Molecular Metallocorrole–Nanorod Photocatalytic System for Sustainable Hydrogen Production

Dong, Kaituo; Le, Trung‐Anh; Nakibli, Yifat; Schleusener, Alexander; Wächtler, Maria; Amirav, Lilac

doi:10.1002/cssc.202201525

Cited by 13 publications

(6 citation statements)

References 41 publications

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“…CdS-based NRs have also shown promise for photochemical applications. In particular, NR-metal heterostructures have shown "perfect" photon to H 2 conversion efficiencies 49 as well as a complete redox catalytic cycle including water splitting, 39 hydrogen peroxide formation, 450 and the oxidative synthesis of organic compounds. 61 These examples illustrate the progress toward applications after two decades of research into colloidal NRs.…”

Section: Discussionmentioning

confidence: 99%

“…This was a major breakthrough in using CdS-based NCs for catalysis, as sacrificial hole scavenging was replaced by a highly desirable and extremely challenging water oxidation reaction. Advances in using metal tipped CdSe/CdS DiRs continue with strategies to combine hydrogen evolution at the metal tip with oxidative chemistry at the surface or at a catalyst. , …”

Section: Charge Transfer From Photoexcited Nrs and Light-driven Chemi...mentioning

confidence: 99%

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Electronic Structure and Excited State Dynamics of Cadmium Chalcogenide Nanorods

et al. 2023

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The cylindrical quasi-one-dimensional shape of colloidal semiconductor nanorods (NRs) gives them unique electronic structure and optical properties. In addition to the band gap tunability common to nanocrystals, NRs have polarized light absorption and emission and high molar absorptivities. NR-shaped heterostructures feature control of electron and hole locations as well as light emission energy and efficiency. We comprehensively review the electronic structure and optical properties of Cd-chalcogenide NRs and NR heterostructures (e.g., CdSe/CdS dot-in-rods, CdSe/ZnS rod-in-rods), which have been widely investigated over the last two decades due in part to promising optoelectronic applications. We start by describing methods for synthesizing these colloidal NRs. We then detail the electronic structure of single-component and heterostructure NRs and follow with a discussion of light absorption and emission in these materials. Next, we describe the excited state dynamics of these NRs, including carrier cooling, carrier and exciton migration, radiative and nonradiative recombination, multiexciton generation and dynamics, and processes that involve trapped carriers. Finally, we describe charge transfer from photoexcited NRs and connect the dynamics of these processes with light-driven chemistry. We end with an outlook that highlights some of the outstanding questions about the excited state properties of Cd-chalcogenide NRs.

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Section: Discussionmentioning

confidence: 99%

Section: Charge Transfer From Photoexcited Nrs and Light-driven Chemi...mentioning

confidence: 99%

Electronic Structure and Excited State Dynamics of Cadmium Chalcogenide Nanorods

et al. 2023

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“…This observation could be related to the prevention of charge carrier recombination by efficient hole quenching on the one hand, and prolonging the stability of the nanostructure by preventing photodegradation on the other hand. The photon-to-hydrogen conversion efficiency is often limited by hole scavenging and the use of an additional hydroxyl anion-radical redox shuttle has been shown to efficiently remove the hole out of the photocatalyst and give a record 100% photon-to-hydrogen generation efficiency [56,61,62].…”

Section: Introductionmentioning

confidence: 99%

Unravelling Dynamics Involving Multiple Charge Carriers in Semiconductor Nanocrystals

Kumar

Wächtler²

2023

Nanomaterials

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The use of colloidal nanocrystals as part of artificial photosynthetic systems has recently gained significant attention, owing to their strong light absorption and highly reproducible, tunable electronic and optical properties. The complete photocatalytic conversion of water to its components is yet to be achieved in a practically suitable and commercially viable manner. To complete this challenging task, we are required to fully understand the mechanistic aspects of the underlying light-driven processes involving not just single charge carriers but also multiple charge carriers in detail. This review focuses on recent progress in understanding charge carrier dynamics in semiconductor nanocrystals and the influence of various parameters such as dimension, composition, and cocatalysts. Transient absorption spectroscopic studies involving single and multiple charge carriers, and the challenges associated with the need for accumulation of multiple charge carriers to drive the targeted chemical reactions, are discussed.

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“…Corrole complexes, or metallocorroles, have been synthesized with a wide variety of transition metals and are of interest for their ability to catalyze hydrogen evolution reactions, − oxygen evolution reactions, , and oxygen reduction reactions. − Metallocorroles also have diverse applications in other areas of molecular catalysis, − small molecule sensing, − and in medicinal applications. − In addition to the highly functionalized hang-man corroles designed to play a more specialized role in catalysis, − substituting metallocorroles in the meso and β positions can significantly alter their reactivities. ,, The formally trianionic corrole can bind transition metals in the +3 oxidation state; however, both experimental and computational work supports ligand noninnocence in copper corroles, where researchers have assigned the electronic structure as formally Cu(II)(corrole • ). − This behavior has been rationalized as an electron transfer from the corrole ligand π orbitals to copper 3d orbitals, resulting in a corrole radical dianion and a reduced metal center. ,, The ligand-to-metal charge transfer is thought to play a significant role in governing the molecular geometries of copper corroles where the radical character in copper corroles is suggested to be the leading factor driving the formation of the characteristic saddled molecular geometry . This saddled structure is not commonly observed in other metallocorrole systems where ligand noninnocence is not reported. ,,− …”

Section: Introductionmentioning

confidence: 99%

Molecular Geometry and Electronic Structure of Copper Corroles

Bhowmick,

Roy Chowdhury,

Vlaisavljevich

2023

Inorg. Chem.

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Copper corroles are known for their unique multiconfigurational electronic structures in the ground state, which arise from the transfer of electrons from the π orbitals of the corrole to the d-orbital of copper. While density functional theory (DFT) provides reasonably good molecular geometries, the determination of the ground spin state and the associated energetics is heavily influenced by functional choice, particularly the percentage of the Hartree–Fock exchange. Using extended multireference perturbation theory methods (XMS-CASPT2), the functional choice can be assessed. The molecular geometries and electronic structures of both the unsubstituted and the meso-triphenyl copper corroles were investigated. A minimal active space was employed for structural characterization, while larger active spaces are required to examine the electronic structure. The XMS-CASPT2 investigations conclusively identify the ground electronic state as a multiconfigurational singlet (S0) with three dominant electronic configurations in its lowest energy and characteristic saddled structure. In contrast, the planar geometry corresponds to the triplet state (T0), which is approximately 5 kcal/mol higher in energy compared to the S0 state for both the bare and substituted copper corroles. Notably, the planarity of the T0 geometry is reduced in the substituted corrole compared with that in the unsubstituted one. By analyzing the potential energy surface (PES) between the S0 and T0 geometries using XMS-CASPT2, the multiconfigurational electronic structure is shown to transition toward a single electron configuration as the saddling angle decreases (i.e., as one approaches the planar geometry). Despite the ability of the functionals to reproduce the minimum energy structures, only the TPSSh-D3 PES is reasonably close to the XMS-CASPT2 surface. Significant deviations along the PES are observed with other functionals.

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Molecular Metallocorrole–Nanorod Photocatalytic System for Sustainable Hydrogen Production

Cited by 13 publications

References 41 publications

Electronic Structure and Excited State Dynamics of Cadmium Chalcogenide Nanorods

Electronic Structure and Excited State Dynamics of Cadmium Chalcogenide Nanorods

Unravelling Dynamics Involving Multiple Charge Carriers in Semiconductor Nanocrystals

Molecular Geometry and Electronic Structure of Copper Corroles

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