Aqueous Photoelectrochemical CO 2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

Shang, Bo; Rooney, Conor L.; Gallagher, David J.; Wang, Bernie T.; Krayev, Andrey; Shema, Hadar; Leitner, Oliver; Harmon, Nia J.; Xiao, Langqiu; Sheehan, Colton; Bottum, Samuel R.; Gross, Elad; Cahoon, James F.; Mallouk, Thomas E.; Wang, Hailiang

doi:10.1002/ange.202215213

Aqueous Photoelectrochemical CO ₂ Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

Journal Article · Mon Dec 19 23:00:00 EST 2022 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202215213· OSTI ID:1905917

Shang, Bo ^[1]; Rooney, Conor L. ^[1]; Gallagher, David J. ^[1]; Wang, Bernie T. ^[1]; Krayev, Andrey ^[2]; Shema, Hadar ^[3]; Leitner, Oliver ^[1]; Harmon, Nia J. ^[1]; Xiao, Langqiu ^[4]; Sheehan, Colton ^[4]; Bottum, Samuel R. ^[5]; Gross, Elad ^[3]; Cahoon, James F. ^[5]; Mallouk, Thomas E. ^[4]; ^[1]

Department of Chemistry Yale University New Haven CT 06520 USA, Energy Sciences Institute Yale University West Haven CT 06516 USA
HORIBA Instruments Inc. 359 Bel Marin Keys Blvd, Suite 18 Novato CA 94949 USA
Institute of Chemistry and Center for Nanoscience and Nanotechnology Hebrew University of Jerusalem Jerusalem 91904 Israel
Department of Chemistry University of Pennsylvania Philadelphia PA 19104 USA
Department of Chemistry University of North Carolina at Chapel Hill Chapel Hill NC 27599-3290 USA

Abstract

We report a precious‐metal‐free molecular catalyst‐based photocathode that is active for aqueous CO ₂ reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3‐aminopropyl)triethoxysilane linker to p‐type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO ₂ to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of −0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s ⁻¹ . To date, this is the only molecular catalyst‐based photoelectrode that is active for the six‐electron reduction of CO ₂ to methanol. This work puts forth a strategy for interfacing molecular catalysts to p‐type semiconductors and demonstrates state‐of‐the‐art performance for photoelectrochemical CO ₂ reduction to CO and methanol.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0021173

OSTI ID:: 1905917

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 4 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (32)

The Development of Cocatalysts for Photoelectrochemical CO ₂ Reduction Chang, Xiaoxia; Wang, Tuo; Yang, Piaoping Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201804710	journal	December 2018
Powering the World with Solar Fuels from Photoelectrochemical CO ₂ Reduction: Basic Principles and Recent Advances Li, Deng; Yang, Kaixin; Lian, Juhong Advanced Energy Materials, Vol. 12, Issue 31 https://doi.org/10.1002/aenm.202201070	journal	June 2022
Aqueous CO₂ Reduction on Si Photocathodes Functionalized by Cobalt Molecular Catalysts/Carbon Nanotubes Wen, Zhibing; Xu, Suxian; Zhu, Yong Angewandte Chemie, Vol. 134, Issue 24 https://doi.org/10.1002/ange.202201086	journal	March 2022
Aqueous CO ₂ Reduction on Si Photocathodes Functionalized by Cobalt Molecular Catalysts/Carbon Nanotubes Wen, Zhibing; Xu, Suxian; Zhu, Yong Angewandte Chemie International Edition, Vol. 61, Issue 24 https://doi.org/10.1002/anie.202201086	journal	March 2022
Solar Fuels: Photoelectrosynthesis of CO from CO ₂ at p-Type Si using Fe Porphyrin Electrocatalysts Alenezi, Khalaf; Ibrahim, Saad K.; Li, Peiyi Chemistry - A European Journal, Vol. 19, Issue 40 https://doi.org/10.1002/chem.201300764	journal	August 2013
Dealloyed Nanoporous Materials for Rechargeable Post‐Lithium Batteries Wu, Xuan; He, Guang; Ding, Yi ChemSusChem, Vol. 13, Issue 13 https://doi.org/10.1002/cssc.202001369	journal	June 2020
Efficient photoelectrocatalytic CO2 reduction by cobalt complexes at silicon electrode Chen, Liangfeng; Wang, Zhuo; Kang, Peng Chinese Journal of Catalysis, Vol. 39, Issue 3 https://doi.org/10.1016/S1872-2067(17)62993-0	journal	March 2018
Progress of porous silicon APTES-functionalization by FTIR investigations Majoul, N.; Aouida, S.; Bessaïs, B. Applied Surface Science, Vol. 331 https://doi.org/10.1016/j.apsusc.2015.01.107	journal	March 2015
A review on progress and perspective of molecular catalysis in photoelectrochemical reduction of CO2 Nandal, Neha; Jain, Suman L. Coordination Chemistry Reviews, Vol. 451 https://doi.org/10.1016/j.ccr.2021.214271	journal	January 2022
Heterogeneous Molecular Catalysts of Metal Phthalocyanines for Electrochemical CO₂ Reduction Reactions Wu, Yueshen; Liang, Yongye; Wang, Hailiang Accounts of Chemical Research, Vol. 54, Issue 16 https://doi.org/10.1021/acs.accounts.1c00200	journal	August 2021
Theoretical Study on the Electro-Reduction of Carbon Dioxide to Methanol Catalyzed by Cobalt Phthalocyanine Shi, Le-Le; Li, Man; You, Bo Inorganic Chemistry, Vol. 61, Issue 42 https://doi.org/10.1021/acs.inorgchem.2c00739	journal	October 2022
A Close Look at the Structure of the TiO ₂ -APTES Interface in Hybrid Nanomaterials and Its Degradation Pathway: An Experimental and Theoretical Study Meroni, Daniela; Lo Presti, Leonardo; Di Liberto, Giovanni The Journal of Physical Chemistry C, Vol. 121, Issue 1 https://doi.org/10.1021/acs.jpcc.6b10720	journal	December 2016
Evolution of the Raman Spectrum with the Chemical Composition of Graphene Oxide López-Díaz, David; López Holgado, Marta; García-Fierro, José L. The Journal of Physical Chemistry C, Vol. 121, Issue 37 https://doi.org/10.1021/acs.jpcc.7b06236	journal	September 2017
Investigation of Cobalt Phthalocyanine at the Solid/Liquid Interface by Electrochemical Tip-Enhanced Raman Spectroscopy Jiang, Song; Chen, Zhu; Chen, Xu The Journal of Physical Chemistry C, Vol. 123, Issue 15 https://doi.org/10.1021/acs.jpcc.9b00513	journal	March 2019
Aggregation and Significant Difference in Reactivity Therein: Blocking the CO₂-to-CH₃OH Reaction Chen, Xiaoyu; Wei, Dongli; Ahlquist, Mårten S. G. Organometallics, Vol. 40, Issue 17 https://doi.org/10.1021/acs.organomet.1c00431	journal	August 2021
Electrocatalytic and Solar-Driven Reduction of Aqueous CO ₂ with Molecular Cobalt Phthalocyanine–Metal Oxide Hybrid Materials Roy, Souvik; Miller, Melanie; Warnan, Julien ACS Catalysis, Vol. 11, Issue 3 https://doi.org/10.1021/acscatal.0c04744	journal	January 2021
Selective Catalytic Electroreduction of CO ₂ at Silicon Nanowires (SiNWs) Photocathodes Using Non-Noble Metal-Based Manganese Carbonyl Bipyridyl Molecular Catalysts in Solution and Grafted onto SiNWs Torralba-Peñalver, Encarnación; Luo, Yun; Compain, Jean-Daniel ACS Catalysis, Vol. 5, Issue 10 https://doi.org/10.1021/acscatal.5b01546	journal	September 2015
Solar-Driven Photocatalytic CO ₂ Reduction in Water Utilizing a Ruthenium Complex Catalyst on p-Type Fe ₂ O ₃ with a Multiheterojunction Sekizawa, Keita; Sato, Shunsuke; Arai, Takeo ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03244	journal	January 2018
Monolayer Molecular Functionalization Enabled by Acid–Base Interaction for High-Performance Photochemical CO₂ Reduction Shang, Bo; Zhao, Fengyi; Choi, Chungseok ACS Energy Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acsenergylett.2c01147	journal	June 2022
Elucidating the Reactivity and Mechanism of CO ₂ Electroreduction at Highly Dispersed Cobalt Phthalocyanine Zhu, Minghui; Ye, Ruquan; Jin, Kyoungsuk ACS Energy Letters, Vol. 3, Issue 6 https://doi.org/10.1021/acsenergylett.8b00519	journal	May 2018
Stable Molecular Photocathode for Solar-Driven CO ₂ Reduction in Aqueous Solutions Li, Ting-Ting; Shan, Bing; Meyer, Thomas J. ACS Energy Letters, Vol. 4, Issue 3 https://doi.org/10.1021/acsenergylett.8b02512	journal	February 2019
Photoelectrochemical CO₂ Reduction toward Multicarbon Products with Silicon Nanowire Photocathodes Interfaced with Copper Nanoparticles Roh, Inwhan; Yu, Sunmoon; Lin, Chung-Kuan Journal of the American Chemical Society, Vol. 144, Issue 18 https://doi.org/10.1021/jacs.2c03702	journal	April 2022
Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures Zhang, Xing; Wu, Zishan; Zhang, Xiao Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14675	journal	March 2017
Stable solar water splitting with wettable organic-layer-protected silicon photocathodes Wu, Bo; Wang, Tuo; Liu, Bin Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32099-1	journal	August 2022
Binary molecular-semiconductor p–n junctions for photoelectrocatalytic CO2 reduction Shan, Bing; Vanka, Srinivas; Li, Ting-Ting Nature Energy, Vol. 4, Issue 4 https://doi.org/10.1038/s41560-019-0345-y	journal	March 2019
Domino electroreduction of CO2 to methanol on a molecular catalyst Wu, Yueshen; Jiang, Zhan; Lu, Xu Nature, Vol. 575, Issue 7784 https://doi.org/10.1038/s41586-019-1760-8	journal	November 2019
Solar-driven reduction of aqueous CO2 with a cobalt bis(terpyridine)-based photocathode Leung, Jane J.; Warnan, Julien; Ly, Khoa H. Nature Catalysis, Vol. 2, Issue 4 https://doi.org/10.1038/s41929-019-0254-2	journal	April 2019
Designing materials for electrochemical carbon dioxide recycling Ross, Michael B.; De Luna, Phil; Li, Yifan Nature Catalysis, Vol. 2, Issue 8 https://doi.org/10.1038/s41929-019-0306-7	journal	July 2019
Electrocatalytic conversion of carbon dioxide for the Paris goals Jordaan, Sarah M.; Wang, Chao Nature Catalysis, Vol. 4, Issue 11 https://doi.org/10.1038/s41929-021-00704-z	journal	November 2021
Tunable, light-assisted co-generation of CO and H ₂ from CO ₂ and H2O by Re(bipy-tbu)(CO) ₃ Cl and p-Si in non-aqueous medium Kumar, Bhupendra; Smieja, Jonathan M.; Sasayama, Alissa F. Chem. Commun., Vol. 48, Issue 2 https://doi.org/10.1039/C1CC16024A	journal	January 2012
Hybrid photocathode consisting of a CuGaO ₂ p-type semiconductor and a Ru( ii )–Re( i ) supramolecular photocatalyst: non-biased visible-light-driven CO ₂ reduction with water oxidation Kumagai, Hiromu; Sahara, Go; Maeda, Kazuhiko Chemical Science, Vol. 8, Issue 6 https://doi.org/10.1039/C7SC00940B	journal	January 2017
Solar-driven CO ₂ to CO reduction utilizing H ₂ O as an electron donor by earth-abundant Mn–bipyridine complex and Ni-modified Fe-oxyhydroxide catalysts activated in a single-compartment reactor Arai, Takeo; Sato, Shunsuke; Sekizawa, Keita Chemical Communications, Vol. 55, Issue 2 https://doi.org/10.1039/C8CC07900E	journal	January 2019

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Aqueous Photoelectrochemical CO₂ Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

Journal Article · Mon Nov 28 23:00:00 EST 2022 · Angewandte Chemie (International Edition) · OSTI ID:2377749

Aqueous Photoelectrochemical CO 2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

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Aqueous Photoelectrochemical CO ₂ Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst