A conductive metal–organic framework photoanode

Pattengale, Brian; Freeze, Jessica; Guberman‐Pfeffer, Matthew J.; Okabe, Ryotaro; Ostresh, Sarah; Chaudhuri, Sanjay; Batista, Víctor S.; Schmuttenmaer, Charles A.

doi:10.1039/d0sc04302h

Cited by 16 publications

(8 citation statements)

References 75 publications

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“…The natural question following these interesting findings is whether these delocalized intralayer charge carriers exhibit photoconductivity. In order to uncover the correlation of intralayer charge carriers and photoconductivity behavior of M-THQ, we measured the photoconductivity of these samples by probing the free carrier dynamics using optical pump terahertz probe (OPTP) spectroscopy. ,,− Figure d shows OPTP dynamics for Cu-THQ and Cu/Zn-THQ following 400 nm excitation. Note that both samples are adequately thick to fully absorb the pump pulse.…”

Section: Resultsmentioning

confidence: 99%

Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks

et al. 2020

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Conductive metal organic frameworks (MOFs) represent a promising class of porous crystalline materials that have demonstrated potential in photo-electronics and photocatalytic applications. However, the lack of fundamental understanding on charge transport (CT) mechanism as well as the correlation of CT mechanism with their structure hampered their further development. Herein, we report the direct evidence of CT mechanism in 2D Cu-THQ MOFs and the correlation of temporal and spatial behaviors of charge carriers with their photoconductivity by combining three advanced spectroscopic methods, including time resolved optical and X-ray absorption spectroscopy and terahertz spectroscopy. In addition to Cu-THQ, the CT in Cu/Zn-THQ after incorporating Zn 2+ guest metal was also examined to uncover the contribution of through space pathway, as the presence of the redox inactive 3d 10 Zn 2+ is expected to perturb the long range in-plane CT. We show that the hot carriers in Cu-THQ generated after photoexcitation are highly mobile and undergo fast localization to a lower energy state (cool carriers) with electrons occupying Cu center and holes in ligands. The cool carriers, which have super long lifetime (>17 ns), are responsible for the long-term photoconductivity in Cu-THQ and transport through the O− Cu−O motif with negligible contribution from interlayer ligand π−π stacking, as incorporation of Zn 2+ in Cu-THQ significantly reduced photoconductivity. These unprecedented results not only demonstrate the capability to experimentally probe CT mechanism but also provide important insight in the rational design of 2D MOFs for photoelectronic and photocatalytic applications.

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Section: Resultsmentioning

confidence: 99%

Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks

et al. 2020

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“…THz spectroscopy is widely used in the field of 2D materials, where it has been applied to graphene, carbon nitride, MXenes, and transition metal dichalcogenides, among others. ,,, To date, THz studies of MoS 2 have focused on only the 2H phase, specifically with samples that range from one layer to a few layers. − Herein, we present the first use of THz spectroscopy on bulk 1T-MoS 2 and the first comparative study with 2H-MoS 2 . Our THz-TDS measurements yield results consistent with a semiconducting material for 2H-MoS 2 and a metallic character for 1T-MoS 2 .…”

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confidence: 99%

Terahertz Conductivity of Semiconducting 2H and Metallic 1T Phases of Molybdenum Disulfide

Capobianco

Younan

Tayvah

et al. 2022

J. Phys. Chem. Lett.

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Molybdenum disulfide (MoS 2 ) has been extensively studied in its commonly occurring semiconducting 2H phase. Recent synthetic advances have enabled the bulk synthesis of the catalytically promising metallic 1T phase. However, the conductivity of bulk 1T-MoS 2 has not been well characterized to ascertain the carrier transport properties. Terahertz (THz) spectroscopy is an ideal technique for obtaining this crucial information because it is a noncontact method of measuring the conductivity of emerging materials with ultrafast time resolution. This work applies THz spectroscopy to bulk 2H-MoS 2 and 1T-MoS 2 , representing the first application of the technique on the 1T phase, with measurements confirming the semiconducting character of 2H-MoS 2 and the metallic character of 1T-MoS 2 . This study provides new insight into the metallic nature of bulk 1T-MoS 2 and a direct comparison to the semiconducting 2H phase that, together with physical characterization to obtain material parameters, are important for optimizing applications in catalysis devices and beyond.

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“…In a further practical application of TTFTB-based MOFs, Pattengale et al developed conductive MOF photoanodes using Zn 2 TTFTB as a photosensitizer and mesoporous TiO 2 nanoparticles as the semiconductor anode. 96 In the photophysical and computational studies therein, TiO 2 sensitized with the Zn 2 TTFTB MOF (Zn 2 TTFTB-TiO 2 ) was compared to TiO 2 sensitized with the TTFTB ligand chromophore (TTFTB-TiO 2 ). Time-resolved THz spectroscopy relied upon TiO 2centered conductivity signals to confirm that photoinduced electron injection from the MOF and ligand were feasible.…”

Section: Sample Preparation and Time-resolved Techniques Appliedmentioning

confidence: 99%

Interrogating Light-initiated Dynamics in Metal–Organic Frameworks with Time-resolved Spectroscopy

et al. 2021

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Time-resolved spectroscopy is an essential part of both fundamental and applied chemical research. Such techniques access light-initiated dynamics on time scales ranging from femtosecond to microsecond. Many techniques falling under this description have been applied to gain significant insight into metal–organic frameworks (MOFs), a diverse class of porous coordination polymers. MOFs are highly tunable, both compositionally and structurally, and unique challenges are encountered in applying time-resolved spectroscopy to interrogate their light-initiated properties. These properties involve various excited state mechanisms such as crystallographically defined energy transfer, charge transfer, and localization within the framework, photoconductivity, and structural dynamics. The field of time-resolved MOF spectroscopic studies is quite nascent; each original report cited in this review was published within the past decade. As such, this review is a timely and comprehensive summary of the most significant contributions in this emerging field, with focuses on the overarching spectroscopic concepts applied and on identifying key challenges and future outlooks moving forward.

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A conductive metal–organic framework photoanode

Abstract: We report the development of photosensitizing arrays based on conductive metal–organic frameworks (MOFs) that enable light harvesting and efficient charge separation.

Cited by 16 publications

References 75 publications

Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks

Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks

Terahertz Conductivity of Semiconducting 2H and Metallic 1T Phases of Molybdenum Disulfide

Interrogating Light-initiated Dynamics in Metal–Organic Frameworks with Time-resolved Spectroscopy

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