Photochemical CO2 Reduction Driven by Water-Soluble Copper(I) Photosensitizer with the Catalysis Accelerated by Multi-Electron Chargeable Cobalt Porphyrin

Xian Zhang, Mihaela Cibian, Arnau Call, Kosei Yamauchi, Ken Sakai

Research output: Contribution to journalArticle

Abstract

Without using precious elements, a highly efficient and selective molecular-based photocatalytic system for CO2-to-CO conversion in fully aqueous media has been developed. Our copper(I)-based water-soluble photosensitizer (CuPS) preserves its highly luminescent and long-lived excited state even in aqueous media. The CuPS-driven CO2 reduction catalyzed by a water-soluble cobalt porphyrin possessing four N-methylpyridinium acceptors at the meso positions (CoTMPyP) achieves the highest catalytic activity among those reported for aqueous systems: TONCO = 2680 and TOFCO max = 1600-2600 h-1 with SelCO2 = 77-90% (selectivity for CO vs H2). The observed photocatalytic enhancement is discussed in terms of the 6-electron chargeable character of CoTMPyP, permitting its rapid release of CO via reduction of CoII to CoI by intramolecular electron transfer from the reducing equivalent stored at one of the acceptors.

Original languageEnglish
Pages (from-to)11263-11273
Number of pages11
JournalACS Catalysis
DOIs
Publication statusAccepted/In press - Jan 1 2019

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Photosensitizing Agents
Photosensitizers
Porphyrins
Carbon Monoxide
Cobalt
Catalysis
Copper
Electrons
Water
Excited states
Catalyst activity
cobalt(III)meso-tetrakis(N-methylpyridinium-4-yl)porphyrin

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

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title = "Photochemical CO2 Reduction Driven by Water-Soluble Copper(I) Photosensitizer with the Catalysis Accelerated by Multi-Electron Chargeable Cobalt Porphyrin",
abstract = "Without using precious elements, a highly efficient and selective molecular-based photocatalytic system for CO2-to-CO conversion in fully aqueous media has been developed. Our copper(I)-based water-soluble photosensitizer (CuPS) preserves its highly luminescent and long-lived excited state even in aqueous media. The CuPS-driven CO2 reduction catalyzed by a water-soluble cobalt porphyrin possessing four N-methylpyridinium acceptors at the meso positions (CoTMPyP) achieves the highest catalytic activity among those reported for aqueous systems: TONCO = 2680 and TOFCO max = 1600-2600 h-1 with SelCO2 = 77-90{\%} (selectivity for CO vs H2). The observed photocatalytic enhancement is discussed in terms of the 6-electron chargeable character of CoTMPyP, permitting its rapid release of CO via reduction of CoII to CoI by intramolecular electron transfer from the reducing equivalent stored at one of the acceptors.",
author = "Xian Zhang and Mihaela Cibian and Arnau Call and Kosei Yamauchi and Ken Sakai",
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T1 - Photochemical CO2 Reduction Driven by Water-Soluble Copper(I) Photosensitizer with the Catalysis Accelerated by Multi-Electron Chargeable Cobalt Porphyrin

AU - Zhang, Xian

AU - Cibian, Mihaela

AU - Call, Arnau

AU - Yamauchi, Kosei

AU - Sakai, Ken

PY - 2019/1/1

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N2 - Without using precious elements, a highly efficient and selective molecular-based photocatalytic system for CO2-to-CO conversion in fully aqueous media has been developed. Our copper(I)-based water-soluble photosensitizer (CuPS) preserves its highly luminescent and long-lived excited state even in aqueous media. The CuPS-driven CO2 reduction catalyzed by a water-soluble cobalt porphyrin possessing four N-methylpyridinium acceptors at the meso positions (CoTMPyP) achieves the highest catalytic activity among those reported for aqueous systems: TONCO = 2680 and TOFCO max = 1600-2600 h-1 with SelCO2 = 77-90% (selectivity for CO vs H2). The observed photocatalytic enhancement is discussed in terms of the 6-electron chargeable character of CoTMPyP, permitting its rapid release of CO via reduction of CoII to CoI by intramolecular electron transfer from the reducing equivalent stored at one of the acceptors.

AB - Without using precious elements, a highly efficient and selective molecular-based photocatalytic system for CO2-to-CO conversion in fully aqueous media has been developed. Our copper(I)-based water-soluble photosensitizer (CuPS) preserves its highly luminescent and long-lived excited state even in aqueous media. The CuPS-driven CO2 reduction catalyzed by a water-soluble cobalt porphyrin possessing four N-methylpyridinium acceptors at the meso positions (CoTMPyP) achieves the highest catalytic activity among those reported for aqueous systems: TONCO = 2680 and TOFCO max = 1600-2600 h-1 with SelCO2 = 77-90% (selectivity for CO vs H2). The observed photocatalytic enhancement is discussed in terms of the 6-electron chargeable character of CoTMPyP, permitting its rapid release of CO via reduction of CoII to CoI by intramolecular electron transfer from the reducing equivalent stored at one of the acceptors.

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