Feeble Single-Atom Pd Catalysts for H2 Production from Formic Acid

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dc.authoridToyao, Takashi/0000-0002-6062-5622
dc.authoridFull name: Esmaeil Doust Khah Heragh, Esmail Doustkhah/0000-0003-1459-1756
dc.authoridMine, Shinya/0000-0002-8339-0301
dc.authoridIde, Yusuke/0000-0002-6901-6954
dc.authoridShimizu, Ken-ichi/0000-0003-0501-0294
dc.authorwosidToyao, Takashi/AAR-1841-2020
dc.authorwosidFull name: Esmaeil Doust Khah Heragh, Esmail Doustkhah/I-7553-2014
dc.authorwosidMine, Shinya/HTS-9265-2023
dc.authorwosidTsunoji, Nao/A-2627-2013
dc.authorwosidIde, Yusuke/B-9547-2013
dc.authorwosidShimizu, Ken-ichi/A-5241-2012
dc.contributor.authorDoustkhah, Esmail
dc.contributor.authorTsunoji, Nao
dc.contributor.authorMine, Shinya
dc.contributor.authorToyao, Takashi
dc.contributor.authorShimizu, Ken-ichi
dc.contributor.authorMorooka, Tetsuro
dc.contributor.authorMasuda, Takuya
dc.date.accessioned2024-05-19T14:46:40Z
dc.date.available2024-05-19T14:46:40Z
dc.date.issued2024
dc.departmentİstinye Üniversitesien_US
dc.description.abstractSingle-atom catalysts are thought to be the pinnacle of catalysis. However, for many reactions, their suitability has yet to be unequivocally proven. Here, we demonstrate why single Pd atoms (Pd-SA) are not catalytically ideal for generating H-2 from formic acid as a H-2 carrier. We loaded Pd-SA on three silica substrates, mesoporous silicas functionalized with thiol, amine, and dithiocarbamate functional groups. The Pd catalytic activity on amino-functionalized silica (SiO2-NH2/Pd-SA) was far higher than that of the thiol-based catalysts (SiO2-S-Pd-SA and SiO2-NHCS2-Pd-SA), while the single-atom stability of SiO2-NH2/Pd-SA against aggregation after the first catalytic cycle was the weakest. In this case, Pd aggregation boosted the reaction yield. Our experiments and calculations demonstrate that Pd-SA in SiO2-NH2/Pd-SA loosely binds with amine groups. This leads to a limited charge transfer from Pd to the amine groups and causes high aggregability and catalytic activity. According to the density functional calculations, the loose binding between Pd and N causes most of Pd's 4d electrons in amino-functionalized SiO2 to remain close to the Fermi level and labile for catalysis. However, Pd-SA chemically binds to the thiol group, resulting in strong hybridization between Pd and S, pulling Pd's 4d states deeper into the conduction band and away from the Fermi level. Consequently, fewer 4d electrons were available for catalysis.en_US
dc.description.sponsorshipHORIZON EUROPE Marie Sklodowska-Curie Actions [21H02034]; JSPS KAKENHI [2022A1827]; Joint Usage/Research Center for Catalysis [120C057]; Brain Circulation Programen_US
dc.description.sponsorshipThis work was supported by JSPS KAKENHI (Grant Numbers 21H02034). This work was also supported by the Joint Usage/Research Center for Catalysis. The XAS measurements were performed at BL14B2 of SPring-8 (proposal No. 2022A1827). E.D. acknowledges the TUBITAK and Horizon-2020 Marie Sk & lstrok;odowska Curie for providing financial support in Co-Funded Brain Circulation Program (Project No. 120C057) framework. We also acknowledge the Scivisional illustration team for their contribution to designing the front cover image.en_US
dc.identifier.doi10.1021/acsami.3c18709
dc.identifier.endpage10259en_US
dc.identifier.issn1944-8244
dc.identifier.issn1944-8252
dc.identifier.issue8en_US
dc.identifier.pmid38241200en_US
dc.identifier.startpage10251en_US
dc.identifier.urihttps://doi.org10.1021/acsami.3c18709
dc.identifier.urihttps://hdl.handle.net/20.500.12713/5569
dc.identifier.volume16en_US
dc.identifier.wosWOS:001162249400001en_US
dc.identifier.wosqualityN/Aen_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.language.isoenen_US
dc.publisherAmer Chemical Socen_US
dc.relation.ispartofAcs Applied Materials & Interfacesen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.snmz20240519_kaen_US
dc.subjectSingle-Atom Catalysis (Sac)en_US
dc.subjectPd Nanoclusteren_US
dc.subjectSilica-Supported Pden_US
dc.subjectPd Dosen_US
dc.subjectMetal-Supportinteractionen_US
dc.subjectCatalyst Reconstructionen_US
dc.subjectLigand-Metalcharge Transferen_US
dc.subjectDensity Functional Theory (Dft)en_US
dc.titleFeeble Single-Atom Pd Catalysts for H2 Production from Formic Aciden_US
dc.typeArticleen_US

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