Boosting CO2 photoreduction by π–π-induced preassembly between a Cu(I) sensitizer and a pyrene-appended Co(II) catalyst

Significance The sunlight-driven reduction of CO2 into products like CO, CH4, etc. can lower the atmospheric CO2 concentration and provide carbon-neutral energy simultaneously, attracting scientists to design photocatalytic systems to facilitate this process. The rational construction of noncovalent interactions between photosensitizers and catalysts may serve as a versatile strategy to boost catalytic efficiency by speeding up the electron transfer. Besides performance, it is also desirable to lower the expense by developing photocatalytic systems based on earth-abundant elements instead of precious metals. Herein, we present the proof of concept into a fully earth-abundant system by installing dynamic π–π interaction between a dual emissive, pyrene-decorated Cu(I) photosensitizer and a pyrene-appended Co(II) catalyst, achieving remarkable catalytic performance for visible-light–driven CO2 reduction.

[1]  K. Yamauchi,et al.  Controlling the Photofunctionality of a Polyanionic Heteroleptic Copper(I) Photosensitizer Using Its Ion-pair Formation with Polycationic Ammonium in Aqueous Media. , 2023, Angewandte Chemie.

[2]  T. Lian,et al.  Homoleptic Al(III) Photosensitizers for Durable CO2 Photoreduction. , 2022, Journal of the American Chemical Society.

[3]  Di-Chang Zhong,et al.  Dual electronic effects achieving a high-performance Ni(II) pincer catalyst for CO2 photoreduction in a noble-metal-free system , 2022, Proceedings of the National Academy of Sciences of the United States of America.

[4]  J. Peters,et al.  Mechanism of a Luminescent Dicopper System That Facilitates Electrophotochemical Coupling of Benzyl Chlorides via a Strongly Reducing Excited State. , 2022, ACS catalysis.

[5]  Yusuke Kuramochi,et al.  Photocatalytic CO2 reduction sensitized by a special-pair mimic porphyrin connected with a rhenium(i) tricarbonyl complex , 2022, Chemical science.

[6]  O. Ishitani,et al.  Utilization of Low-Concentration CO2 with Molecular Catalysts Assisted by CO2-Capturing Ability of Catalysts, Additives, or Reaction Media. , 2022, Journal of the American Chemical Society.

[7]  Gangfeng Ouyang,et al.  Co-facial π–π Interaction Expedites Sensitizer-to-Catalyst Electron Transfer for High-Performance CO2 Photoreduction , 2022, JACS Au.

[8]  Eric C. D. Tan,et al.  Early-stage evaluation of catalyst manufacturing cost and environmental impact using CatCost , 2022, Nature Catalysis.

[9]  Gangfeng Ouyang,et al.  CH-π interaction boosts photocatalytic CO2 reduction activity of a molecular cobalt catalyst anchored on carbon nitride , 2021, Cell Reports Physical Science.

[10]  O. Ishitani,et al.  Highly Functional Dinuclear CuI-Complex Photosensitizers for Photocatalytic CO2 Reduction , 2021, ACS Catalysis.

[11]  Liang‐Nian He,et al.  Prolonging the Triplet State Lifetimes of Rhenium Complexes with Imidazole-pyridine Framework for Efficient CO2 Photoreduction. , 2021, Chemistry.

[12]  K. Yamauchi,et al.  Earth-Abundant Photocatalytic CO2 Reduction by Multielectron Chargeable Cobalt Porphyrin Catalysts: High CO/H2 Selectivity in Water Based on Phase Mismatch in Frontier MO Association , 2021, ACS Catalysis.

[13]  M. Beller,et al.  Heteroleptic copper complexes with nitrogen and phosphorus ligands in photocatalysis: Overview and perspectives , 2021, Chem Catalysis.

[14]  K. Gordon,et al.  Excited-State Switching in Rhenium(I) Bipyridyl Complexes with Donor-Donor and Donor-Acceptor Substituents. , 2021, Journal of the American Chemical Society.

[15]  Long Jiang,et al.  Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore , 2021, Nature Communications.

[16]  M. Robert,et al.  Molecular Electrochemical Reduction of CO2 beyond Two Electrons , 2021 .

[17]  Long Jiang,et al.  Rapid electron transfer via dynamic coordinative interaction boosts quantum efficiency for photocatalytic CO2 reduction , 2021, Nature Communications.

[18]  Liang‐Nian He,et al.  A rhenium catalyst with bifunctional pyrene groups boosts natural light-driven CO2 reduction , 2020, Green Chemistry.

[19]  Pradipta Purkayastha,et al.  Unusually Large Singlet Oxygen (1 O2 ) Production by Very Weakly Emissive Pyrene-Functionalized Iridium(III) Complex: Interplay between Excited 3 ILCT/3 IL and 3 MLCT States , 2020 .

[20]  Shuang Yao,et al.  Facile electron delivery from graphene template to ultrathin metal-organic layers for boosting CO2 photoreduction , 2020, Nature communications.

[21]  C. J. McAdam,et al.  Excited-State Switching Frustrates the Tuning of Properties in Triphenylamine-Donor-Ligand Rhenium(I) and Platinum(II) Complexes. , 2020, Inorganic chemistry.

[22]  Chunhui Huang,et al.  Two‐Coordinate Copper(I)/NHC Complexes: Dual Emission Properties and Ultralong Room‐Temperature Phosphorescence , 2020, Angewandte Chemie.

[23]  Yusuke Kuramochi,et al.  Photocatalytic CO2 Reduction Mediated by Electron Transfer via Excited Triplet State of Zn(II) Porphyrin. , 2019, Journal of the American Chemical Society.

[24]  K. Yamauchi,et al.  Photochemical CO2 Reduction Driven by Water-Soluble Copper(I) Photosensitizer with the Catalysis Accelerated by Multi-Electron Chargeable Cobalt Porphyrin , 2019, ACS Catalysis.

[25]  C. Kubiak,et al.  Improving Photocatalysis for the Reduction of CO2 through non-Covalent Supramolecular Assembly. , 2019, Journal of the American Chemical Society.

[26]  Hai-Hua Huang,et al.  A Molecular Cobalt Hydrogen Evolution Catalyst Showing High Activity and Outstanding Tolerance to CO and O 2 , 2019, Angewandte Chemie.

[27]  J. Guthmuller,et al.  Effect of the Catalytic Center on the Electron Transfer Dynamics in Hydrogen-Evolving Ruthenium-Based Photocatalysts Investigated by Theoretical Calculations , 2019, The Journal of Physical Chemistry C.

[28]  O. Reiser,et al.  Copper’s rapid ascent in visible-light photoredox catalysis , 2019, Science.

[29]  E. Reisner,et al.  Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes , 2019, Chemical reviews.

[30]  R. Haiges,et al.  Eliminating nonradiative decay in Cu(I) emitters: >99% quantum efficiency and microsecond lifetime , 2019, Science.

[31]  R. Ludwig,et al.  Selective Earth-Abundant System for CO2 Reduction: Comparing Photo- and Electrocatalytic Processes , 2019, ACS Catalysis.

[32]  O. Ishitani,et al.  Highly Efficient and Robust Photocatalytic Systems for CO2 Reduction Consisting of a Cu(I) Photosensitizer and Mn(I) Catalysts. , 2018, Journal of the American Chemical Society.

[33]  Tongbu Lu,et al.  Robust and Long-Lived Excited State Ru(II) Polyimine Photosensitizers Boost Hydrogen Production , 2018, ACS Catalysis.

[34]  J. Guthmuller,et al.  Theoretical Investigation of the Electron-Transfer Dynamics and Photodegradation Pathways in a Hydrogen-Evolving Ruthenium-Palladium Photocatalyst. , 2018, Chemistry.

[35]  Xiaoyi Zhang,et al.  Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy. , 2018, Chemistry.

[36]  S. Gräfe,et al.  An artificial photosynthetic system for photoaccumulation of two electrons on a fused dipyridophenazine (dppz)–pyridoquinolinone ligand† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc04348a , 2018, Chemical science.

[37]  K. Onda,et al.  Investigation of excited state, reductive quenching, and intramolecular electron transfer of Ru(ii)–Re(i) supramolecular photocatalysts for CO2 reduction using time-resolved IR measurements† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc05338j , 2018, Chemical science.

[38]  O. Wenger,et al.  Photoredox Catalysis with Metal Complexes Made from Earth-Abundant Elements. , 2018, Chemistry.

[39]  B. Dietzek,et al.  Heteroleptic diimine–diphosphine Cu(I) complexes as an alternative towards noble-metal based photosensitizers: Design strategies, photophysical properties and perspective applications , 2018 .

[40]  T. Lu,et al.  Nickel complexes as molecular catalysts for water splitting and CO2 reduction , 2017, Coordination Chemistry Reviews.

[41]  S. Gräfe,et al.  Photochemistry and Electron Transfer Kinetics in a Photocatalyst Model Assessed by Marcus Theory and Quantum Dynamics , 2017 .

[42]  M. Beller,et al.  Earth-abundant photocatalytic systems for the visible-light-driven reduction of CO2 to CO , 2017 .

[43]  M. Beller,et al.  Heteroleptic Copper Photosensitizers: Why an Extended π-System Does Not Automatically Lead to Enhanced Hydrogen Production. , 2017, Chemistry.

[44]  S. Gräfe,et al.  Synthesis of three series of ruthenium tris-diimine complexes containing acridine-based π-extended ligands using an efficient "chemistry on the complex" approach. , 2016, Dalton transactions.

[45]  Claudio Cometto,et al.  Highly Efficient and Selective Photocatalytic CO2 Reduction by Iron and Cobalt Quaterpyridine Complexes. , 2016, Journal of the American Chemical Society.

[46]  O. Ishitani,et al.  Photocatalytic CO2 Reduction Using Cu(I) Photosensitizers with a Fe(II) Catalyst. , 2016, Journal of the American Chemical Society.

[47]  M. W. George,et al.  Comparison of rhenium–porphyrin dyads for CO2 photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy , 2015, Chemical science.

[48]  M. Robert,et al.  Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center. , 2015, Journal of the American Chemical Society.

[49]  M. O. Wolf,et al.  Tuning the emission lifetime in bis-cyclometalated iridium(III) complexes bearing iminopyrene ligands. , 2014, Inorganic chemistry.

[50]  R. Ludwig,et al.  Death and Rebirth: Photocatalytic Hydrogen Production by a Self-Organizing Copper–Iron System , 2014 .

[51]  E. Vauthey,et al.  Bimolecular photoinduced electron transfer beyond the diffusion limit: the Rehm-Weller experiment revisited with femtosecond time resolution. , 2014, Journal of the American Chemical Society.

[52]  Robie A. Hennigar,et al.  Exploitation of long-lived 3IL excited states for metal-organic photodynamic therapy: verification in a metastatic melanoma model. , 2013, Journal of the American Chemical Society.

[53]  Nicola Armaroli,et al.  Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands. , 2013, Inorganic chemistry.

[54]  O. Ishitani,et al.  Substantial improvement in the efficiency and durability of a photocatalyst for carbon dioxide reduction using a benzoimidazole derivative as an electron donor , 2013 .

[55]  M. Beller,et al.  Photocatalytic water reduction with copper-based photosensitizers: a noble-metal-free system. , 2013, Angewandte Chemie.

[56]  S. Bernhard,et al.  Orchestrated photocatalytic water reduction using surface-adsorbing iridium photosensitizers. , 2011, Journal of the American Chemical Society.

[57]  A. Yu,et al.  Hydride, hydrogen atom, proton, and electron transfer driving forces of various five-membered heterocyclic organic hydrides and their reaction intermediates in acetonitrile. , 2008, Journal of the American Chemical Society.

[58]  Su Ho Kim,et al.  Fluorescence ratiometry of monomer/excimer emissions in a space-through PET system. , 2005, The Journal of organic chemistry.

[59]  Wenxing Yang,et al.  Impaired conjugation boosts CO2 electroreduction by Ni(II) macrocyclic catalysts immobilized on carbon nanotubes , 2023, Journal of Materials Chemistry A.

[60]  K. Onda,et al.  xcited state , reductive quenching , and intramolecular electron transfer of Ru ( II ) – Re ( I ) supramolecular photocatalysts for CO 2 reduction using time-resolved IR measurements † , 2017 .

[61]  O. Ishitani,et al.  Highly efficient visible-light-driven CO2 reduction to CO using a Ru(II)–Re(I) supramolecular photocatalyst in an aqueous solution , 2016 .

[62]  N. Armaroli.  Photoactive mono- and polynuclear Cu(I)–phenanthrolines. A viable alternative to Ru(II)–polypyridines? , 2001 .

[63]  Zane L. Berge,et al.  Overview and perspectives , 1995 .

[64]  Highly Functional Dinuclear CuIComplex Photosensitizers for Photocatalytic CO2 Reduction , 2022 .