Redox-active metal–organic frameworks for energy conversion and storage

Calbo, Joaquín; Golomb, Matthias; Walsh, Aron

doi:10.1039/c9ta04680a

Cited by 260 publications

(180 citation statements)

References 218 publications

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“…[47] In this direction, redox-activeb uildingb locks are ideal candidates to attain high electrical conductivity because the charged elocalization in the framework can be promoted by generating mixed-valence MOFs upon partial oxidation or reduction of donor and acceptorf ragments, respectively. [48][49][50] In general, COFs also exhibit low electrical conductivity that is strongly dependent on the conjugation and charged elocalization of the framework, and on the intermoleculari nteractions between the layers, whereas the use of electroactive building blocks is an efficient strategyt of abricate COF-based electronic and optoelectronic devices. [51] Concerninge nergy storagea nd relateda pplications, [7,52] redox-active MOFs and COFs have been widely explored as electrode materials for which electrical and ionic conductivity and stability are criticalf or the electrochemical performance of the frameworks.…”

Section: Electroactive Building Blockmentioning

confidence: 99%

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Souto

Strutyński

Melle‐Franco

et al. 2020

Chemistry A European J

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Electroactive organic molecules have received a lot of attention in the field of electronics because of their fascinating electronic properties, easy functionalization and potential low cost towards their implementation in electronic devices. In recent years, electroactive organic molecules have also emerged as promising building blocks for the design and construction of crystalline porous frameworks such as metal–organic frameworks (MOFs) and covalent‐organic frameworks (COFs) for applications in electronics. Such porous materials present certain additional advantages such as, for example, an immense structural and functional versatility, combination of porosity with multiple electronic properties and the possibility of tuning their physical properties by post‐synthetic modifications. In this Review, we summarize the main electroactive organic building blocks used in the past few years for the design and construction of functional porous materials (MOFs and COFs) for electronics with special emphasis on their electronic structure and function relationships. The different building blocks have been classified based on the electronic nature and main function of the resulting porous frameworks. The design and synthesis of novel electroactive organic molecules is encouraged towards the construction of functional porous frameworks exhibiting new functions and applications in electronics.

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Section: Electroactive Building Blockmentioning

confidence: 99%

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Souto

Strutyński

Melle‐Franco

et al. 2020

Chemistry A European J

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“…The porous nature of this family of compounds as well as their structural diversity has led to a wide range of potential applications being investigated. The properties of these materials which could lead to applications include: gas adsorption/separation [ 1 , 2 , 3 , 4 ], catalysis [ 5 , 6 ], drug delivery and biomedicine [ 7 , 8 ], photoluminescence sensors [ 9 , 10 , 11 , 12 , 13 ], magnetism [ 14 , 15 , 16 , 17 ], proton conductivity [ 18 , 19 , 20 , 21 ], or mechanical energy storage, among others [ 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 ]. Prior to its further use for an application, significant effort must be devoted to the characterization of the thermal and mechanical stability of MOFs [ 41 , 42 ].…”

Section: Introductionmentioning

confidence: 99%

Influence of Thermal and Mechanical Stimuli on the Behavior of Al-CAU-13 Metal–Organic Framework

et al. 2020

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The response of the metal–organic framework aluminum-1,4-cyclohexanedicarboxylate or Al-CAU-13 (CAU: Christian Albrecht University) to the application of thermal and mechanical stimuli was investigated using synchrotron powder X-ray diffraction (SPXRD). Variable temperature in situ SPXRD data, over the range 80–500 K, revealed a complex evolution of the structure of the water guest containing Al-CAU-13•H2O, the dehydration process from ca. 310 to 370 K, and also the evolution of the guest free Al-CAU-13 structure between ca. 370 and 500 K. Rietveld refinement allowed this complexity to be rationalized in the different regions of heating. The Berman thermal Equation of State was determined for the two structures (Al-CAU-13•H2O and Al-CAU-13). Diamond anvil cell studies at elevated pressure (from ambient to up to ca. 11 GPa) revealed similarities in the structural responses on application of pressure and temperature. The ability of the pressure medium to penetrate the framework was also found to be important: non-penetrating silicone oil caused pressure induced amorphization, whereas penetrating helium showed no plastic deformation of the structure. Third-order Vinet equations of state were calculated and show Al-CAU-13•H2O is a hard compound for a metal–organic framework material. The mechanical response of Al-CAU-13, with tetramethylpyrazine guests replacing water, was also investigated. Although the connectivity of the structure is the same, all the linkers have a linear e,e-conformation and the structure adopts a more open, wine-rack-like arrangement, which demonstrates negative linear compressibility (NLC) similar to Al-MIL-53 and a significantly softer mechanical response. The origin of this variation in behavior is attributed to the different linker conformation, demonstrating the influence of the S-shaped a,a-conformation on the response of the framework to external stimuli.

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“…A significant factor that limits the utility of framework materials in electrochemical processes is inadequate contact between the framework and electrode surface, which increases interfacial resistance and limiting electron diffusion. 29 There are several methods to create a stronger framework–electrode interface. The most universally applied method is to make an ink containing the framework, a chemical binder (generally Nafion), and a conductive carbon material.…”

Section: Framework Design Considerations For Electrocatalysismentioning

confidence: 99%

From Molecules to Porous Materials: Integrating Discrete Electrocatalytic Active Sites into Extended Frameworks

et al. 2020

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Metal–organic and covalent–organic frameworks can serve as a bridge between the realms of homo- and heterogeneous catalytic systems. While there are numerous molecular complexes developed for electrocatalysis, homogeneous catalysts are hindered by slow catalyst diffusion, catalyst deactivation, and poor product yield. Heterogeneous catalysts can compensate for these shortcomings, yet they lack the synthetic and chemical tunability to promote rational design. To narrow this knowledge gap, there is a burgeoning field of framework-related research that incorporates molecular catalysts within porous architectures, resulting in an exceptional catalytic performance as compared to their molecular analogues. Framework materials provide structural stability to these catalysts, alter their electronic environments, and are easily tunable for increased catalytic activity. This Outlook compares molecular catalysts and corresponding framework materials to evaluate the effects of such integration on electrocatalytic performance. We describe several different classes of molecular motifs that have been included in framework materials and explore how framework design strategies improve on the catalytic behavior of their homogeneous counterparts. Finally, we will provide an outlook on new directions to drive fundamental research at the intersection of reticular-and electrochemistry.

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Redox-active metal–organic frameworks for energy conversion and storage

Abstract: We review progress in the study of electroactive MOFs with redox activity for energy conversion and storage. Recent advances in mixed-valence MOFs are highlighted, which have led to record conductivities towards metallic porous materials.

Cited by 260 publications

References 218 publications

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Influence of Thermal and Mechanical Stimuli on the Behavior of Al-CAU-13 Metal–Organic Framework

From Molecules to Porous Materials: Integrating Discrete Electrocatalytic Active Sites into Extended Frameworks

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