Metal-organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability and richness of their structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple and selective heterogeneous interactions and activations in these MOF-based nanocatalysts. Pyrolysis of MOF-nanoparticle composites forms highly porous N- or P-doped graphitized MOF-derived nanomaterials that are increasingly used as efficient catalysts especially in electro- and photocatalysis. This review first briefly summarizes this background of MOF nanoparticle catalysis and then comprehensively reviews the fast-growing literature reported during the last years. The major parts are catalysis of organic and molecular reactions, electrocatalysis, photocatalysis, and views of prospects. Major challenges of our society are addressed using these well-defined heterogeneous catalysts in the fields of synthesis, energy, and environment. In spite of the many achievements, enormous progress is still necessary to improve our understanding of the processes involved beyond the proof-of-concept, particularly for selective methane oxidation, hydrogen production, water splitting, CO2 reduction to methanol, nitrogen fixation, and water depollution.

State of the Art and Prospects in Metal-Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis.

More than 95% (in volume) of all of today’s chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic rese...

Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives

Visible light-induced photocatalysis is a promising way for environmental remediation due to efficient utilization of solar energy. Recently, metal–organic frameworks (MOFs) have attracted increasing attention in the field of photocatalysis. In comparison with traditional metal oxide semiconductors, MOFs have many advantages, such as high specific surface area, rich topology and easily tunable porous structure. In this review, we aim to summarize and illustrate recent advances in MOF-based photocatalysis for environmental remediation under visible light, including wastewater treatment, air purification and disinfection. A series of strategies have been designed to modify and regulate pristine MOFs for enhanced photocatalytic performance, such as ligand functionalization, mixed-metal/linker strategy, metal ion/ligand immobilization, dye sensitization, metal nanoparticle loading, carbon material decoration, semiconductor coupling, MOF/COF coupling, carrier loading and magnetic recycling. The above modifications may result in extended visible light absorption, efficient generation, separation and transfer of photogenerated charges, as well as good recyclability. However, there are still many challenges and obstacles. In order to meet the requirements of using MOF photocatalysis as a friendly and stable technology for low-cost practical applications, its future development prospects are also discussed.

/pdf/recent-advances-in-mof-based-photocatalysis-environmental-3m7z4g349c.pdf

Recent advances in MOF-based photocatalysis: environmental remediation under visible light

The photocatalytic hydrogen evolution on inorganic semiconductors has been studied for several decades. However, the conversion efficiency of solar energy is still poor caused by the recombination of photo-generated electron-hole pairs. Semiconductors - metal organic frameworks (MOFs) hybrid photocatalysts are being regarded as promising candidates due to large surface area and porosity. Here we reported the coordinative integration of a composite material with efficient capacity of H2 evolution driven by solar light, namely TiO2@ZIF-8, made up of titanium dioxide hollow nanospheres (TiO2 HNPs) externally decorated with zeolitic imidazolate framework-8 (ZIF-8) via a facile sonochemical route. The resulting composite demonstrates the high dispersion of ZIF-8 on the surface of TiO2 HNPs and this kind of close connection makes for an efficient photocatalyst through the synergistic effect. Up to 50.89% of apparent quantum efficiency (AQE), the hybrid double-shell HNPs exhibits 3.5 times higher H2 evolution rate (HER) than the bare TiO2 HNPs under solar light and shows good stability and recyclability. It is further proposed by photoluminescence spectra and optoelectronic measurement that the remarkably enhanced photocatalytic activity of TiO2@ZIF-8 is not only attributed to the efficient charge separation with electron injection from ZIF-8 to TiO2 HNPs, but also more active reaction sites provided by cavity structure of ZIF-8. Overall, this work exemplifies that surface engineering of semiconductors with MOFs is a great strategy to achieve advanced photocatalytic performance for solar energy conversion.

Self-template synthesis of double-shell TiO2@ZIF-8 hollow nanospheres via sonocrystallization with enhanced photocatalytic activities in hydrogen generation

The synthesis strategies and photocatalytic performances of TiO2/MOFs composites: A state-of-the-art review

The development of efficient catalysts with a visible-light response is of great importance in photocatalysis. Porphyrinic metal-organic frameworks (porph-MOFs) have recently been shown as promising photocatalyst candidates due to their large surface area, high visible light harvesting efficiency, and semiconductive properties, but challenges still remain because of their rapid charge recombination. Herein, we report the design of an effectively visible-light-driven composite material, namely TP-222(Zn), containing zirconium-based porph-MOF PCN-222(Zn) linked TiO2 nanoparticles (NPs) via the compound 4-mercaptopyridine which is axially bonded to the porphyrin central Zn metal in the PCN-222(Zn) and anchored onto the surface of TiO2 NPs. The resulting composite material demonstrates the high dispersion of TiO2 NPs and their close contact with the porph-MOF matrix, and serves as an effective photocatalyst for degrading organic contaminants under visible light irradiation due to their synergistic effect. It is further confirmed by fluorescence spectroscopy and electrochemical impedance spectroscopy that the remarkably enhanced photocatalytic activity of the TP-222(Zn) composite is attributed to the efficient charge separation with electron injection from PCN-222(Zn) to TiO2 NPs. In addition, the TP-222(Zn) composite shows excellent stability and recyclability as a result of the axially coordinative interaction between TiO2 NPs/PCN-222(Zn) and the 4-mercaptopyridine. Overall, this work provides a new strategy for the fabrication of highly efficient porph-MOF-based composite materials for visible light-driven photocatalysis.

Coordinative integration of a metal-porphyrinic framework and TiO2 nanoparticles for the formation of composite photocatalysts with enhanced visible-light-driven photocatalytic activities

Several mesoporous TiO2 (MT) materials were synthesized under different conditions following a hydrothermal procedure using poly(ethylene-glycol)-block-poly(propylene-glycol)-block-poly(ethylene-glycol) (P123) as the template and titanium isopropoxide as the titanium source. The molar ratios of Ti/P123, and the pH values of the reaction solution in an autoclave were investigated. Various techniques such as Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), laser Raman spectrometry (LRS), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products. Then, these materials were assembled into dye-sensitized solar cells (DSSCs). Analysis of the J–V curves and electrochemical impedance spectroscopy (EIS) were applied to characterize the cells. The results indicated that the specific surface area and crystalline structure of these materials provide the possibility of high photocurrent for the cells, and that the structural characteristics of the specimens led to increased electron transfer resistance of the cells, which was beneficial for the improvement of the photovoltage of the DSSCs. The highest photoelectric conversion efficiency of the cells involving MT materials reached 8.33%, which, compared with that of P25-based solar cell (5.88%), increased by 41.7%.

Preparation of dye-sensitized solar cells with high photocurrent and photovoltage by using mesoporous titanium dioxide particles as photoanode material

In this paper, we first investigated the optimal amount of ammonia to add, using ammonia as the single dopant for use in dye-sensitized solar cells (DSSCs). Using this optimal amount of ammonia, urea was introduced as the second N dopant. The DSSCs produced by double-N doped samples combine the advantages of increased visible light absorption with ammonia as the nitrogen dopant and enlarged interface area with urea as the second nitrogen dopant. Not only was Voc increased, but Jsc was also enhanced. We observed that the double-N doped sample forms a new microstructure with more mesopores, which enhance the transfer of electrolyte. Because these mesopores are the combination core of generated electrons and holes, they need to be kept in delicate balance. When urea is brought in as the double-N dopant, the doped amount of N atoms was improved. As a result, η is increased to 7.58%, a 14% improvement compared with single-N doped TiO2.

Double-N doping: a new discovery about N-doped TiO2applied in dye-sensitized solar cells

Synthesis of nano-TiO 2 assisted by diethylene glycol for use in high efficiency dye-sensitized solar cells

https://robots.iopscience.iop.org/article/10.1149/2.0191802jes/pdf

Template Controlled Synthesis of Mesoporous TiO2 Particles for Efficient Photoanodes in Dye Sensitized Solar Cells

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