Photoinduced interfacial charge separation dynamics in zeolitic imidazolate framework

Owing to their porous structure and tunable framework, zeolitic imidazolate frameworks (ZIFs) have garnered considerable attention as promising photocatalytic materials. However, little is known regarding their photophysical properties. In this work, we report the photoinduced charge separation dynamics in a ZIF-67 thin film through interfacial electron transfer (ET) to methylene blue (MB+) via ultrafast transient absorption spectroscopy. We show that the ET process occurs through two distinct pathways, including an ultrafast (\u3c200 fs) process from the [CoII(mim)2] units located on the surface of ZIF-67 film that are directly in contact with MB+ and a relatively slower ET process with a 101.4 ps time constant from the units in the bulk of the film that were isolated from MB+ by the surface units. This first direct evidence of the ET process from ZIF-67 to electron acceptor strongly suggests that ZIF materials may be used as intrinsic photocatalytic materials rather than inert hosts

The Effect of Mo Doping on The Charge Separation Dynamics and Photocurrent Performance of BiVO\u3csub\u3e4\u3c/sub\u3e Photoanodes

Doping with electron-rich elements in BiVO4 photoanodes has been demonstrated as a desirable approach for improving their carrier mobility and charge separation efficiency. However, the effect of doping and dopant concentration on the carrier dynamics and photoelectrochemical performance remains unclear. In this work, we examined the effects of Mo doping on the charge separation dynamics and photocurrent performance in BiVO4photoanodes. We show that the photocurrent of BiVO4 photoanodes increases with increasing concentration of the Mo dopant, which can be attributed to both the improved carrier mobility resulting from increased electron density and charge separation efficiency due to the diminishing of trap states upon Mo doping. The effect of doping on the electronic structure, carrier dynamics and photocurrent performance of BiVO4 photoanodes resulting from W and Mo dopants was also compared and discussed in this study. The knowledge gained from this work will provide important insights into the optimization of the carrier mobility and charge separation efficiency of BiVO4 photoanodes by controlling the dopants and their concentrations

Implicating the Contributions of Surface and Bulk States on Carrier Trapping and Photocurrent Performance of BiVO\u3csub\u3e4\u3c/sub\u3e Photoanodes

Monoclinic-scheelite BiVO4 has been widely studied as a promising oxygen evolution reaction (OER) catalyst in artificial photosynthesis. Though significant progress to improve or augment its catalysis performance has been made, fundamental understanding of its relatively poor performance as a bare material is lacking. In this paper, we report the correlation of the surface structure and trap states with charge separation efficiency and OER performance of bare BiVO4 photoanodes viavarying the sample thickness. Using X-ray absorption spectroscopy (XAS), we observed a more compacted, symmetric Bi center in the surface state. Using transient absorption (TA) spectroscopy, we show that the structural properties of the surface lead to shallow and deep hole trap states and electron trapping that occurs at the surface of the material. Despite more severe carrier trapping on the surface, our OER measurements demonstrate that a significant bulk structure is required for light absorption but is only beneficial until the carrier mobility becomes the limiting factor in photoelectrochemical cell studies

Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications

Zeolitic imidazolate frameworks (ZIFs) have emerged as a novel class of porous metal–organic frameworks (MOFs) for catalysis application because of their exceptional thermal and chemical stability. Inspired by the broad absorption of ZIF-67 in UV–vis-near IR region, we explored its excited state and charge separation dynamics, properties essential for photocatalytic applications, using optical (OTA) and X-ray transient absorption (XTA) spectroscopy. OTA results show that an exceptionally long-lived excited state is formed after photoexcitation. This long-lived excited state was confirmed to be the charge-separated (CS) state with ligand-to-metal charge-transfer character using XTA. The surprisingly long-lived CS state, together with its intrinsic hybrid nature, all point to its potential application in heterogeneous photocatalysis and energy conversion

Composition Effect on the Carrier Dynamics and Catalytic Performance of CuInS\u3csub\u3e2\u3c/sub\u3e/ZnS Quantum Dots for Light Driven Hydrogen Generation

Water soluble CuInS2/ZnS quantum dots (QDs) represent one of the most promising single component photocatalysts for the hydrogen evolution reaction (HER). In this work, we report the effect of cation composition in CuInS2/ZnS QDs on the carrier relaxation and charge separation dynamics as well as their photocatalytic performance for the HER. With decreasing Cu to In ratio (increasing Cu deficiency), we observed slightly faster electron trapping and carrier recombination but significantly improved photocatalytic activity for the HER. This can be attributed to the enhanced electron transfer (ET) from the sacrificial donor to CuInS2/ZnS QDs resulting from the lower valence band (larger driving force for ET) of QDs with higher Cu deficiency. This work not only provides important insight into the mechanistic origins of the HER but also demonstrated that altering the composition in CuInS2/ZnS QDs is a viable approach to further improve their performance for solar to fuel conversion

Unravelling the Correlation of Electronic Structure and Carrier Dynamics in CuInS\u3csub\u3e2\u3c/sub\u3e Nanoparticles

In this work, we report the direct correlation of photoinduced carrier dynamics and electronic structure of CuInS2 (CIS) nanoparticles (NPs) using the combination of multiple spectroscopic techniques including steady-state X-ray absorption spectroscopy (XAS), optical transient absorption (OTA), and X-ray transient (XTA) absorption spectroscopy. XAS results show that CIS NPs contain a large amount of surface Cu atoms with ≪four-coordination, which is more severe in CIS NPs with shorter nucleation times, indicating the presence of more Cu defect states in CIS NPs with smaller size particles. Using the combination of OTA and XTA spectroscopy, we show that electrons are trapped at states with mainly In or S nature while holes are trapped in sites characteristic of Cu. While there is no direct correlation of ultrafast trapping dynamics with NP nucleation time, charge recombination is significantly inhibited in CIS NPs with larger particles. These results suggest the key roles that Cu defect sites play in carrier dynamics and imply the possibility to control the carrier dynamics by controlling the surface structure at the Cu site in CIS NPs

Donor–Acceptor Fluorophores for Energy-Transfer-Mediated Photocatalysis

Triplet–triplet energy transfer (EnT) is a fundamental activation pathway in photocatalysis. In this work, we report the mechanistic origins of the triplet excited state of carbazole-cyanobenzene donor–acceptor (D–A) fluorophores in EnT-based photocatalytic reactions and demonstrate the key factors that control the accessibility of the 3LE (locally excited triplet state) and 3CT (charge-transfer triplet state) via a combined photochemical and transient absorption spectroscopic study. We found that the energy order between 1CT (charge transfer singlet state) and 3LE dictates the accessibility of 3LE/3CT for EnT, which can be effectively engineered by varying solvent polarity and D–A character to depopulate 3LE and facilitate EnT from the chemically more tunable 3CT state for photosensitization. Following the above design principle, a new D–A fluorophore with strong D–A character and weak redox potential is identified, which exhibits high efficiency for Ni(II)-catalyzed cross-coupling of carboxylic acids and aryl halides with a wide substrate scope and high selectivity. Our results not only provide key fundamental insight on the EnT mechanism of D–A fluorophores but also establish its wide utility in EnT-mediated photocatalytic reactions

Direct Observation of Node-to-Node Communication in Zeolitic Imidazolate Frameworks

Zeolitic imidazolate frameworks (ZIFs) with open-shell transition metal nodes represent a promising class of highly ordered light harvesting antennas for photoenergy applications. However, their charge transport properties within the framework, the key criterion to achieve efficient photoenergy conversion, are not yet explored. Herein, we report the first direct evidence of a charge transport pathway through node-to-node communication in both ground state and excited state ZIFs using the combination of paramagnetic susceptibility measurements and time-resolved optical and X-ray absorption spectroscopy. These findings provide unprecedented new insights into the photoactivity and charge transport nature of ZIF frameworks, paving the way for their novel application as light harvesting arrays in diverse photoenergy conversion devices

Unravelling the Correlation of Electronic Structure and Carrier Dynamics in CuInS2 Nanoparticles

In this work, we report the direct correlation of photoinduced carrier dynamics and electronic structure of CuInS2 (CIS) nanoparticles (NPs) using the combination of multiple spectroscopic techniques including steady-state X-ray absorption spectroscopy (XAS), optical transient absorption (OTA), and X-ray transient (XTA) absorption spectroscopy. XAS results show that CIS NPs contain a large amount of surface Cu atoms with ≪four-coordination, which is more severe in CIS NPs with shorter nucleation times, indicating the presence of more Cu defect states in CIS NPs with smaller size particles. Using the combination of OTA and XTA spectroscopy, we show that electrons are trapped at states with mainly In or S nature while holes are trapped in sites characteristic of Cu. While there is no direct correlation of ultrafast trapping dynamics with NP nucleation time, charge recombination is significantly inhibited in CIS NPs with larger particles. These results suggest the key roles that Cu defect sites play in carrier dynamics and imply the possibility to control the carrier dynamics by controlling the surface structure at the Cu site in CIS NPs

Conformational States of Cytochrome P450 Oxidoreductase Evaluated by Förster Resonance Energy Transfer Using Ultrafast Transient Absorption Spectroscopy

NADPH-cytochrome P450 oxidoreductase (CYPOR) was shown to undergo large conformational rearrangements in its functional cycle. Using a new Förster resonance energy transfer (FRET) approach based on femtosecond transient absorption spectroscopy (TA), we determined the donor–acceptor distance distribution in the reduced and oxidized states of CYPOR. The unmatched time resolution of TA allowed the quantitative assessment of the donor–acceptor FRET, indicating that CYPOR assumes a closed conformation in both reduced and oxidized states in the absence of the redox partner. The described ultrafast TA measurements of FRET with readily available red–infrared fluorescent labels open new opportunities for structural studies in chromophore-rich proteins and their complexes