Hot-electron leading-out strategy for constructing photostable HOF catalysts with outstanding H2 evolution activity

Zhang, Nan; Yin, Qi; Guo, Song; Chen, Kai‐Kai; Liu, Tian‐Fu; Wang, Ping; Zhang, Zhiming; Lu, Tong‐Bu

doi:10.1016/j.apcatb.2021.120337

Cited by 36 publications

(21 citation statements)

References 46 publications

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“…The best rates for the nonporphyrinic nano-MOF and nano-COF composites lie on the same order of magnitude, with the largest value of ∼22.7 mmol g –1 h –1 . For nonporphyrinic MOFs, the two best rates are 26.1 and 31.2 mmol g –1 h –1 , and for nonporphyrinic COFs, the best rates are 23.41, 24.3, 26.02, 26.73, 36.99, and 46.4 mmol g –1 h –1 . It is noteworthy that the absorption bands of these photocatalysts do not necessarily cover the whole visible spectrum.…”

Section: Discussionmentioning

confidence: 98%

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Asselin

Harvey

2022

ACS Appl. Nano Mater.

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Porphyrin-based materials are excellent chromophores because they strongly absorb visible light and their relatively low-energy lowest unoccupied molecular orbitals thermodynamically favor photoinduced electron transfer. They can generate charge-transfer excited states with and without cocatalyst(s) and ease energy transfer and ultrafast excitation energy migration. Combined with synthetic accessibility, these qualities make them ideal building blocks for porous metal− organic framework (MOF)-and covalent−organic framework (COF)-based photocatalysts to produce solar fuels. This review first describes the structures of the most common porphyrinic MOFs and COFs and their excited-state properties and semiconducting behavior as well as that of derived composites. The generally accepted mechanisms of formation of H 2 , CH 4 and derivatives, and N 2 are then reviewed, followed by the detailed examples of nano-MOFs and nano-COFs used for the said purpose: characteristic parameters such as rates of production, turnover numbers (TONs), turnover frequencies (TOFs), and apparent quantum efficiencies are described and compared. This shows that porphyrin-based MOFs and COFs are efficient solar-fuelproducing photocatalysts, with characteristics comparable to those of nonporphyrinic MOF and COF photocatalysts, although, on some occasions, the rates of production fall short of record values. Conversely, porphyrinic MOFs and COFs exhibit the greatest TONs and TOFs of any solar-fuel-producing MOFs or COFs but still face shortcomings concerning selectivity in CH 4 production because of the many possible side products. Importantly, while the best rate of photoproduction of solar fuels has been observed from nanoscale photocatalysts, there seem to be no drastic differences in the rate (within μmol −1 h −1 and mmol g −1 h −1 ) between nanoscale and microscale heterogeneous photocatalysts. This observation suggests that the more active sites are mostly located at or near the surface of the particles. Overall, nanosized porphyrin-based MOFs and COFs show rich and promising photocatalytic properties for generating solar fuels but still have room for improvement.

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Section: Discussionmentioning

confidence: 98%

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Asselin

Harvey

2022

ACS Appl. Nano Mater.

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“…The close contact between the photosensitizer and the catalytic site is beneficial to enhancing charge transfer, which is another factor that affects the performance of a photocatalyst. , In recent years, developing catalysts with heterogeneous structures has been demonstrated to be an effective strategy to improve the efficiency of charge transfer in the photocatalytic process. − Hydrogen-bonded organic frameworks (HOFs) are excellent candidates to incorporate into heterogeneous structure catalysts because of their well-defined structures, open channels, easy tailorability, and excellent recyclability. − In particular, HOFs with large π-conjugated porphyrin building blocks not only can operate as photosensitizers in heterogeneous structures by transferring photoelectrons to the catalytic sites, but their high porosity may also help with CO 2 enrichment to further accelerate the photoreduction process.…”

Section: Introductionmentioning

confidence: 99%

Facile Preparation of Hydrogen-Bonded Organic Framework/Cu₂O Heterostructure Films via Electrophoretic Deposition for Efficient CO₂ Photoreduction

Zhang

Fang

et al. 2022

ACS Appl. Mater. Interfaces

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Photocatalytic CO 2 reduction is one of the most cost-effective and environmentally friendly techniques of converting CO 2 into high-value compounds and/or fuels. However, the performance of most current photocatalytic CO 2 reduction catalysts is less than satisfactory for practical applications. Here, we synthesized a heterogeneous structure by integrating Cu 2 O and a porphyrin hydrogen-bonded organic framework (PFC-45), which was then fabricated into a thin-film catalyst on carbolic paper (CP) using a facile electrophoretic deposition technology. With improved electron−hole separation efficiency and visible-light-harvesting ability, this film (PFC-45/Cu 2 O@CP) significantly enhanced CO 2 -to-CO photoreduction, exceeding 2.4 and 3.2 times that of PFC-45@CP and PFC-45/Cu 2 O particles, respectively. Remarkably, PFC-45/Cu 2 O@CP also exhibited high selectivity (99%) and outstanding activity (11.81 μmol g −1 h −1 ) for photocatalytic CO 2 reduction in pure water without any sacrificial agent. This work demonstrates a new strategy to design photocatalysts for efficient CO 2 reduction.

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“…Photocatalytic water splitting has been expected to act as an alternative approach to meet energy demands and overcome environmental concerns relating to fossil fuels. 1–4 The scientific community has reached a consensus that g-C 3 N 4 -based photocatalysts are some of the most promising photocatalytic materials. 5–8 However, both the existence of abundant recombination centers for photogenerated carriers and the weak light absorption of g-C 3 N 4 are regarded as the biggest barriers to practical application.…”

Section: Introductionmentioning

confidence: 99%

Shearing bridge bonds in carbon nitride vesicles with enhanced hot carrier utilization for photocatalytic hydrogen production

Liu

Zhang

et al. 2022

Catal. Sci. Technol.

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Hot-electron leading-out strategy for constructing photostable HOF catalysts with outstanding H2 evolution activity

Cited by 36 publications

References 46 publications

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Facile Preparation of Hydrogen-Bonded Organic Framework/Cu₂O Heterostructure Films via Electrophoretic Deposition for Efficient CO₂ Photoreduction

Shearing bridge bonds in carbon nitride vesicles with enhanced hot carrier utilization for photocatalytic hydrogen production

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Hot-electron leading-out strategy for constructing photostable HOF catalysts with outstanding H2 evolution activity

Cited by 36 publications

References 46 publications

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Visible-Light-Driven Production of Solar Fuels Catalyzed by Nanosized Porphyrin-Based Metal–Organic Frameworks and Covalent–Organic Frameworks: A Review

Facile Preparation of Hydrogen-Bonded Organic Framework/Cu2O Heterostructure Films via Electrophoretic Deposition for Efficient CO2 Photoreduction

Shearing bridge bonds in carbon nitride vesicles with enhanced hot carrier utilization for photocatalytic hydrogen production

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Facile Preparation of Hydrogen-Bonded Organic Framework/Cu₂O Heterostructure Films via Electrophoretic Deposition for Efficient CO₂ Photoreduction