experiment file setup for nitrogen porosimetry of metal&#45;organic frameworks &#40;mofs&#41;

Utilizzo della porosimetria ad azoto per caratterizzare strutture metallo-organiche

Relevance of surface area and pore volume 
The accurate characterization of porous materials is imperative to understanding their potential applications. Surface area and pore volume are important quantitative metrics that provide insight into metal-organic framework (MOF) performance in a variety of applications, including gas adsorption, separation, catalysis, and sensing1.
The surface area of a MOF is a parameter that quantifies the amount of surface available for interactions with guest molecules and can affect its performance in various applications2,3. In gas adsorption applications, the surface area of a MOF reflects binding site availability and affinity, which is directly related to its separation performance4. In catalysis applications, MOF surface area can affect the number of active sites and their accessibility to reactant molecules and, thus, their catalytic activity5. The quantity and accessibility of active sites are also relevant in sensing applications, as more guest interactions with active sites lead to improved sensitivity (and potentially selectivity)6. The surface area can also affect the stability of the MOF under extreme conditions, as a larger surface area can indicate a higher number of surface defects7.
The pore volume of a MOF is a parameter that quantifies the amount of void space within the porous structure. It is defined as the total volume of the pores in the MOF, which includes both the open (accessible) and closed (inaccessible) pores. The pore volume of a MOF can affect its performance in various applications, including gas adsorption, separation, and catalysis. Like surface area, the pore volume of a MOF is directly related to its capacity for gas uptake and storage and its ability to allow guest molecules to reach adsorptive or catalytic sites8.
Using nitrogen sorption to determine surface area and pore volume 
Both surface area and pore volume are typically measured using gas adsorption techniques, most commonly nitrogen sorption. Nitrogen is chosen as the adsorbate in Brunauer-Emmett-Teller (BET) analysis due to its quadrupole moment, where the orientation of the nitrogen molecule is dependent on the surface chemistry of the adsorbent, allowing for the formation of a monolayer. The plot of nitrogen uptake as a function of pressure can be used to obtain information about the surface and pore sizes of the MOF. The material surface area and total pore volume can be calculated using the sorption data9. The overall goal of the method detailed here is to obtain nitrogen sorption data and use that data to calculate MOF surface area and pore volume.
The BET method10 is a widely used technique for determining the specific surface area of a porous material, based on the principle that the adsorption of a gas onto a solid surface is a function of the surface area, the properties of the gas molecule, and the system. A known amount of an adsorbate gas (such as nitrogen) is introduced to the sample material over a given pressure range, and the amount of gas adsorbed onto the surface is measured at each pressure increment. The data is used to calculate the specific surface area by relating the adsorbate uptake, pressure, and monolayer capacity, which is represented by the BET equation9:
<img alt="Equation 1" src="/files/ftp_upload/65716/65716eq01.jpg" style="margin: auto;" /> (equation 1; eq. 1)
where: 
p = equilibrium pressure of adsorbate (Pa) 
p0 = adsorbate saturation pressure (Pa) 
n = adsorbate uptake amount (m3/g) 
nm = monolayer capacity (m3/g) 
C = BET constant (unitless)
The monolayer capacity is related to the total surface area by the following equation:
<img alt="Equation 2" src="/files/ftp_upload/65716/65716eq02.jpg" style="margin: auto;" /> (equation 2; eq. 2)
where: 
St = total MOF surface area (m2) 
nm = monolayer capacity (m3/g) 
NAv = Avogadro&#39;s number (molecule/mol) 
scs = cross sectional area of adsorbate molecule (m2/molecule) 
Vmolar = adsorbate molar volume (m3/mol)
The Barrett-Joyner-Halenda (BJH) method11 is a common procedure that utilizes desorption data to calculate the total pore volume. Like the BET method, a known amount of adsorbate gas (often nitrogen) is introduced to the sample. The partial pressure of the adsorbate is then incrementally decreased, and the volume of gas desorbed at each step is measured. Under the assumption that desorption in each pore first occurs in the capillary volume, followed by a reduction in adsorbed layer thickness, the BJH equation relates the volume desorbed to the adsorbed layer thickness, pore radius, and pore volume. This relationship can be represented with a BJH pore size distribution plot, which plots pore radius against pore volume. The distribution is integrated with respect to pore size to determine the total pore volume. The BJH equation12 is written as:
<img alt="Equation 3" src="/files/ftp_upload/65716/65716eq03.jpg" style="margin: auto;" /> (equation 3; eq. 3)
where: 
n = desorption step (unitless) 
vn = volume of pores emptied of capillary condensate (m3) 
&#916;Vn = volume of adsorbate removed from pores (m3) 
&#916;tn = change in adsorbed layer thickness (m) 
A = surface area of pores involved in desorption (m2) 
Rn = BJH constant dependent on average pore size (unitless) 
c = BJH constant, dependent on average adsorbed layer thickness (unitless)

Autore in primo piano: Caratterizzazione di materiali porosi per favorire lo sviluppo di robuste strutture metallo-organiche con comportamento di adsorbimento 

Determinazione delle aree superficiali e dei volumi dei pori delle strutture metallo-organiche

Our group focuses on synthesizing and characterizing porous materials for applications like water harvesting, air purification, and capturing carbon dioxide. What we're really interested in, is understanding how the size, volume, connectivity, and chemistry of the pores, impact the absorption performance, and then using those insights to inform our work on materials design. So robust characterization techniques are essential.Characterization is an essential aspect of any porous material research. X-ray diffraction, gas absorption techniques, and thermal analysis techniques are among the top methods for characterization. These can also be used to study structural stability, which is a crucial feature of any material used for real world applications.Surface area and pore volume are two of the most important properties of porous materials. These properties can be measured using commercially available instruments that operate with established methods and software. Nitrogen as an absorbate is inexpensive, readily available, and safe.The measurements are quick and reliable.

Watch this Scientific Journal Video about Experiment File Setup for Nitrogen Porosimetry of Metal-Organic Frameworks MOFs at JoVE.com

Experiment File Setup for Nitrogen Porosimetry of Metal-Organic Frameworks (MOFs)  

Configurazione del file dell'esperimento per la porosimetria dell'azoto di strutture metallo-organiche (MOF)

Iniziare creando un file di esempio nel software dello strumento di assorbimento. A tale scopo, aprire il software dello strumento, fare clic su file, quindi su nuovo campione. Nella scheda della descrizione del campione, immettere il nome del campione, la massa e la densità del campione.Per impostare i parametri di analisi, aprire la scheda delle condizioni di analisi e selezionare il gas e l'azoto assorbenti e le condizioni di analisi come metodo BET. Quindi fare clic sul pulsante dello spazio libero e inserire se lo spazio libero deve essere misurato dallo strumento, inserito dall'utente o calcolato. Selezionare se il dewar dell'azoto verrà abbassato durante la misurazione e se il sistema eseguirà un test per il degassamento del campione.Quindi, seleziona PO e inserisci se verrà misurato dal tubo PO, inserito dall'utente o calcolato. Immettere il valore dell'ordine di acquisto, se applicabile. Selezionate T, immettete la temperatura di analisi di 77 kelvin e fate clic su OK.Nel passaggio successivo, selezionare il riempimento e impostare se il campione verrà riempito prima e dopo l'analisi. Se si sceglie una delle due opzioni, selezionare l'identità del gas di riempimento come azoto e fare clic su OK. Nella sezione di raccolta dell'isoterma, selezionare le pressioni target.Fare clic su pressioni, quindi immettere i valori di pressione isotermica da un P su P0 compreso tra zero e uno a intervalli di 0,005 e fare clic su OK. Quindi fare clic su opzioni e immettere la tolleranza di pressione relativa del 5% prima di fare clic su OK. Infine, apri la scheda delle opzioni del report e seleziona i grafici di analisi dei dati da segnalare.Fare clic su Salva con nome, assegnare un nome al file e selezionare una cartella di destinazione.

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Research

JoVE Journal

Chemistry

Experiment File Setup for Nitrogen Porosimetry of Metal&#45;Organic Frameworks &#40;MOFs&#41;

413 Views.  Georgia Institute of Technology. Iniziare creando un file di esempio nel software dello strumento di assorbimento. A tale scopo, aprire il software dello strumento, fare clic su file, quindi su nuovo campione. Nella scheda della descrizione del campione, immettere il nome del campione, la massa e la densità del campione.Per impostare i parametri di analisi, aprire la scheda delle condizioni di analisi e selezionare il gas e l'azoto assorbenti e le condizioni di analisi come metodo BET. Quindi fare clic sul pulsante d...

Video: Experiment File Setup for Nitrogen Porosimetry of Metal-Organic Frameworks (MOFs)  

Determining Surface Areas and Pore Volumes of Metal-Organic Frameworks

The surface area and pore volume of a metal-organic framework (MOF) can provide insight into its structure and potential applications. Both parameters are commonly determined using the data from nitrogen sorption experiments; commercial instruments to perform these measurements are also widely available. These instruments will calculate structural parameters, but it is essential to understand how to select input data and when calculation methods apply to the sample MOF. This article outlines the use of the Brunauer-Emmett-Teller (BET) method and Barrett-Joyner-Halenda (BJH) method for the calculation of surface area and pore volume, respectively. Example calculations are performed on the representative MOF UiO-66. Although widely applicable to MOFs, sample materials and adsorption data must meet certain criteria for the calculated results to be considered accurate, in addition to proper sample preparation. The assumptions and limitations of these methods are also discussed, along with alternative and complementary techniques for the MOF pore space characterization.

This article describes the use of nitrogen porosimetry to characterize metal-organic frameworks, using UiO-66 as a representative material.

The surface area and pore volume of a metal-organic framework (MOF) can provide insight into its structure and potential applications. Both parameters are ...

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Chimica

Preparation of the Metal&#45;Organic Framework &#40;MOF&#41; Sample for Nitrogen Porosimetry

Preparation of the Metal-Organic Framework (MOF) Sample for Nitrogen Porosimetry  

Begin by measuring the mass of an empty sample tube. Then load 30 to 50 milligrams of the metal organic framework or MOF UIO 66 into the sample tube, and measure the mass of the sample loaded tube. Next, attach the sample tube to the sample preparation system while securing the seal with a 0.5 inch O-ring.Place the tube inside the heating mantle. Set the temperature controller to the designated activation temperature of 120 degrees Celsius. Then open the valve connecting the system to the vacuum and wait for the pressure to stabilize before leaving the sample for the designated activation time of 24 hours.After that, remove the tube from the heating mantle and allow the sample to cool to room temperature. Backfill the sample tube with nitrogen and remove it from the preparation system. Finally, measure the mass of the sample tube along with the activated sample.Using the equation displayed, calculate the mass of the activated sample.