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dc.contributor.authorRodríguez-Jiménez, Santiago
dc.contributor.authorSong, Hongwei
dc.contributor.authorLam, Erwin
dc.contributor.authorWright, Demelza
dc.contributor.authorPannwitz, Andrea
dc.contributor.authorBonke, Shannon A
dc.contributor.authorBaumberg, Jeremy J
dc.contributor.authorBonnet, Sylvestre
dc.contributor.authorHammarström, Leif
dc.contributor.authorReisner, Erwin
dc.date.accessioned2022-05-04T23:30:18Z
dc.date.available2022-05-04T23:30:18Z
dc.date.issued2022-06-01
dc.identifier.issn0002-7863
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/336734
dc.description.abstractLight-driven conversion of CO2 to chemicals provides a sustainable alternative to fossil fuels, but homogeneous systems are typically limited by cross reactivity between different redox half reactions and inefficient charge separation. Herein, we present the bioinspired development of amphiphilic photosensitizer and catalyst pairs that self-assemble in lipid membranes to overcome some of these limitations and enable photocatalytic CO2 reduction in liposomes using precious metal-free catalysts. Using sodium ascorbate as a sacrificial electron source, a membrane-anchored alkylated cobalt porphyrin demonstrates higher catalytic CO production (1456 vs 312 turnovers) and selectivity (77 vs 11%) compared to its water-soluble nonalkylated counterpart. Time-resolved and steady-state spectroscopy revealed that self-assembly facilitates this performance enhancement by enabling a charge-separation state lifetime increase of up to two orders of magnitude in the dye while allowing for a ninefold faster electron transfer to the catalyst. Spectroelectrochemistry and density functional theory calculations of the alkylated Co porphyrin catalyst support a four-electron-charging mechanism that activates the catalyst prior to catalysis, together with key catalytic intermediates. Our molecular liposome system therefore benefits from membrane immobilization and provides a versatile and efficient platform for photocatalysis.
dc.publisherAmerican Chemical Society (ACS)
dc.rightsAll Rights Reserved
dc.rights.urihttp://www.rioxx.net/licenses/all-rights-reserved
dc.titleSelf-Assembled Liposomes Enhance Electron Transfer for Efficient Photocatalytic CO2 Reduction.
dc.typeArticle
dc.publisher.departmentDepartment of Chemistry
dc.date.updated2022-05-04T09:43:51Z
prism.publicationNameJ Am Chem Soc
dc.identifier.doi10.17863/CAM.84155
dcterms.dateAccepted2022-05-03
rioxxterms.versionofrecord10.1021/jacs.2c01725
rioxxterms.versionAM
dc.contributor.orcidRodríguez-Jiménez, Santiago [0000-0002-2979-8525]
dc.contributor.orcidSong, Hongwei [0000-0002-9439-7621]
dc.contributor.orcidLam, Erwin [0000-0002-8641-7928]
dc.contributor.orcidWright, Demelza [0000-0002-8854-2714]
dc.contributor.orcidPannwitz, Andrea [0000-0001-9633-0730]
dc.contributor.orcidBonke, Shannon A [0000-0002-3285-4356]
dc.contributor.orcidBaumberg, Jeremy J [0000-0002-9606-9488]
dc.contributor.orcidBonnet, Sylvestre [0000-0002-5810-3657]
dc.contributor.orcidHammarström, Leif [0000-0002-9933-9084]
dc.contributor.orcidReisner, Erwin [0000-0002-7781-1616]
dc.identifier.eissn1520-5126
rioxxterms.typeJournal Article/Review
pubs.funder-project-idEuropean Commission Horizon 2020 (H2020) Future and Emerging Technologies (FET) (828838)
pubs.funder-project-idEuropean Commission Horizon 2020 (H2020) Marie Sk?odowska-Curie actions (891338)
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/R020965/1)
pubs.funder-project-idEuropean Commission Horizon 2020 (H2020) ERC (883703)
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/P030467/1)
cam.issuedOnline2022-05-20
datacite.issupplementedby.urlhttps://doi.org/10.17863/CAM.84150
cam.orpheus.successWed Jun 08 08:57:17 BST 2022 - Embargo updated
cam.orpheus.counter1
cam.depositDate2022-05-04
pubs.licence-identifierapollo-deposit-licence-2-1
pubs.licence-display-nameApollo Repository Deposit Licence Agreement
rioxxterms.freetoread.startdate2023-05-20


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