Enhancing Photocatalytic Hydrogen Production via the Construction of Robust Multivariate Ti‐MOF/COF Composites

Chen, Cheng‐Xia; Xiong, Yi; Zhong, Xin; Lan, Pui Ching; Wei, Zhang‐Wen; Pan, Hongjun; Su, Peiyang; Song, Yujie; Chen, Yifan; Nafady, Ayman; Sirajuddin, Sirajuddin; Ma, Shengqian

doi:10.1002/anie.202114071

Cited by 100 publications

(33 citation statements)

References 84 publications

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“…Additionally, the high porosity of MOFs also guarantees the large surface area of the resulted MOF/COF photocatalysts and can facilitate the mass transfer during the catalytic reaction . The integrated MOF/COF systems have already been proved to achieve superior performance compared to the corresponding single component. − However, the development of MOF/COF photocatalysts for water splitting has just begun and only very few such photocatalysts were reported to exhibit excellent hydrogen evolution rate, but which still needed the help of Pt cocatalysts. ,, …”

Section: Introductionmentioning

confidence: 99%

In Situ Fabrication of Porous MOF/COF Hybrid Photocatalysts for Visible-Light-Driven Hydrogen Evolution

Xue

Pan

Huang

et al. 2021

ACS Appl. Mater. Interfaces

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Construction of porous metal–organic framework (MOF)/covalent organic framework (COF) hybrid photocatalysts for enriched structures and unprecedented properties is still a great challenge but highly desirable. Herein, a new series of Cu3(HHTP)2-MOF/Tp-Pa-1-COF hybrids with different MOF content are successfully fabricated. The as-prepared MOF/COF hybrids exhibit intimate interaction based on the coordination of Cu ions with the carbonyl oxygen and enamine nitrogen groups in Tp-Pa-1. The integrated conductive Cu3(HHTP)2 is able to act as an excellent electron extractor instead of noble metal cocatalysts to significantly promote the charge transfer and inhibit the recombination of photogenerated electron–hole pairs. As a results, the optimized photocatalyst with Cu3(HHTP)2:Tp-Pa-1 ratio of 1:15 achieves the highest hydrogen evolution rate of 1.76 mmol·h–1·g–1 under visible-light irradiation, which is about 93 times higher than that of the pure Tp-Pa-1 and even slightly higher than that of the Tp-Pa-1 with Pt (3 wt %) as a cocatalyst.

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Section: Introductionmentioning

confidence: 99%

In Situ Fabrication of Porous MOF/COF Hybrid Photocatalysts for Visible-Light-Driven Hydrogen Evolution

Xue

Pan

Huang

et al. 2021

ACS Appl. Mater. Interfaces

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“…Micro- and nanosized porphyrin-based MOFs, ,,− ,,,− MOF/COF composites, and COFs − have been thoroughly investigated and are found to be efficient photocatalysts for H 2 evolution, where the porphyrin or metalloporphyrin chromophore acts as a photosensitizer through either energy or electron transfer. This process triggers the donation of e – from the charge-separated state to the proton, followed by filling of the hole using a sacrificial electron donor.…”

Section: Photocatalytic H2 Evolutionmentioning

confidence: 99%

“…Ma, Chen, and collaborators reported the synthesis and characterization of a hybrid nanocomposite of porphyrin-based MOFs and COFs, referred to as MTV-Ti-MOFs/COFs . The two-step synthesis consists first of preparing Pd(TCPP)/PCN-415(NH 2 ) from Ti( i PPr) 4 /ZrCl 4 , Pd(TCPP), and NH 2 BDC (Figure a,b) in solvothermal conditions.…”

Section: Photocatalytic H2 Evolutionmentioning

confidence: 99%

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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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“…Additionally, a plethora of structural configurations (MOF isomers) may be achieved by varied synthetic conditions from a single metal–ligand combination . As a result, MOFs have potential applications in gas separations, − catalysis, − energy storage, − sensing, − and drug delivery. , …”

Section: Introductionmentioning

confidence: 99%

Energetic Systematics of Metal–Organic Frameworks: A Case Study of Al(III)-Trimesate MOF Isomers

Goncharov

Strzelecki

et al. 2022

Inorg. Chem.

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Thermal stability and thermodynamic properties of aluminum(III)-1,3,5-benzenetricarboxylate (Al-BTC) metal−organic frameworks (MOFs), including MIL-96, MIL-100, and MIL-110, have been investigated through a suite of calorimetric and X-ray techniques. In situ high-temperature X-ray diffraction (HT-XRD) and thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC) revealed that these MOFs undergo thermal amorphization prior to ligand combustion. Thermal stabilities of Al-BTC MOFs follow the increasing order MIL-110 < MIL-96 < MIL-100, based on estimated amorphization temperatures. Their thermodynamic stabilities were directly measured by high-temperature drop combustion calorimetry. Normalized (per mole of Al) enthalpies of formation (ΔH* f ) of MIL-96, MIL-100, and MIL-110 from Al 2 O 3, H 3 BTC, and H 2 O (only Al 2 O 3 and H 3 BTC for MIL-100) were determined to be −56.9 ± 13.7, −36.2 ± 17.9, and 62.8 ± 11.6 kJ/mol•Al, respectively. Our results demonstrate that MIL-96 and MIL-100 are thermodynamically favorable, while MIL-110 is metastable, in agreement with thermal and hydrothermal stability trends. The enthalpic preferences of MIL-96 and MIL-100 may be attributed to their shared trinuclear μ 3 -oxo-bridged (Al 3 (μ 3 -O)) secondary building units (SBUs) promoting stabilization of Al polyhedra by the ligands within these frameworks, in comparison to the sterically strained Al 8 octamer cluster cores formed in MIL-110. Furthermore, similar ΔH* f of MIL-96 and MIL-100 explain their concurrent formation as physical mixtures often encountered during synthesis, implying the importance of kinetic factors that may facilitate the formation of Al-BTC framework isomers. More importantly, the normalized formation enthalpies of Al-BTC MOF isomers follow a negative correlation with the ratio of charged coordinated substituents to linkers (normalized per mole of Al within the MOF formula unit), with enthalpic preference given to systems with smaller (O 2− + OH − )/ligand ratios. This trend has been successfully extended to the previously measured ΔH* f of several Zn 4 O-based frameworks (e.g., MOF-5, MOF-5(DEF), MOF-177, UMCM-1), all of which have been found to be metastable with respect to their dense phases (ZnO, H 2 O, and ligands). The result suggests that carboxylate MOFs with higher metal coordination environments attain more enthalpic stabilization from the coordinated ligands. Thus, the formation of some lanthanide/actinide, transition metal, and main group carboxylate frameworks may be energetically more favored, which, however, requires further studies.

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Enhancing Photocatalytic Hydrogen Production via the Construction of Robust Multivariate Ti‐MOF/COF Composites

Cited by 100 publications

References 84 publications

In Situ Fabrication of Porous MOF/COF Hybrid Photocatalysts for Visible-Light-Driven Hydrogen Evolution

In Situ Fabrication of Porous MOF/COF Hybrid Photocatalysts for Visible-Light-Driven Hydrogen Evolution

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

Energetic Systematics of Metal–Organic Frameworks: A Case Study of Al(III)-Trimesate MOF Isomers

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