Boosting photo-Fenton process enabled by ligand-to-cluster charge transfer excitations in iron-based metal organic framework

Li, Wenqiang; Wang, Yixuan; Chen, Jiaqi; Hou, Nannan; Li, Yuanming; Liu, Xiaocheng; Ding, Rong-Rong; Zhou, Guannan; Li, Qi; Zhou, Xiaoguo; Mu, Yang

doi:10.1016/j.apcatb.2021.120882

Cited by 73 publications

(29 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Principally, the low resistance and small arc radius in the EIS-Nyquist plot imply fast charge transfer in the semiconductor, and the experimental results showed that the resistance of Cu-MOF was greatly reduced under light illumination conditions (Figure c). Furthermore, the transient photoluminescence spectra demonstrate the stronger separation efficiency of Cu-MOF for photogenerated electron and hole pairs (Figure d), which further explains the properties of Cu-MOF as a well-performing photocatalyst. , …”

Section: Resultsmentioning

confidence: 74%

See 1 more Smart Citation

Application of Copper(II)–Organic Frameworks Bearing Dilophine Derivatives in Photocatalysis and Guest Separation

Chen

Liu

et al. 2022

Inorg. Chem.

View full text Add to dashboard Cite

The functionalized design of metal−organic frameworks (MOFs) has been rapidly developed in the last 20 years, and its broad applicability has been demonstrated in many fields. MOFs with desired functions can be assembled using predesigned organic linkers with specific metal nodes, which possess the ordered functional sites and open structures. Although a large number of carboxylic acid junctions have been used to construct MOFs, it is still a great challenge to realize their multifunctionality. In particular, there is a relative lack of research on MOFs as direct photocatalysts, which require not only abundant active sites and open structures but also adsorption groups and effective electron−hole separation performance. To this end, MOFs constructed from the carboxylic acid ligands derived from lophine-based derivatives and copper ions were deliberately used as a photocatalyst, and then, their application in dye degradation and aromatic alcohol conversion was investigated. In addition, in combination with the abundant Lewis sites of copper ions and imidazole sites, the material shows not only the adsorption and separation of C 2 series and dyes but also the application of dye degradation and conversion of aromatic alcohols under illumination conditions. The corresponding results fully illustrate that the MOF constructed by using lophine derivatives can be an effective way to prepare photocatalysts. The subsequent research ideas will focus on designing a series of MOFs constructed with multilinked moieties of lophine groups and exploring their application strategies in the field of photocatalysis.

show abstract

Section: Resultsmentioning

confidence: 74%

“…Obtaining from the related results, the lowest unoccupied molecular orbital (LUMO) of Cu-MOF at pH = 6.8 is −0.42 V vs Ag/AgCl, which is −0.22 V vs NHE. Thus, the highest occupied molecular orbital (HOMO) of Cu-MOF can be calculated to be 3.07 V …”

Section: Resultsmentioning

confidence: 99%

Application of Copper(II)–Organic Frameworks Bearing Dilophine Derivatives in Photocatalysis and Guest Separation

Chen

Liu

et al. 2022

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…Zr6O4(OH)4 mainly comes from the O 2p orbital of the oxygen ligand, while the Zr 4d orbital in the Zr-O nucleus dominates in the higher LUMO. The results show that the HOMO→ LUMO transition on Zr6O4(OH)4 ascribed to the O 2p→ Zr 4d charge transfer, which further corresponds to π (Fe-TCPP ligand)→ π * (Zr-oxo SBUs) orbital LCCT transition [58]. Therefore, DFT calculation proves that the D-A electron conduction path can be reconstructed in MOF-525 through cooperative excitation of MLCT and LCCT to improve electron separation and transmission efficiency.…”

Section: Density Functional Theory Calculationsmentioning

confidence: 85%

“…The UV light can co-stimulate the LCCT and MLCT transitions in MOF-525-Fe/Zr, which further improves the migration rate of photoelectrons, inhibiting the recombination of photoelectron-hole pairs. LCCT and MLCT effectively reduce the charge transfer resistance, and improve the carrier density and optical stability [57,58].…”

Section: Analysis Of Photoelectric Propertiesmentioning

confidence: 99%

Reconstruction of Electronic Structure of MOF-525 via Metalloporphyrin for Enhanced Photoelectro-Fenton Process

Han

Lin

et al. 2022

Catalysts

View full text Add to dashboard Cite

Photoelectro-Fenton (PEF) process can continuously promote the occurrence of Fenton reaction and the generation of active species, which is an advanced oxidation technology for pollutant degradation. However, the lack of bifunctional catalysts restricts the development of PEF technology. In this study, the electronic rearrangement MOF-525 modified by metalloporphyrin (named MOF-525-Fe/Zr) was prepared, to load on the carbon felt as a novel cathode catalyst, which is used in PEF process. A series of characterization and photoelectric chemical properties tests combined with DFT calculation showed that the modification of MOF-525 could not only have the large specific surface area and multistage pore structure but also co-stimulate the metal-to-ligand charge transfer (MLCT) and ligand-to-cluster charge transfer (LCCT) by photoelectric synergy. These charge transitions provide periodic electron donor-acceptor conduction paths in MOF-525-Fe/Zr, which can improve the active species formation and transfer efficiency. Owing to their favorable pore and electronic structure as well as stability, MOF-525-Fe/Zr shows great promise for the application in the catalytic process of PEF. Sulfamethoxazole (SMX) degradation was enhanced by MOF-525-Fe/Zr with the TOC removal rate above 75% both in river water and tap water. Finally, the reasonable pathway of PEF catalytic degradation of SMX was proposed by HPLC-MS analysis. In conclusion, this study provides a new idea for reconstructing the electronic structure of MOFs catalyst and broadening the practical application of PEF technology.

show abstract

“…Besides, with the concentration increase of NH 2 -MIL-101(Fe) in reaction system under same time irradiation, the fluorescence intensity enhances firstly and then gradually decrease, indicating the photocatalytic activity is concentration-dependent ( Figure 5 b). Previous studies have demonstrated that ligand-to-cluster charge transfer (LCCT) mechanism contributes to the photocatalytic performance of amine-functionalized metal (M) containing metal organic frameworks ( Zhang et al., 2016 ; Li et al., 2002 ). Specifically, the NH 2 functionality of NH 2 –H 2 DBC molecular in NH 2 -MIL-101(Fe) effectively absorb the visible light, and then the NH 2 –H 2 DBC will transfer photoelectrons to Fe–O clusters.…”

Section: Resultsmentioning

confidence: 99%

Porous NH2-MIL-101(Fe) metal organic framework for effective photocatalytic degradation of azo dye in wastewater treatment

Wang

Guo

2022

Heliyon

View full text Add to dashboard Cite

Boosting photo-Fenton process enabled by ligand-to-cluster charge transfer excitations in iron-based metal organic framework

Cited by 73 publications

References 58 publications

Application of Copper(II)–Organic Frameworks Bearing Dilophine Derivatives in Photocatalysis and Guest Separation

Application of Copper(II)–Organic Frameworks Bearing Dilophine Derivatives in Photocatalysis and Guest Separation

Reconstruction of Electronic Structure of MOF-525 via Metalloporphyrin for Enhanced Photoelectro-Fenton Process

Porous NH2-MIL-101(Fe) metal organic framework for effective photocatalytic degradation of azo dye in wastewater treatment

Contact Info

Product

Resources

About