Molecules

Research

Jump to: Review

12 pages, 5519 KiB

Open AccessArticle

Porphyrin-Based MOF Thin Film on Transparent Conducting Oxide: Investigation of Growth, Porosity and Photoelectrochemical Properties

by Ben Gikonyo, Fangbing Liu, Saly Hawila, Aude Demessence, Herme G. Baldovi, Sergio Navalón, Catherine Marichy and Alexandra Fateeva

Molecules 2023, 28(15), 5876; https://doi.org/10.3390/molecules28155876 - 04 Aug 2023

Viewed by 1027

Abstract

Synthesizing metal-organic frameworks (MOFs) composites with a controlled morphology is an important requirement to access materials of desired patterning and composition. Since the last decade, MOF growth from sacrificial metal oxide layer is increasingly developed as it represents an efficient pathway to functionalize [...] Read more.

Synthesizing metal-organic frameworks (MOFs) composites with a controlled morphology is an important requirement to access materials of desired patterning and composition. Since the last decade, MOF growth from sacrificial metal oxide layer is increasingly developed as it represents an efficient pathway to functionalize a large number of substrates. In this study, porphyrin-based Al-PMOF thin films were grown on conductive transparent oxide substrates from sacrificial layers of ALD-deposited alumina oxide. The control of the solvent composition and the number of atomic layer deposition (ALD) cycles allow us to tune the crystallinity, morphology and thickness of the produced thin films. Photophysical studies evidence that Al-PMOF thin films present light absorption and emission properties governed by the porphyrinic linker, without any quenching upon increasing the film thickness. Al-PMOF thin films obtained through this methodology present a remarkably high optical quality both in terms of transparency and coverage. The porosity of the samples is demonstrated by ellipsometry and used for Zn(II) insertion inside the MOF thin film. The multifunctional transparent, porous and luminescent thin film grown on fluorine-doped tin oxide (FTO) is used as an electrode capable of photoinduced charge separation upon simulated sunlight irradiation. Full article

(This article belongs to the Special Issue Metal-Organic Framework-Based Composites: Synthesis and Applications)

► Show Figures

Figure 1

20 pages, 4680 KiB

Open AccessArticle

Preparation of Polyoxometalate-Based Composite by Solidification of Highly Active Cobalt-Containing Polytungstate on Polymeric Ionic Liquid for the Efficient Isolation of Proteinase K

by Jiaxuan Yang, Ning Chu and Xuwei Chen

Molecules 2023, 28(8), 3307; https://doi.org/10.3390/molecules28083307 - 07 Apr 2023

Cited by 2 | Viewed by 1330

Abstract

A novel porous polyoxometalate (POM)-based composite (Co₄PW–PDDVAC) was prepared via the solidification of water-soluble polytungstate (Co₄PW) on the polymeric ionic liquid dimethyldodecyl-4-polyethylene benzyl ammonium chloride (PDDVAC) via a cation-exchange reaction. The solidification was confirmed by EDS, SEM, FT-IR, TGA, [...] Read more.

A novel porous polyoxometalate (POM)-based composite (Co₄PW–PDDVAC) was prepared via the solidification of water-soluble polytungstate (Co₄PW) on the polymeric ionic liquid dimethyldodecyl-4-polyethylene benzyl ammonium chloride (PDDVAC) via a cation-exchange reaction. The solidification was confirmed by EDS, SEM, FT-IR, TGA, and so on. The strong covalent coordination and hydrogen-bonding interaction between the highly active Co²⁺ of the Co₄PW and the aspartic acid residues of proteinase K endowed the obtained Co₄PW–PDDVAC composite with excellent proteinase K adsorption properties. Thermodynamic investigations indicate that the adsorption behavior of proteinase K was consistent with the linear Langmuir isothermal model, giving an adsorption capacity as high as 1428 mg g⁻¹. The Co₄PW–PDDVAC composite was applied in the selective isolation of highly active proteinase K from Tritirachium album Limber crude enzyme fluid. Full article

(This article belongs to the Special Issue Metal-Organic Framework-Based Composites: Synthesis and Applications)

► Show Figures

Graphical abstract

12 pages, 2700 KiB

Open AccessArticle

High-Branched Organosilicon Epoxy Resin with Low Viscosity, Excellent Toughness, Hydrophobicity, and Dielectric Property

by Min Yu, Zeyuan Chen, Jie Li, Jihuai Tan and Xinbao Zhu

Molecules 2023, 28(6), 2826; https://doi.org/10.3390/molecules28062826 - 21 Mar 2023

Cited by 2 | Viewed by 1610

Abstract

Rapidly developing technology places higher demands on materials, thus the simultaneous improvement of materials’ multiple properties is a hot research topic. In this work, a high-branched silicone epoxy resin (QSiE) was synthesized and applied to the curing system of bisphenol A epoxy resin [...] Read more.

Rapidly developing technology places higher demands on materials, thus the simultaneous improvement of materials’ multiple properties is a hot research topic. In this work, a high-branched silicone epoxy resin (QSiE) was synthesized and applied to the curing system of bisphenol A epoxy resin (DGEBA) for modification investigations. When 6 wt% QSiE was added to the system, the viscosity dropped by 51.8%. The mechanical property testing results indicated that QSiE could significantly enhance the material’s toughness while preserving good rigidity. The impact strength was enhanced by 1.31 times when 6wt% of QSiE was introduced. Additionally, the silicon skeleton in QSiE has low surface energy and low polarizability, which could endow the material with good hydrophobic and dielectric properties. This work provided a new idea for the preparation of high-performance epoxy resin additives, and provided a broad prospect for cutting-edge applications of epoxy resins. Full article

(This article belongs to the Special Issue Metal-Organic Framework-Based Composites: Synthesis and Applications)

► Show Figures

Figure 1

12 pages, 4368 KiB

Open AccessArticle

A Facile Method to Fabricate Al₂O₃-SiO₂ Aerogels with Low Shrinkage up to 1200 °C

by Yulin Tian, Xiaodong Wang, Yu Wu, Xiaoxue Zhang, Chun Li, Yijun Wang and Jun Shen

Molecules 2023, 28(6), 2743; https://doi.org/10.3390/molecules28062743 - 17 Mar 2023

Cited by 3 | Viewed by 1567

Abstract

Monolithic Al₂O₃-SiO₂ composite aerogels were synthesized by using inexpensive aluminum chloride hexahydrate (AlCl₃·6H₂O) and tetraethyl orthosilicate (TEOS). By adjusting the molar ratio of Al and Si, the best ratio of high-temperature resistance was found. [...] Read more.

Monolithic Al₂O₃-SiO₂ composite aerogels were synthesized by using inexpensive aluminum chloride hexahydrate (AlCl₃·6H₂O) and tetraethyl orthosilicate (TEOS). By adjusting the molar ratio of Al and Si, the best ratio of high-temperature resistance was found. The resultant aerogels (Al:Si = 9:1) exhibit high thermal performance, which can be identified by the low linear shrinkage of 5% and high specific surface area (SSA) of 283 m²/g at 1200 °C. Alumina in these aerogels mainly exists in the boehmite phase and gradually transforms into the θ-Al₂O₃ phase in the process of heating to 1200 °C. No α-Al₂O₃ is detected in the heating process. These Al₂O₃-SiO₂ composite aerogels are derived from a simple, low-priced and safe method. With their high thermal performance, these aerogels will have a wide application in high-temperature field. Full article

(This article belongs to the Special Issue Metal-Organic Framework-Based Composites: Synthesis and Applications)

► Show Figures

Figure 1

14 pages, 4428 KiB

Open AccessArticle

Nanoscale Two-Dimensional Fe^II- and Co^II-Based Metal–Organic Frameworks of Porphyrin Ligand for the Photodynamic Therapy of Breast Cancer

by Qing Li, Bo-Wei Xu, Yi-Ming Zou, Ru-Jie Niu, Jin-Xiang Chen, Wen-Hua Zhang and David James. Young

Molecules 2023, 28(5), 2125; https://doi.org/10.3390/molecules28052125 - 24 Feb 2023

Cited by 2 | Viewed by 1892

Abstract

The delivery of biocompatible reagents into cancer cells can elicit an anticancer effect by taking advantage of the unique characteristics of the tumor microenvironment (TME). In this work, we report that nanoscale two-dimensional Fe^II- and Co^II-based metal–organic frameworks (NMOFs) [...] Read more.

The delivery of biocompatible reagents into cancer cells can elicit an anticancer effect by taking advantage of the unique characteristics of the tumor microenvironment (TME). In this work, we report that nanoscale two-dimensional Fe^II- and Co^II-based metal–organic frameworks (NMOFs) of porphyrin ligand meso-tetrakis (6-(hydroxymethyl) pyridin-3-yl) porphyrin (THPP) can catalyze the generation of hydroxyl radicals (•OH) and O₂ in the presence of H₂O₂ that is overexpressed in the TME. Photodynamic therapy consumes the generated O₂ to produce a singlet oxygen (¹O₂). Both •OH and ¹O₂ are reactive oxygen species (ROS) that inhibit cancer cell proliferation. The Fe^II- and Co^II-based NMOFs were non-toxic in the dark but cytotoxic when irradiated with 660 nm light. This preliminary work points to the potential of porphyrin-based ligands of transition metals as anticancer drugs by synergizing different therapeutic modalities. Full article

(This article belongs to the Special Issue Metal-Organic Framework-Based Composites: Synthesis and Applications)

► Show Figures

Graphical abstract

14 pages, 3239 KiB

Open AccessArticle

BiVO₄–Deposited MIL–101–NH₂ for Efficient Photocatalytic Elimination of Cr(VI)

by Huiwen Sun, Qihang Dai, Ju Liu, Tiantian Zhou, Muhua Chen, Zhengchun Cai, Xinbao Zhu and Bo Fu

Molecules 2023, 28(3), 1218; https://doi.org/10.3390/molecules28031218 - 26 Jan 2023

Cited by 2 | Viewed by 1458

Abstract

In this study, a flower–like BiVO₄/MIL–101–NH₂ composite is synthesized by a facile and surfactant–free process. The –COO⁻–Bi³⁺ ionic bond construction was conductive to enhance the interface affinity between BiVO₄ and MIL–101–NH₂. Due to the [...] Read more.

In this study, a flower–like BiVO₄/MIL–101–NH₂ composite is synthesized by a facile and surfactant–free process. The –COO⁻–Bi³⁺ ionic bond construction was conductive to enhance the interface affinity between BiVO₄ and MIL–101–NH₂. Due to the highly efficient light capture and sufficient electron traps induced by oxygen vacancies and the formation of a heterostructure, the improved separation and transportation rates of charge carriers are realized. In addition, the MIL–101–NH₂/BiVO₄ composite is favorable for Cr(VI) photocatalytic removal (91.2%). Moreover, FNBV–3 (Fe/Bi = 0.25) also exhibited an excellent reusability after five cycles. Full article

(This article belongs to the Special Issue Metal-Organic Framework-Based Composites: Synthesis and Applications)

► Show Figures

Figure 1

Review

Jump to: Research

27 pages, 6144 KiB

Open AccessReview

Porphyrin-Based Metal-Organic Framework Materials: Design, Construction, and Application in the Field of Photocatalysis

by Chuanyin Tang, Xiaoyu Li, Yingxu Hu, Xin Du, Shuo Wang, Bo Chen and Shengjie Wang

Molecules 2024, 29(2), 467; https://doi.org/10.3390/molecules29020467 - 17 Jan 2024

Cited by 1 | Viewed by 1694

Abstract

Metal-organic frameworks (MOFs) are a novel category of porous crystalline materials with an exceptionally high surface area and adjustable pore structure. They possess a designable composition and can be easily functionalized with different units. Porphyrins with conjugated tetrapyrrole macrocyclic structures can absorb light [...] Read more.

Metal-organic frameworks (MOFs) are a novel category of porous crystalline materials with an exceptionally high surface area and adjustable pore structure. They possess a designable composition and can be easily functionalized with different units. Porphyrins with conjugated tetrapyrrole macrocyclic structures can absorb light from ultraviolet to visible light regions, and their structures and properties can be facilely regulated by altering their peripheral groups or central metal ions. Porphyrin-based MOFs constructed from porphyrin ligands and metal nodes combine the unique features of porphyrins and MOFs as well as overcoming their respective limitations. This paper reviewed the design and construction, light absorption and charge transfer pathways, and strategy for improving the photocatalytic performance of porphyrin-based MOFs, and highlighted the recent progress in the field of CO₂ reduction, hydrogen evolution, organic synthesis, organic pollutant removal, and nitrogen fixation. The intrinsic relationships between the structure and the property of porphyrin-based MOFs received special attention, especially the relationships between the arrangements of porphyrin ligands and metal nods and the charge transfer mechanism. We attempted to provide more valuable information for the design and construction of advanced photocatalysts in the future. Finally, the challenges and future perspectives of the porphyrin-based MOFs are also discussed. Full article

(This article belongs to the Special Issue Metal-Organic Framework-Based Composites: Synthesis and Applications)

► Show Figures

Graphical abstract

21 pages, 5484 KiB

Open AccessReview

Advance Progress on Luminescent Sensing of Nitroaromatics by Crystalline Lanthanide–Organic Complexes

by Yixia Ren, Zhihu Ma, Ting Gao and Yucang Liang

Molecules 2023, 28(11), 4481; https://doi.org/10.3390/molecules28114481 - 01 Jun 2023

Cited by 6 | Viewed by 1377

Abstract

Water environment pollution is becoming an increasingly serious issue due to industrial pollutants with the rapid development of modern industry. Among many pollutants, the toxic and explosive nitroaromatics are used extensively in the chemical industry, resulting in environmental pollution of soil and groundwater. [...] Read more.

Water environment pollution is becoming an increasingly serious issue due to industrial pollutants with the rapid development of modern industry. Among many pollutants, the toxic and explosive nitroaromatics are used extensively in the chemical industry, resulting in environmental pollution of soil and groundwater. Therefore, the detection of nitroaromatics is of great significance to environmental monitoring, citizen life and homeland security. Lanthanide–organic complexes with controllable structural features and excellent optical performance have been rationally designed and successfully prepared and used as lanthanide-based sensors for the detection of nitroaromatics. This review will focus on crystalline luminescent lanthanide–organic sensing materials with different dimensional structures, including the 0D discrete structure, 1D and 2D coordination polymers and the 3D framework. Large numbers of studies have shown that several nitroaromatics could be detected by crystalline lanthanide–organic-complex-based sensors, for instance, nitrobenzene (NB), nitrophenol (4-NP or 2-NP), trinitrophenol (TNP) and so on. The various fluorescence detection mechanisms were summarized and sorted out in the review, which might help researchers or readers to comprehensively understand the mechanism of the fluorescence detection of nitroaromatics and provide a theoretical basis for the rational design of new crystalline lanthanide–organic complex-based sensors. Full article

(This article belongs to the Special Issue Metal-Organic Framework-Based Composites: Synthesis and Applications)

► Show Figures