Visible photoelectrochemical water splitting into H2 and O2 in a dye-sensitized photoelectrosynthesis cell

Alibabaei, Leila; Sherman, Benjamin D.; Norris, Michael R.; Brennaman, M. Kyle; Meyer, Thomas J.

doi:10.1073/pnas.1506111112

Visible photoelectrochemical water splitting into H₂ and O₂ in a dye-sensitized photoelectrosynthesis cell

Journal Article · Mon Apr 27 00:00:00 EDT 2015 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1506111112· OSTI ID:1210802

Alibabaei, Leila ^[1]; Sherman, Benjamin D. ^[1]; Norris, Michael R. ^[2]; Brennaman, M. Kyle ^[1]; Meyer, Thomas J. ^[1]

Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry

A hybrid strategy for solar water splitting is exploited here based on a dye-sensitized photoelectrosynthesis cell (DSPEC) with a mesoporous SnO₂/TiO₂ core/shell nanostructured electrode derivatized with a surface-bound Ru(II) polypyridyl-based chromophore–catalyst assembly. The assembly, [(4,4’-(PO₃H₂)₂bpy)₂Ru(4-Mebpy-4’-bimpy)Ru(tpy)(OH₂)]⁴⁺ ([RuaII-RubII-OH₂]⁴⁺, combines both a light absorber and a water oxidation catalyst in a single molecule. It was attached to the TiO₂ shell by phosphonate-surface oxide binding. The oxide-bound assembly was further stabilized on the surface by atomic layer deposition (ALD) of either Al₂O₃ or TiO₂ overlayers. Illumination of the resulting fluorine-doped tin oxide (FTO)|SnO₂/TiO₂|-[Ru_a^II-Ru_b^II-OH₂]⁴⁺(Al₂O₃ or TiO₂) photoanodes in photoelectrochemical cells with a Pt cathode and a small applied bias resulted in visible-light water splitting as shown by direct measurements of both evolved H₂ and O₂. The performance of the resulting DSPECs varies with shell thickness and the nature and extent of the oxide overlayer. Use of the SnO₂/TiO₂ core/shell compared with nanoITO/TiO₂ with the same assembly results in photocurrent enhancements of ~5. In conclusion, systematic variations in shell thickness and ALD overlayer lead to photocurrent densities as high as 1.97 mA/cm² with 445-nm, ~90-mW/cm² illumination in a phosphate buffer at pH 7.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC). Center for Solar Fuels (UNC EFRC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Contributing Organization:: Duke University; Georgia Institute of Technology; North Carolina Central University; Research Triangle Institute; UNC partners with University of North Carolina (lead); University; University of Florida

Grant/Contract Number:: SC0001011

OSTI ID:: 1210802

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 19 Vol. 112; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

References (30)

Effect of an Ultrathin TiO₂ Layer Coated on Submicrometer-Sized ZnO Nanocrystallite Aggregates by Atomic Layer Deposition on the Performance of Dye-Sensitized Solar Cells Park, Kwangsuk; Zhang, Qifeng; Garcia, Betzaida Battalla Advanced Materials, Vol. 22, Issue 21, p. 2329-2332 https://doi.org/10.1002/adma.200903219	journal	April 2010
Low-Overpotential Water Oxidation by a Surface-Bound Ruthenium-Chromophore-Ruthenium-Catalyst Assembly Norris, Michael R.; Concepcion, Javier J.; Fang, Zhen Angewandte Chemie International Edition, Vol. 52, Issue 51 https://doi.org/10.1002/anie.201305951	journal	November 2013
Electrochemical Instability of Phosphonate-Derivatized, Ruthenium(III) Polypyridyl Complexes on Metal Oxide Surfaces Hyde, Jacob T.; Hanson, Kenneth; Vannucci, Aaron K. ACS Applied Materials & Interfaces, Vol. 7, Issue 18 https://doi.org/10.1021/acsami.5b01000	journal	May 2015
Low-Temperature Crystalline Titanium Dioxide by Atomic Layer Deposition for Dye-Sensitized Solar Cells Chandiran, Aravind Kumar; Yella, Aswani; Stefik, Morgan ACS Applied Materials & Interfaces, Vol. 5, Issue 8 https://doi.org/10.1021/am400866s	journal	January 2013
Stabilization of [Ru(bpy) ₂ (4,4′-(PO ₃ H ₂ )bpy)] ²⁺ on Mesoporous TiO ₂ with Atomic Layer Deposition of Al ₂ O ₃ Hanson, Kenneth; Losego, Mark D.; Kalanyan, Berç Chemistry of Materials, Vol. 25, Issue 1 https://doi.org/10.1021/cm303172w	journal	December 2012
Solar Water Splitting Cells Walter, Michael G.; Warren, Emily L.; McKone, James R. Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473 https://doi.org/10.1021/cr1002326	journal	November 2010
Visible Light-Driven Water Splitting in Photoelectrochemical Cells with Supramolecular Catalysts on Photoanodes Ding, Xin; Gao, Yan; Zhang, Linlin ACS Catalysis, Vol. 4, Issue 7 https://doi.org/10.1021/cs500518k	journal	May 2014
Chemical Approaches to Artificial Photosynthesis. 2 Alstrum-Acevedo, James H.; Brennaman, M. Kyle; Meyer, Thomas J. Inorganic Chemistry, Vol. 44, Issue 20 https://doi.org/10.1021/ic050904r	journal	October 2005
Visible Region Photooxidation on TiO ₂ with a Chromophore−Catalyst Molecular Assembly Treadway, Joseph A.; Moss, John A.; Meyer, Thomas J. Inorganic Chemistry, Vol. 38, Issue 20 https://doi.org/10.1021/ic990466m	journal	October 1999
Visible Light Driven Water Splitting in a Molecular Device with Unprecedentedly High Photocurrent Density Gao, Yan; Ding, Xin; Liu, Jianhui Journal of the American Chemical Society, Vol. 135, Issue 11 https://doi.org/10.1021/ja400402d	journal	March 2013
One-Electron Activation of Water Oxidation Catalysis Tamaki, Yusuke; Vannucci, Aaron K.; Dares, Christopher J. Journal of the American Chemical Society, Vol. 136, Issue 19 https://doi.org/10.1021/ja502637s	journal	May 2014
Effects of Electron Trapping and Protonation on the Efficiency of Water-Splitting Dye-Sensitized Solar Cells Swierk, John R.; McCool, Nicholas S.; Saunders, Timothy P. Journal of the American Chemical Society, Vol. 136, Issue 31 https://doi.org/10.1021/ja5040705	journal	July 2014
Visible Light Driven Benzyl Alcohol Dehydrogenation in a Dye-Sensitized Photoelectrosynthesis Cell Song, Wenjing; Vannucci, Aaron K.; Farnum, Byron H. Journal of the American Chemical Society, Vol. 136, Issue 27 https://doi.org/10.1021/ja505022f	journal	June 2014
Photoassisted Overall Water Splitting in a Visible Light-Absorbing Dye-Sensitized Photoelectrochemical Cell Youngblood, W. Justin; Lee, Seung-Hyun Anna; Kobayashi, Yoji Journal of the American Chemical Society, Vol. 131, Issue 3, p. 926-927 https://doi.org/10.1021/ja809108y	journal	January 2009
Solar Driven Water Oxidation by a Bioinspired Manganese Molecular Catalyst Brimblecombe, Robin; Koo, Annette; Dismukes, G. Charles Journal of the American Chemical Society, Vol. 132, Issue 9 https://doi.org/10.1021/ja910055a	journal	March 2010
Stabilizing Small Molecules on Metal Oxide Surfaces Using Atomic Layer Deposition Hanson, Kenneth; Losego, Mark D.; Kalanyan, Berç Nano Letters, Vol. 13, Issue 10 https://doi.org/10.1021/nl402416s	journal	September 2013
Atomic Layer Deposition of TiO ₂ on Mesoporous nanoITO: Conductive Core–Shell Photoanodes for Dye-Sensitized Solar Cells Alibabaei, Leila; Farnum, Byron H.; Kalanyan, Berç Nano Letters, Vol. 14, Issue 6 https://doi.org/10.1021/nl5006433	journal	May 2014
Radial Electron Collection in Dye-Sensitized Solar Cells Martinson, Alex B. F.; Elam, Jeffrey W.; Liu, Jun Nano Letters, Vol. 8, Issue 9, p. 2862-2866 https://doi.org/10.1021/nl8015285	journal	September 2008
Fast Transporting ZnO–TiO ₂ Coaxial Photoanodes for Dye-Sensitized Solar Cells Based on ALD-Modified SiO ₂ Aerogel Frameworks Williams, Vennesa O.; Jeong, Nak Cheon; Prasittichai, Chaiya ACS Nano, Vol. 6, Issue 7 https://doi.org/10.1021/nn3015695	journal	June 2012
A visible light water-splitting cell with a photoanode formed by codeposition of a high-potential porphyrin and an iridium water-oxidation catalyst Moore, Gary F.; Blakemore, James D.; Milot, Rebecca L. Energy & Environmental Science, Vol. 4, Issue 7 https://doi.org/10.1039/c1ee01037a	journal	January 2011
Polyoxometalate water oxidation catalysts and the production of green fuel Lv, Hongjin; Geletii, Yurii V.; Zhao, Chongchao Chemical Society Reviews, Vol. 41, Issue 22, p. 7572-7589 https://doi.org/10.1039/c2cs35292c	journal	January 2012
Applications of metal oxide materials in dye sensitized photoelectrosynthesis cells for making solar fuels: let the molecules do the work Alibabaei, Leila; Luo, Hanlin; House, Ralph L. Journal of Materials Chemistry A, Vol. 1, Issue 13 https://doi.org/10.1039/c2ta00935h	journal	January 2013
Energy and environment policy case for a global project on artificial photosynthesis Faunce, Thomas A.; Lubitz, Wolfgang; Rutherford, A. W. (Bill) Energy & Environmental Science, Vol. 6, Issue 3 https://doi.org/10.1039/c3ee00063j	journal	January 2013
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
Concerted O atom-proton transfer in the O--O bond forming step in water oxidation Chen, Z.; Concepcion, J. J.; Hu, X. Proceedings of the National Academy of Sciences, Vol. 107, Issue 16, p. 7225-7229 https://doi.org/10.1073/pnas.1001132107	journal	April 2010
Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator Zhao, Y.; Swierk, J. R.; Megiatto, J. D. Proceedings of the National Academy of Sciences, Vol. 109, Issue 39 https://doi.org/10.1073/pnas.1118339109	journal	April 2012
Chemical approaches to artificial photosynthesis Concepcion, J. J.; House, R. L.; Papanikolas, J. M. Proceedings of the National Academy of Sciences, Vol. 109, Issue 39 https://doi.org/10.1073/pnas.1212254109	journal	September 2012
Solar water splitting in a molecular photoelectrochemical cell Alibabaei, L.; Brennaman, M. K.; Norris, M. R. Proceedings of the National Academy of Sciences, Vol. 110, Issue 50 https://doi.org/10.1073/pnas.1319628110	journal	November 2013
Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation Vannucci, A. K.; Alibabaei, L.; Losego, M. D. Proceedings of the National Academy of Sciences, Vol. 110, Issue 52 https://doi.org/10.1073/pnas.1319832110	journal	November 2013
Making solar fuels by artificial photosynthesis Song, Wenjing; Chen, Zuofeng; Brennaman, M. Kyle Pure and Applied Chemistry, Vol. 83, Issue 4 https://doi.org/10.1351/PAC-CON-10-11-09	journal	March 2011

Cited By (29)

Recent Advances in Sensitized Photocathodes: From Molecular Dyes to Semiconducting Quantum Dots Wu, Hao-Lin; Li, Xu-Bing; Tung, Chen-Ho Advanced Science, Vol. 5, Issue 4 https://doi.org/10.1002/advs.201700684	journal	January 2018
Solution‐Processed Self‐Powered Transparent Ultraviolet Photodetectors with Ultrafast Response Speed for High‐Performance Communication System Fang, Huajing; Zheng, Cheng; Wu, Liangliang Advanced Functional Materials, Vol. 29, Issue 20 https://doi.org/10.1002/adfm.201809013	journal	February 2019
Photoelectrocatalytic Materials for Solar Water Splitting Yao, Tingting; An, Xiurui; Han, Hongxian Advanced Energy Materials, Vol. 8, Issue 21 https://doi.org/10.1002/aenm.201800210	journal	May 2018
A Million Turnover Molecular Anode for Catalytic Water Oxidation Creus, Jordi; Matheu, Roc; Peñafiel, Itziar Angewandte Chemie, Vol. 128, Issue 49 https://doi.org/10.1002/ange.201609167	journal	November 2016
Light‐Driven Water Splitting Mediated by Photogenerated Bromine Sheridan, Matthew V.; Wang, Ying; Wang, Degao Angewandte Chemie, Vol. 130, Issue 13 https://doi.org/10.1002/ange.201708879	journal	March 2018
A Million Turnover Molecular Anode for Catalytic Water Oxidation Creus, Jordi; Matheu, Roc; Peñafiel, Itziar Angewandte Chemie International Edition, Vol. 55, Issue 49 https://doi.org/10.1002/anie.201609167	journal	November 2016
Light-Driven Water Splitting Mediated by Photogenerated Bromine Sheridan, Matthew V.; Wang, Ying; Wang, Degao Angewandte Chemie International Edition, Vol. 57, Issue 13 https://doi.org/10.1002/anie.201708879	journal	March 2018
Ru-bis(pyridine)pyrazolate (bpp)-Based Water-Oxidation Catalysts Anchored on TiO ₂ : The Importance of the Nature and Position of the Anchoring Group Francàs, Laia; Richmond, Craig; Garrido-Barros, Pablo Chemistry - A European Journal, Vol. 22, Issue 15 https://doi.org/10.1002/chem.201504015	journal	February 2016
Behavior of Ru-bda Water-Oxidation Catalysts in Low Oxidation States Matheu, Roc; Ghaderian, Abolfazl; Francàs, Laia Chemistry - A European Journal, Vol. 24, Issue 49 https://doi.org/10.1002/chem.201801236	journal	August 2018
Directly Photoexcited Oxides for Photoelectrochemical Water Splitting Pan, Linfeng; Vlachopoulos, Nick; Hagfeldt, Anders ChemSusChem, Vol. 12, Issue 19 https://doi.org/10.1002/cssc.201900849	journal	September 2019
Solar Energy Conversion in Photoelectrochemical Systems Caramori, Stefano; Ronconi, Federico; Argazzi, Roberto Lecture Notes in Chemistry https://doi.org/10.1007/978-3-319-31671-0_2	book	July 2016
Developing a scalable artificial photosynthesis technology through nanomaterials by design Lewis, Nathan S. Nature Nanotechnology, Vol. 11, Issue 12 https://doi.org/10.1038/nnano.2016.194	journal	December 2016
Spectroscopic signatures of ligand field states in {Ru ^II (imine)} complexes Cadranel, Alejandro; Pieslinger, German E.; Tongying, Pornthip Dalton Transactions, Vol. 45, Issue 13 https://doi.org/10.1039/c5dt04332h	journal	January 2016
An aqueous, organic dye derivatized SnO ₂ /TiO ₂ core/shell photoanode Wee, Kyung-Ryang; Sherman, Benjamin D.; Brennaman, M. Kyle Journal of Materials Chemistry A, Vol. 4, Issue 8 https://doi.org/10.1039/c5ta06678f	journal	January 2016
Charge injection into nanostructured TiO ₂ electrodes from the photogenerated reduced form of a new Ru( ii ) polypyridine compound: the “anti-biomimetic” mechanism at work Ronconi, Federico; Santoni, Marie-Pierre; Nastasi, Francesco Dalton Transactions, Vol. 45, Issue 36 https://doi.org/10.1039/c6dt01970f	journal	January 2016
Long-lived charge separation in dye–semiconductor assemblies: a pathway to multi-electron transfer reactions Sundin, Elin; Abrahamsson, Maria Chemical Communications, Vol. 54, Issue 42 https://doi.org/10.1039/c8cc01071d	journal	January 2018
Production of solar chemicals: gaining selectivity with hybrid molecule/semiconductor assemblies Hennessey, Seán; Farràs, Pau Chemical Communications, Vol. 54, Issue 50 https://doi.org/10.1039/c8cc02487a	journal	January 2018
Core–shell structured titanium dioxide nanomaterials for solar energy utilization Li, Wei; Elzatahry, Ahmed; Aldhayan, Dhaifallah Chemical Society Reviews, Vol. 47, Issue 22 https://doi.org/10.1039/c8cs00443a	journal	January 2018
Dinuclear metal complexes: multifunctional properties and applications Li, Guangfu; Zhu, Dongxia; Wang, Xinlong Chemical Society Reviews, Vol. 49, Issue 3 https://doi.org/10.1039/c8cs00660a	journal	January 2020
Dye sensitized photoelectrolysis cells Yun, Sining; Vlachopoulos, Nick; Qurashi, Ahsanulhaq Chemical Society Reviews, Vol. 48, Issue 14 https://doi.org/10.1039/c8cs00987b	journal	January 2019
Light-driven water oxidation by a dye-sensitized photoanode with a chromophore/catalyst assembly on a mesoporous double-shell electrode Liu, Qing; Wang, Degao; Shan, Bing The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5048780	journal	January 2019
Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems Katsoukis, Georgios; Frei, Heinz The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5052453	journal	January 2019
Barriers for interfacial back-electron transfer: A comparison between TiO ₂ and SnO ₂ /TiO ₂ core/shell structures Troian-Gautier, Ludovic; Sampaio, Renato N.; Piechota, Eric J. The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5054604	journal	January 2019
Solar photothermochemical alkane reverse combustion Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H. Proceedings of the National Academy of Sciences, Vol. 113, Issue 10 https://doi.org/10.1073/pnas.1516945113	journal	February 2016
Stabilized photoanodes for water oxidation by integration of organic dyes, water oxidation catalysts, and electron-transfer mediators Wang, Degao; Eberhart, Michael S.; Sheridan, Matthew V. Proceedings of the National Academy of Sciences, Vol. 115, Issue 34 https://doi.org/10.1073/pnas.1802903115	journal	August 2018
Dye-sensitized photoelectrochemical water oxidation through a buried junction Xu, Pengtao; Huang, Tian; Huang, Jianbin Proceedings of the National Academy of Sciences, Vol. 115, Issue 27 https://doi.org/10.1073/pnas.1804728115	journal	June 2018
Titanium dioxide thin films by atomic layer deposition: a review Niemelä, Janne-Petteri; Marin, Giovanni; Karppinen, Maarit Semiconductor Science and Technology, Vol. 32, Issue 9 https://doi.org/10.1088/1361-6641/aa78ce	journal	August 2017
Inorganic Photochemistry and Solar Energy Harvesting: Current Developments and Challenges to Solar Fuel Production Sousa, Sinval F.; Souza, Breno L.; Barros, Cristiane L. International Journal of Photoenergy, Vol. 2019 https://doi.org/10.1155/2019/9624092	journal	January 2019
Electronic Properties of Electron-Deficient Zn(II) Porphyrins for HBr Splitting Berardi, Serena; Caramori, Stefano; Benazzi, Elisabetta Applied Sciences, Vol. 9, Issue 13 https://doi.org/10.3390/app9132739	journal	July 2019

Similar Records

Solar water splitting in a molecular photoelectrochemical cell

Patent · Mon Nov 05 23:00:00 EST 2018 · OSTI ID:1493296

Light-Driven Water Splitting by a Covalently Linked Ruthenium-Based Chromophore–Catalyst Assembly

Journal Article · Thu Dec 08 19:00:00 EST 2016 · ACS Energy Letters · OSTI ID:1349575

Chromophore-Catalyst Assembly for Water Oxidation Prepared by Atomic Layer Deposition

Journal Article · Sun Oct 15 20:00:00 EDT 2017 · ACS Applied Materials and Interfaces · OSTI ID:1469971

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (heterogeneous)
catalysis (homogeneous)
charge transport
electrodes - solar
hydrogen and fuel cells
materials and chemistry by design
photosynthesis (natural and artificial)
solar (fuels)
solar (photovoltaic)
synthesis (novel materials)
synthesis (self-assembly)