Name: Electron Spin Resonance (ESR) Spectra of Cu-THQ MOF
Uploaded: 2023-06-09T14:10:00
Description: Watch this Scientific Journal Video about Electron Spin Resonance ESR Spectra of Cu-THQ MOF at JoVE.com

electron spin resonance (esr) spectra of cu-thq mof

Caratterizzazione magnetometrica di MOF Redox-Active Elettrochimica allo Stato Solido

Since the term metal-organic framework (MOF) was introduced in the late 1990s, and especially in the 2010s, the most representative scientific concepts concerning MOFs have arisen from their structural porosity, including guest encapsulation, separation, catalytic properties, and molecule sensing1,2,3,4. Meanwhile, scientists were quick to realize that it is essential for MOFs to possess stimuli-responsive electronic properties in order to integrate them into modern smart devices. This idea triggered the spawning and flourishing of the conductive two-dimensional (2D) MOF family in the past 10 years, thereby opening the gate for MOFs to play key roles in electronics5 and, more attractively, in electrochemical energy storage devices6. These 2D MOFs have been incorporated as active materials in alkali metal batteries, aqueous batteries, pseudocapacitors, and supercapacitors7,8,9, and have exhibited tremendous capacity as well as excellent stability. However, to design better-performing 2D MOFs, it is crucial to understand their charge storage mechanisms in detail. Therefore, this article aims to provide a comprehensive understanding of the electrochemical mechanisms of MOFs, which can aid in the rational design of better-performing MOFs for energy storage applications.
In 2014, we first reported the solid-state electrochemical mechanisms of MOFs with redox-active sites on both metal cations and ligands10,11.&#160;These mechanisms were interpreted with the help of various in situ and ex situ spectroscopic techniques, such as X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS), X-ray diffraction (XRD), and solid-state nuclear magnetic resonance (NMR). Since then, this research paradigm has become a trend in studies of the solid-state electrochemistry of molecular-based materials12. These methods work fine for identifying the redox events of conventional MOFs with carboxylate bridging ligands, as the molecular orbitals and energy levels of metal cluster building blocks and organic ligands are almost independent of each other in such MOFs12,13.
However, when encountering the strongly correlated 2D MOFs with significant &#960;-d conjugation, the limitations of these spectroscopic methods were exposed. One of these limitations is that the band levels of most aforementioned 2D MOFs cannot be considered as a simple combination of metal clusters and ligands, but are rather a hybridization of them, while most of the spectroscopic methods only provide averaged, qualitative information about the oxidation states14. The other limitation is that the interpretation of these data is always based on the assumption of localized atomic orbitals. Therefore, the intermediate states with metal-ligand hybridization and delocalized electronic states are usually overlooked and described incorrectly with only these spectroscopic methods15. It is necessary to develop new probes for the electronic states of these electrochemical intermediates of not only 2D MOFs, but also other materials with similar conjugated or strongly correlated electronic structures, such as covalent organic frameworks16, molecular conductors, and conjugated polymers17.
The most common and powerful tools for assessing the electronic structures of materials are electron spin resonance (ESR) and superconducting quantum interference device (SQUID) magnetic susceptibility measurements18,19. As both rely on unpaired electrons in the system, these tools can provide tentative information about the spin densities, spin distributions, and spin-spin interactions. ESR offers sensitive detection of unpaired electrons, while magnetic susceptibility measurement gives more quantitative signals for upper properties20. Unfortunately, both techniques unavoidably face great challenges when used to analyze the electrochemical intermediates. This is because target samples are not pure, but rather a mixture of target material, conductive additive, binder, and byproduct from the electrolyte, so the obtained data21,22 are the sum of contributions from both the material and the impurities. Meanwhile, most intermediates are sensitive to the environment, including air, water, certain electrolytes, or any other unpredictable perturbations; extra care is necessary while handling and measuring intermediates. Trial and error is normally necessary while dealing with a new combination of electrode material and electrolyte.
Here, we present a new paradigm, called electrochemical magnetometry, for analyzing the electronic states or spin states of 2D MOFs and similar materials using a series of techniques, utilizing electrochemistry and temperature-variable ex situ ESR spectroscopy as well as ex situ magnetic susceptibility measurements20. To demonstrate the effectiveness of this approach, we use Cu3THQ2 (THQ = 1,2,4,5-tetrahydroxybenzoquinone; referred to as Cu-THQ), a representative 2D MOF, as an example. We explain the selection of conductive additives and electrolytes, the fabrication of electrodes and electrochemical cells, as well as details on sample handling and measurement, including possible issues during measurement. By comparing with classic characterizations such as XRD and XAFS, electrochemical magnetometry can provide a comprehensive understanding of the electrochemical mechanism of most MOFs. This approach is capable of capturing unique intermediate states and avoiding incorrect assignment of redox events. The elucidation of energy storage mechanisms using electrochemical magnetometry can also contribute to a better understanding of the structure-function relationships in MOFs, leading to more intelligent synthetic strategies for MOFs and other conjugated materials.

Autore in primo piano: Caratterizzazione magnetometrica di intermedi nell'elettrochimica allo stato solido di strutture metallo-organiche redox attive  

Caratterizzazione magnetometrica di intermedi nell'elettrochimica allo stato solido di strutture metallo-organiche redox-attive

Our research interest lies in understanding the electronic and spin states of 2D pi-d conjugated metal organic frameworks and their correlation with their electrochemical behavior of this MOFs in solid-state energy storage devices. In the last five years, many new 2D-conjugating MOF materials have been reported and studied for their use as active materials in electrochemical cells. However, the mechanism of their charge storage processes is still unclear.Spectroscopic methods, including X-ray diffraction, X-ray photoelectron spectroscopy, and the X-ray absorption fine structure are the mostly common used techniques in this field. Those techniques are crucial for categorizing the specific element's crystal structure and oxygen states. It is not possible to separate a 2D MOF from the device while analyzing its electrochemical intermediate state.Measurement must be taken on a mixture that includes conductive additives and binders. However, to accurately determine the MOF's electrochemical behavior, it is necessary to calibrate the contribution of these additives. Most spectroscopic measures assume well localized electrons in MOFs, but our protocol provides a physical view and reveals strongly-correlated phenomena in these materials.We will continue to better understand the electronic, magnetic, and quantum properties of 2D-conjugated MOFs and bridge the gap between coordination chemistry and solid-state physics through physical insights.

Watch this Scientific Journal Video about Electron Spin Resonance ESR Spectra of Cu-THQ MOF at JoVE.com

Electron Spin Resonance (ESR) Spectra of Cu-THQ MOF  

Spettri di risonanza di spin elettronico (ESR) di Cu-THQ MOF

Collegare la provetta a un tubo di gomma e sigillarla con una valvola. Quindi, fiammare la testa di tenuta della provetta sotto vuoto. Impostare lo spettrometro ESR.Quindi, inserire la provetta preparata nella cavità del microonde e centrare il campione. Quindi, per registrare la VES del campione, scegliere i parametri ottimali come la potenza delle microonde, il tempo di sweep del campo magnetico, la larghezza dello sweep del campo centrale, la frequenza e la larghezza della modulazione, l'ampiezza del canale e la costante di tempo. Quindi, spazzare il campo magnetico e registrare lo spettro ESR.Regolare la quantità di inserimento del marcatore di manganese a 800 e catturare lo spettro ESR con il marcatore di manganese come dimostrato in precedenza. Calibrare il campo magnetico utilizzando sei linee ipersottili per ioni bivalenti di manganese. Il MOF THQ in rame presentava un'ampia linea ESR.Quando il THQ del rame è stato ridotto a 1,5 volt, il segnale degli ioni di rame è scomparso e il segnale radicale è rimasto, indicando che gli ioni sono stati ridotti in rame. La misurazione quantitativa della VES ha confermato che il MOF THQ di rame aveva il 96% di ioni di rame nello stato paramagnetico. La larghezza della linea ESR dello ione rame si è ridotta con la diminuzione della temperatura, mentre lo spostamento chimico è rimasto costante, indicando una significativa interazione anti-ferromagnetica.Un termine paramagnetico significativo indipendente dalla temperatura è stato osservato nella suscettibilità allo spin ESR rispetto alla suscettibilità magnetica del calamaro.

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Chemistry

Electron Spin Resonance (ESR) Spectra of Cu-THQ MOF

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Electrochemical energy storage has been a widely discussed application of redox-active metal-organic frameworks (MOFs) in the past 5 years. Although MOFs ...