Photocatalytic Aqueous CO2Reduction to CO and CH4Sensitized by Ullazine Supramolecular Polymers

Oliver Dumele; Luka Dordević; Hiroaki Sai; Thomas J. Cotey; M. Hussain Sangji; Kohei Sato; Adam J. Dannenhoffer; Samuel I. Stupp

doi:10.1021/jacs.1c12155

Photocatalytic Aqueous CO₂Reduction to CO and CH₄Sensitized by Ullazine Supramolecular Polymers

Oliver Dumele, Luka Dordević, Hiroaki Sai, Thomas J. Cotey, M. Hussain Sangji, Kohei Sato, Adam J. Dannenhoffer, Samuel I. Stupp^*

^*Corresponding author for this work

Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

54 Scopus citations

Abstract

There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO₂reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO₂photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH₄comparable to those obtained with a precious metal-based [Ru(phen)₃](PF₆)₂sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. The present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.

Original language	English (US)
Pages (from-to)	3127-3136
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	144
Issue number	7
DOIs	https://doi.org/10.1021/jacs.1c12155
State	Published - Feb 23 2022

Funding

This work was supported by the Center for Bio-Inspired Energy Science (CBES), an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0000989. O.D. acknowledges funding by the Swiss National Science Foundation (SNF, Project P2EZP2_168881) via an Early Postdoc.Mobility fellowship and the National Academy of Sciences Leopoldina (Germany) for a postdoctoral fellowship (Grant LPDS 2016-4). Use of the Advanced Photon Source (APS) was supported by the Basic Energy Sciences program of the U.S. Department of Energy Office of Science under Contract DE-AC02-06CH11357. Angle-dependent X-ray experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS. DND-CAT is supported by Northwestern University, E. I. DuPont de Nemours & Co., and the Dow Chemical Company. We thank the Biological Imaging Facility at Northwestern for the use of TEM equipment and the Electron Probe Instrumentation Center facilities of the Northwestern University Atomic and Nanoscale Characterization Experimental Center for the use of TEM and SEM equipment. Single-crystal X-ray diffraction, NMR spectroscopy, and mass spectrometry equipment at the Integrated Molecular Structure Education and Research Center was supported by the National Science Foundation under Grant CHE-9871268. We thank Charlotte Stern for crystallographic advice. The authors also thank Mark Seniw for his help in preparing the schematics used in the manuscript.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/jacs.1c12155

Cite this

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abstract = "There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO2reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO2photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH4comparable to those obtained with a precious metal-based [Ru(phen)3](PF6)2sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. The present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.",

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AU - Stupp, Samuel I.

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N2 - There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO2reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO2photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH4comparable to those obtained with a precious metal-based [Ru(phen)3](PF6)2sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. The present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.

AB - There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO2reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO2photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH4comparable to those obtained with a precious metal-based [Ru(phen)3](PF6)2sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. The present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.

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Photocatalytic Aqueous CO₂Reduction to CO and CH₄Sensitized by Ullazine Supramolecular Polymers

Abstract

Funding

ASJC Scopus subject areas

UN SDGs

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CCDC 1878608: Experimental Crystal Structure Determination

CCDC 1878616: Experimental Crystal Structure Determination

CCDC 1878609: Experimental Crystal Structure Determination

Cite this

Photocatalytic Aqueous CO2Reduction to CO and CH4Sensitized by Ullazine Supramolecular Polymers

Abstract

Funding

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1878608: Experimental Crystal Structure Determination

CCDC 1878616: Experimental Crystal Structure Determination

CCDC 1878609: Experimental Crystal Structure Determination

Cite this

Photocatalytic Aqueous CO₂Reduction to CO and CH₄Sensitized by Ullazine Supramolecular Polymers