalyst
journal, January 2011

  • Moore, Gary F.; Blakemore, James D.; Milot, Rebecca L.
  • Energy & Environmental Science, Vol. 4, Issue 7
  • DOI: 10.1039/c1ee01037a

Molecular Chromophore–Catalyst Assemblies for Solar Fuel Applications
journal, August 2015


Water splitting dye-sensitized solar cells
journal, June 2017


Photodriven Oxidation of Surface-Bound Iridium-Based Molecular Water-Oxidation Catalysts on Perylene-3,4-dicarboximide-Sensitized TiO 2 Electrodes Protected by an Al 2 O 3 Layer
journal, February 2017

  • Kamire, Rebecca J.; Materna, Kelly L.; Hoffeditz, William L.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 7
  • DOI: 10.1021/acs.jpcc.6b11672

A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II
journal, May 2016

  • Schulze, Marcus; Kunz, Valentin; Frischmann, Peter D.
  • Nature Chemistry, Vol. 8, Issue 6
  • DOI: 10.1038/nchem.2503

Highly Efficient Bioinspired Molecular Ru Water Oxidation Catalysts with Negatively Charged Backbone Ligands
journal, June 2015


A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II
journal, March 2012

  • Duan, Lele; Bozoglian, Fernando; Mandal, Sukanta
  • Nature Chemistry, Vol. 4, Issue 5
  • DOI: 10.1038/nchem.1301

Highly efficient and robust molecular ruthenium catalysts for water oxidation
journal, July 2012

  • Duan, L.; Araujo, C. M.; Ahlquist, M. S. G.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
  • DOI: 10.1073/pnas.1118347109

Supramolecular Approaches to Improve the Performance of Ruthenium-Based Water Oxidation Catalysts
journal, June 2017

  • Kunz, Valentin; Schmidt, David; Röhr, Merle I. S.
  • Advanced Energy Materials, Vol. 7, Issue 16
  • DOI: 10.1002/aenm.201602939

Heterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor
journal, July 2016

  • Materna, Kelly L.; Rudshteyn, Benjamin; Brennan, Bradley J.
  • ACS Catalysis, Vol. 6, Issue 8
  • DOI: 10.1021/acscatal.6b01101

Mechanisms of molecular water oxidation in solution and on oxide surfaces
journal, January 2017

  • Meyer, Thomas J.; Sheridan, Matthew V.; Sherman, Benjamin D.
  • Chemical Society Reviews, Vol. 46, Issue 20
  • DOI: 10.1039/C7CS00465F

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling
journal, January 2017

  • Shaffer, David W.; Xie, Yan; Concepcion, Javier J.
  • Chemical Society Reviews, Vol. 46, Issue 20
  • DOI: 10.1039/C7CS00542C

A molecular catalyst for water oxidation that binds to metal oxide surfaces
journal, March 2015

  • Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7469

A Million Turnover Molecular Anode for Catalytic Water Oxidation
journal, November 2016

  • Creus, Jordi; Matheu, Roc; Peñafiel, Itziar
  • Angewandte Chemie International Edition, Vol. 55, Issue 49
  • DOI: 10.1002/anie.201609167

Two Electrode Collector–Generator Method for the Detection of Electrochemically or Photoelectrochemically Produced O 2
journal, July 2016

  • Sherman, Benjamin D.; Sheridan, Matthew V.; Dares, Christopher J.
  • Analytical Chemistry, Vol. 88, Issue 14
  • DOI: 10.1021/acs.analchem.6b00738

Synthesis of a series of trifluoromethylazoles and determination of pK a of acidic and basic trifluoromethyl heterocycles by 19F NMR spectroscopy
journal, January 1996

  • Jones, Brian G.; Branch, Sarah K.; Thompson, Andrew S.
  • Journal of the Chemical Society, Perkin Transactions 1, Issue 22
  • DOI: 10.1039/p19960002685

Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex
journal, April 2015

  • Song, Na; Concepcion, Javier J.; Binstead, Robert A.
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 16
  • DOI: 10.1073/pnas.1500245112

Stabilization of a Ruthenium(II) Polypyridyl Dye on Nanocrystalline TiO 2 by an Electropolymerized Overlayer
journal, October 2013

  • Lapides, Alexander M.; Ashford, Dennis L.; Hanson, Kenneth
  • Journal of the American Chemical Society, Vol. 135, Issue 41
  • DOI: 10.1021/ja4055977

Self-assembled molecular p/n junctions for applications in dye-sensitized solar energy conversion
journal, June 2016

  • Farnum, Byron H.; Wee, Kyung-Ryang; Meyer, Thomas J.
  • Nature Chemistry, Vol. 8, Issue 9
  • DOI: 10.1038/nchem.2536

Self-Assembled Bilayer Films of Ruthenium(II)/Polypyridyl Complexes through Layer-by-Layer Deposition on Nanostructured Metal Oxides
journal, November 2012

  • Hanson, Kenneth; Torelli, Daniel A.; Vannucci, Aaron K.
  • Angewandte Chemie International Edition, Vol. 51, Issue 51
  • DOI: 10.1002/anie.201206882

Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes
journal, November 2016


Electro-assembly of a Chromophore-Catalyst Bilayer for Water Oxidation and Photocatalytic Water Splitting
journal, February 2015

  • Ashford, Dennis L.; Sherman, Benjamin D.; Binstead, Robert A.
  • Angewandte Chemie International Edition, Vol. 54, Issue 16
  • DOI: 10.1002/anie.201410944

Evaluation of Chromophore and Assembly Design in Light-Driven Water Splitting with a Molecular Water Oxidation Catalyst
journal, June 2016


Plasmon-enhanced light-driven water oxidation by a dye-sensitized photoanode
journal, August 2017

  • Wang, Degao; Sherman, Benjamin D.; Farnum, Byron H.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 37
  • DOI: 10.1073/pnas.1708336114

Inner Layer Control of Performance in a Dye-Sensitized Photoelectrosynthesis Cell
journal, March 2017

  • Wang, Degao; Farnum, Byron H.; Sheridan, Matthew V.
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 39
  • DOI: 10.1021/acsami.7b00225

Light-Driven Water Splitting with a Molecular Electroassembly-Based Core/Shell Photoanode
journal, July 2015

  • Sherman, Benjamin D.; Ashford, Dennis L.; Lapides, Alexander M.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 16
  • DOI: 10.1021/acs.jpclett.5b01370

Layer-by-Layer Molecular Assemblies for Dye-Sensitized Photoelectrosynthesis Cells Prepared by Atomic Layer Deposition
journal, August 2017

  • Wang, Degao; Sheridan, Matthew V.; Shan, Bing
  • Journal of the American Chemical Society, Vol. 139, Issue 41
  • DOI: 10.1021/jacs.7b07216

Visible Light-Driven Water Splitting in Photoelectrochemical Cells with Supramolecular Catalysts on Photoanodes
journal, May 2014

  • Ding, Xin; Gao, Yan; Zhang, Linlin
  • ACS Catalysis, Vol. 4, Issue 7
  • DOI: 10.1021/cs500518k

Self-Assembled Bilayers on Indium–Tin Oxide (SAB-ITO) Electrodes: A Design for Chromophore–Catalyst Photoanodes
journal, August 2012

  • Glasson, Christopher R. K.; Song, Wenjing; Ashford, Dennis L.
  • Inorganic Chemistry, Vol. 51, Issue 16
  • DOI: 10.1021/ic300636w

Stabilizing Small Molecules on Metal Oxide Surfaces Using Atomic Layer Deposition
journal, September 2013

  • Hanson, Kenneth; Losego, Mark D.; Kalanyan, Berç
  • Nano Letters, Vol. 13, Issue 10
  • DOI: 10.1021/nl402416s

Dye Stabilization and Enhanced Photoelectrode Wettability in Water-Based Dye-Sensitized Solar Cells through Post-assembly Atomic Layer Deposition of TiO 2
journal, July 2013

  • Son, Ho-Jin; Prasittichai, Chaiya; Mondloch, Joseph E.
  • Journal of the American Chemical Society, Vol. 135, Issue 31
  • DOI: 10.1021/ja406538a

Molecular-Scale Interface Engineering of TiO2 Nanocrystals: Improve the Efficiency and Stability of Dye-Sensitized Solar Cells
journal, December 2003

  • Wang, P.; Zakeeruddin, S. M.; Humphry-Baker, R.
  • Advanced Materials, Vol. 15, Issue 24
  • DOI: 10.1002/adma.200306084

Effect of Interfacial Engineering in Solid-State Nanostructured Sb 2 S 3 Heterojunction Solar Cells
journal, September 2012

  • Fukumoto, Takafumi; Moehl, Thomas; Niwa, Yusuke
  • Advanced Energy Materials, Vol. 3, Issue 1
  • DOI: 10.1002/aenm.201200540

Enhance the Performance of Dye-Sensitized Solar Cells by Co-grafting Amphiphilic Sensitizer and Hexadecylmalonic Acid on TiO 2 Nanocrystals
journal, December 2003

  • Wang, Peng; Zakeeruddin, Shaik M.; Comte, Pascal
  • The Journal of Physical Chemistry B, Vol. 107, Issue 51
  • DOI: 10.1021/jp0365965

Efficient Light-Driven Oxidation of Alcohols Using an Organic Chromophore–Catalyst Assembly Anchored to TiO 2
journal, March 2016

  • Pho, Toan V.; Sheridan, Matthew V.; Morseth, Zachary A.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 14
  • DOI: 10.1021/acsami.6b00932

Dipicolinic acid: a strong anchoring group with tunable redox and spectral behavior for stable dye-sensitized solar cells
journal, January 2015

  • Gabrielsson, Erik; Tian, Haining; Eriksson, Susanna K.
  • Chemical Communications, Vol. 51, Issue 18
  • DOI: 10.1039/C4CC06432A

Works referencing / citing this record:

A stable dye-sensitized photoelectrosynthesis cell mediated by a NiO overlayer for water oxidation
journal, September 2019

  • Wang, Degao; Niu, Fujun; Mortelliti, Michael J.
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 23
  • DOI: 10.1073/pnas.1821687116

Angstrom Thick ZnO Passivation Layer to Improve the Photoelectrochemical Water Splitting Performance of a TiO2 Nanowire Photoanode: The Role of Deposition Temperature
journal, November 2018


Improvement of dye-sensitized solar cell performances through introducing europium dye with multiple excitation: dual enhancement in light absorption
journal, January 2019

  • Zhang, Lingyun; Wang, Xinzhe; Sun, Xuhui
  • New Journal of Chemistry, Vol. 43, Issue 33
  • DOI: 10.1039/c9nj02985k

Vertical Step‐Growth Polymerization Driven by Electrochemical Stimuli from an Electrode
journal, December 2018

  • Zhang, Jian; Du, Jia; Wang, Jinxin
  • Angewandte Chemie International Edition, Vol. 57, Issue 51
  • DOI: 10.1002/anie.201809567

Core–shell structured titanium dioxide nanomaterials for solar energy utilization
journal, January 2018

  • Li, Wei; Elzatahry, Ahmed; Aldhayan, Dhaifallah
  • Chemical Society Reviews, Vol. 47, Issue 22
  • DOI: 10.1039/c8cs00443a

Production of solar chemicals: gaining selectivity with hybrid molecule/semiconductor assemblies
journal, January 2018

  • Hennessey, Seán; Farràs, Pau
  • Chemical Communications, Vol. 54, Issue 50
  • DOI: 10.1039/c8cc02487a

The development of molecular water oxidation catalysts
journal, April 2019

  • Matheu, Roc; Garrido-Barros, Pablo; Gil-Sepulcre, Marcos
  • Nature Reviews Chemistry, Vol. 3, Issue 5
  • DOI: 10.1038/s41570-019-0096-0

Inorganic Photochemistry and Solar Energy Harvesting: Current Developments and Challenges to Solar Fuel Production
journal, January 2019

  • Sousa, Sinval F.; Souza, Breno L.; Barros, Cristiane L.
  • International Journal of Photoenergy, Vol. 2019
  • DOI: 10.1155/2019/9624092

Quantum Chemical Study of the Mechanism of Water Oxidation Catalyzed by a Heterotrinuclear Ru 2 Mn Complex
journal, February 2019

  • Li, Ying‐Ying; Gimbert, Carolina; Llobet, Antoni
  • ChemSusChem, Vol. 12, Issue 5
  • DOI: 10.1002/cssc.201802395

Hybrid Photoelectrochemical Water Splitting Systems: From Interface Design to System Assembly
journal, June 2019


Light-driven water oxidation by a dye-sensitized photoanode with a chromophore/catalyst assembly on a mesoporous double-shell electrode
journal, January 2019

  • Liu, Qing; Wang, Degao; Shan, Bing
  • The Journal of Chemical Physics, Vol. 150, Issue 4
  • DOI: 10.1063/1.5048780

Vertical Step‐Growth Polymerization Driven by Electrochemical Stimuli from an Electrode
journal, December 2018


Three dimensional carbon substrate materials for electrolysis of water
journal, June 2018


Stabilized photoanodes for water oxidation by integration of organic dyes, water oxidation catalysts, and electron-transfer mediators
journal, August 2018

  • Wang, Degao; Eberhart, Michael S.; Sheridan, Matthew V.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 34
  • DOI: 10.1073/pnas.1802903115

A donor-chromophore-catalyst assembly for solar CO 2 reduction
journal, January 2019

  • Wang, Degao; Wang, Ying; Brady, Matthew D.
  • Chemical Science, Vol. 10, Issue 16
  • DOI: 10.1039/c8sc03316a