With the increasing demand for fuel causing serious environmental pollution, it is urgent to develop new and environmentally friendly energy conversion devices. These energy conversion devices, however, require good, inexpensive materials for electrodes and so on. The multifunctional properties of porphyrins enable framework materials (e.g., metal-organic frameworks and covalent organic frameworks) to be applied in energy conversion devices due to their simple synthesis, high chemical stability, abundant metallic active sites, adjustable crystalline structure and high specific surface area. Herein, the types of porphyrin structural blocks are briefly reviewed. They can be used as organic ligands or directly assembled with framework materials to generate high-performance electro-/photo-catalysts. These types of catalysts applied in electro-/photo-catalytic water splitting, electro-/photo-catalytic carbon dioxide reduction, and electrocatalytic oxygen reduction are also summarized and introduced. At the end of the article, we present the challenges of porphyrin-based framework materials in the above application and corresponding solutions. We expect porphyrin-based framework materials to flourish energy conversion in the coming years. 

https://www.sciopen.com/article_pdf/1529713025819033601.pdf

Porphyrin-based Framework Materials for Energy Conversion

Covalent organic framework-based materials: Synthesis, modification, and application in environmental remediation

Metal–organic frameworks (MOFs), composed of metal ions/clusters and organic ligands and possessing inherent crystallinity, a definite structure, a tunable pore, and multiple functionalizations, have shown potential for numerous applications Recently, luminescent MOFs (LMOFs) have attracted much attention as sensing materials because their structural and chemical tunability can afford good selectivity through pore-sieving functions with different pore sizes or host framework–guest interactions Meanwhile, MOFs with high internal surface areas can concentrate analytes to a high density, thereby decreasing detection limits and exhibiting high sensitivity Numerous LMOFs have been synthesized and employed for sensing applications Here, the recent advances of LMOFs as chemical sensors based on “mechanism–response” were summarized, including collapse of frameworks, overlap, cation exchange, ligand exchange, reaction- and redox-based mechanisms, electron transfer, energy transfer, hydrogen bonding, linker–analyte interaction, synergistic effects, and multiple interactions Moreover, in this review, present challenges and future opportunities in this field are discussed This review could be a valuable reference for the rational construction and sensing applications of LMOFs

Luminescent metal-organic frameworks as chemical sensors based on "mechanism-response": a review.

Artful union of a zirconium-porphyrin MOF/GO composite for fabricating an aptamer-based electrochemical sensor with superb detecting performance

Excessive emissions of carbon dioxide (CO2) in the atmosphere result in a series of energy and environmental issues all around the word Thus, it is urgent to prepare efficient materials for the conversion of CO2 as a C1 source into energy-related chemical products Porous metal–organic frameworks (MOFs) are a class of rapidly growing crystalline materials, which have attracted significant attention for application in the conversion of CO2 into cyclic carbonates In this review article, the developments made in recent years with respect to the application of MOFs as heterogeneous catalysts for the energy-related conversion of CO2 into cyclic carbonates are highlighted; moreover, we have further discussed the opportunities and challenges in the use of MOFs in this field

Metal-organic frameworks for the energy-related conversion of CO2 into cyclic carbonates.

Exploration and construction of novel porous core-shell composites is of crucial significance due to their prospectively enhanced performances and far-ranging applications. Herein, microporous UiO-66-NH2 as a MOF core is coated by a mesoporous TAPB-DMTP−COF shell to construct the UiO-66-NH2@COF composite via a covalent linking approach. Importantly, the composite with retentive crystallinity and hierarchical porosity significantly improves the electrochemical detection performance, for instance ATP and antibiotic, because this composite has the high affinity between the phosphate groups of aptamers and dense Zr(IV) sites, and strong π-π stacking interaction between aptamers and this MOF@COF. The synthetic strategy in this systematic research expands a rational design for other MOF@COF core-shell hybrid materials to expand their promising applications.

Crystal engineering of MOF@COF core-shell composites for ultra-sensitively electrochemical detection

Metal–organic frameworks (MOFs) are a burgeoning class of crystalline materials constructed from metal cations/clusters and organic ligands with various potential applications. Thus, luminescent MOFs display potential applications in smart sensing with excellent sensitivity, accuracy, anti-jamming, stability, and selectivity. MOFs possess their intrinsic luminescent property from metal cations, organic ligands, and other luminescent species via ingenious design and post-modification. Luminescent MOFs can be used as advanced detection materials for various antibiotics through their luminescent signal response, including the emission intensity and location. Herein, for the first time, we intend to provide a comprehensive overview on the state-of-the-art methods and challenges of antibiotic detection by luminescent MOFs.

/pdf/state-of-the-art-methods-and-challenges-of-luminescent-metal-gm897f6o99.pdf

State of the art methods and challenges of luminescent metal–organic frameworks for antibiotic detection

A novel porous organic polymer (POP) was designed and prepared by the coupled polymerization of 1, 3, 6, 8-Tetraphenylpyrene and α, α′-dibromo-p-xylen. The as-synthesized POP is an extended π-conjugation framework with high surface area, excellent stability and large pore cavity, thus bestowing the outstanding carrying capacity of aptamer strands through π-π stacking interaction to rationally fabricate a ultrasensitive electrochemical aptasensor. The biosensor exhibits the lowest limit of detection of 1.33 fg·mL–1 (3.30 fM) for detecting trace ampicillin (AMP) by using electrochemical impedance spectroscopy. Furthermore, this biosensor can accurately monitor AMP in multiple real samples. This work provides the greatly potential applications of POPs in the fabrication of electrochemical biosensors for sensitively detecting antibiotics or other analytes.

Design and fabrication of an electrochemical sensing platform based on a porous organic polymer for ultrasensitive ampicillin detection

Gold (Au) nanoparticle-embedded covalent organic frameworks (namely Au@COFs) were ingeniously designed and prepared by using a straightforward impregnation-reduction method. This composite not only owns outstanding stability, rich π functional sites, superior electroconductibility, high surface area, and well-ordered porous structures, but also possesses relatively strong non-covalent affinity toward aptamers, synergistically resulting in the establishment of highly efficient electrochemical aptasensors for detecting analytes. Ciprofloxacin (CIP), for instance, is selected and investigated as a research model to estimate the feasibility and superiority of Au@COF-based aptasensors. The as-made Au@COF-based aptasensor exhibits awesome sensing performance with the lowest limit of detection of 2.34 fg mL−1 (7.06 fM) in a concentration range from 1.0 × 10−5 to 0.5 ng mL−1 as determined by analyzing electrochemical impedance signals, which is approximately attributed to numerous aptamer strands on the surface of COFs via strong π–π stacking interaction and the contribution of electrical conductivity from trapped Au nanoparticles. Concurrently, the fabricated aptasensor reveals excellent repeatability, circularity, selectivity, and stability as well as precise detection capability in a variety of real samples. This strategy provides a workable concept for developing and synthesizing of metal nanoparticle-built-in COF composites and their aptasensors in the extended electrochemical detection field.

Rongrong Yuan

Papers

Crystal engineering of MOF@COF core-shell composites for ultra-sensitively electrochemical detection

State of the art methods and challenges of luminescent metal–organic frameworks for antibiotic detection

Artful union of a zirconium-porphyrin MOF/GO composite for fabricating an aptamer-based electrochemical sensor with superb detecting performance

Design and fabrication of an electrochemical sensing platform based on a porous organic polymer for ultrasensitive ampicillin detection

Elaborately manufacturing an electrochemical aptasensor based on gold nanoparticle/COF composites for amplified detection performance