Mapping the Ultrafast Mechanistic Pathways of Co Photocatalysts in Pure Water through Time‐Resolved X‐ray Spectroscopy

Velasco, Lucia; Liu, Cunming; Zhang, Xiaoyi; Grau, Sergi; Gil‐Sepulcre, Marcos; Gimbert‐Suriñach, Carolina; Picón, Antonio; Llobet, Antoni; DeBeer, Serena; Moonshiram, Dooshaye

doi:10.1002/cssc.202300719

Title: Mapping the Ultrafast Mechanistic Pathways of Co Photocatalysts in Pure Water through Time‐Resolved X‐ray Spectroscopy

Journal Article · Thu Aug 24 00:00:00 EDT 2023 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.202300719· OSTI ID:1996600

Velasco, Lucia ^[1]; Liu, Cunming ^[2]; Zhang, Xiaoyi ^[2]; Grau, Sergi ^[3]; Gil‐Sepulcre, Marcos ^[3]; Gimbert‐Suriñach, Carolina ^[4];

^[5]; Llobet, Antoni ^[4]; DeBeer, Serena ^[6];

^[1]

Instituto de Ciencia de Materiales de Madrid Consejo Superior de Investigaciones Científicas Sor Juana Inés de la Cruz, 3 28049 Madrid Spain
X-ray Science Division Argonne National Laboratory 9700 S. Cass Avenue Lemont IL 60439 U.S.A
Institute of Chemical Research of Catalonia (ICIQ) Avinguda Països Catalans 16 43007 Tarragona Spain
Institute of Chemical Research of Catalonia (ICIQ) Avinguda Països Catalans 16 43007 Tarragona Spain, Departament de Química Universitat Autònoma de Barcelona Cerdanyola del Vallès 08193 Barcelona Spain
Departamento de Química Universidad Autonoma de Madrid 28049 Madrid Spain
Max Planck Institute for Chemical Energy Conversion Stiftstr. 34–36 45470 Mülheim an der Ruhr Germany

Abstract Nanosecond time‐resolved X‐ray (tr‐XAS) and optical transient absorption spectroscopy (OTA) are applied to study 3 multimolecular photocatalytic systems with [Ru(bpy) ₃ ] ²⁺ photoabsorber, ascorbic acid electron donor and Co catalysts with methylene ( 1 ), hydroxomethylene ( 2 ) and methyl ( 3 ) amine substituents in pure water. OTA and tr‐XAS of 1 and 2 show that the favored catalytic pathway involves reductive quenching of the excited photosensitizer and electron transfer to the catalyst to form a Co ^II square pyramidal intermediate with a bonded aqua molecule followed by a Co ^I square planar derivative that decays within ≈8 μs. By contrast, a Co ^I square pyramidal intermediate with a longer decay lifetime of ≈35 μs is formed from an analogous Co ^II geometry for 3 in H ₂ O. These results highlight the protonation of Co ^I to form the elusive hydride species to be the rate limiting step and show that the catalytic rate can be enhanced through hydrogen containing pendant amines that act as H−H bond formation proton relays.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1996600

Alternate ID(s):: OSTI ID: 2008012; OSTI ID: 2228729

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Vol. 16 Journal Issue: 21; ISSN 1864-5631

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Co hydrogen evolution catalysts
Time-resolved x-ray absorption spectroscopy
TD-DFT calculations
Optical transient absorption spectroscopy

Title: Mapping the Ultrafast Mechanistic Pathways of Co Photocatalysts in Pure Water through Time‐Resolved X‐ray Spectroscopy

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