Interaction of a Porphyrin Aluminum Metal–Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT Computations
The study presents complementary experiments and quantum chemical DFT computations to reveal the molecular-level interactions of an advanced nanomaterial, porphyrin aluminum metal–organic framework (compound <b>2</b>), with the volatile organic sulfur compound diethyl sulfide (DES). Firs...
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| Format: | Article |
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MDPI AG
2023-11-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/13/22/2916 |
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| author | Shaheed Ullah Michael L. McKee Alexander Samokhvalov |
| author_facet | Shaheed Ullah Michael L. McKee Alexander Samokhvalov |
| author_sort | Shaheed Ullah |
| collection | DOAJ |
| description | The study presents complementary experiments and quantum chemical DFT computations to reveal the molecular-level interactions of an advanced nanomaterial, porphyrin aluminum metal–organic framework (compound <b>2</b>), with the volatile organic sulfur compound diethyl sulfide (DES). First, the intermolecular host–guest interactions during the sorption of DES were explored under dynamic conditions, using the vapor of DES in flowing air. The in situ time-dependent ATR-FTIR spectroscopy in a controlled atmosphere was significantly improved though the use of a new facilely built spectroscopic mini-chamber. The binding site of DES in compound <b>2</b> involves the μ(O–H) and COO<sup>-</sup> groups of the linker of the sorbent. Further, the chemical kinetics of the sorption of DES was investigated, and it follows the Langmuir adsorption kinetic model. That is, depending on the time interval, the process obeys either the pseudo-first- or pseudo-second-order rate law. For the Langmuir adsorption of the pseudo-first order, the rate constant is r<sub>obs</sub> = 0.165 ± 0.017 min<sup>−1</sup>. Next, the interaction of compound <b>2</b> with the saturated vapor of DES yields the adsorption complex compound <b>3</b> [Al-MOF-TCPPH<sub>2</sub>]<sub>2</sub>(DES)<sub>7</sub>. The adsorbed amount of DES is very large at 36.5 wt.% or 365 mg/g sorbent, one of the highest values reported on any sorbent. The molecular modes of bonding of DES in the complex were investigated through quantum chemical DFT computations. The adsorption complex was facilely regenerated by gentle heating. The advanced functional material in this work has significant potential in the environmental remediation of diethyl sulfide and related volatile organic sulfur compounds in air, and it is an interesting target of mechanistic studies of sorption. |
| first_indexed | 2024-03-09T16:34:29Z |
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| language | English |
| last_indexed | 2024-03-09T16:34:29Z |
| publishDate | 2023-11-01 |
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| series | Nanomaterials |
| spelling | doaj.art-9a09a0dd2be842eebd13495763b449ac2023-11-24T14:58:45ZengMDPI AGNanomaterials2079-49912023-11-011322291610.3390/nano13222916Interaction of a Porphyrin Aluminum Metal–Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT ComputationsShaheed Ullah0Michael L. McKee1Alexander Samokhvalov2Department of Chemistry, Morgan State University, 1700 East Cold Spring Lane, Baltimore, MD 21251, USADepartment of Chemistry and Biochemistry, 179 Chemistry Building, Auburn University, Auburn, AL 36849, USADepartment of Chemistry, Morgan State University, 1700 East Cold Spring Lane, Baltimore, MD 21251, USAThe study presents complementary experiments and quantum chemical DFT computations to reveal the molecular-level interactions of an advanced nanomaterial, porphyrin aluminum metal–organic framework (compound <b>2</b>), with the volatile organic sulfur compound diethyl sulfide (DES). First, the intermolecular host–guest interactions during the sorption of DES were explored under dynamic conditions, using the vapor of DES in flowing air. The in situ time-dependent ATR-FTIR spectroscopy in a controlled atmosphere was significantly improved though the use of a new facilely built spectroscopic mini-chamber. The binding site of DES in compound <b>2</b> involves the μ(O–H) and COO<sup>-</sup> groups of the linker of the sorbent. Further, the chemical kinetics of the sorption of DES was investigated, and it follows the Langmuir adsorption kinetic model. That is, depending on the time interval, the process obeys either the pseudo-first- or pseudo-second-order rate law. For the Langmuir adsorption of the pseudo-first order, the rate constant is r<sub>obs</sub> = 0.165 ± 0.017 min<sup>−1</sup>. Next, the interaction of compound <b>2</b> with the saturated vapor of DES yields the adsorption complex compound <b>3</b> [Al-MOF-TCPPH<sub>2</sub>]<sub>2</sub>(DES)<sub>7</sub>. The adsorbed amount of DES is very large at 36.5 wt.% or 365 mg/g sorbent, one of the highest values reported on any sorbent. The molecular modes of bonding of DES in the complex were investigated through quantum chemical DFT computations. The adsorption complex was facilely regenerated by gentle heating. The advanced functional material in this work has significant potential in the environmental remediation of diethyl sulfide and related volatile organic sulfur compounds in air, and it is an interesting target of mechanistic studies of sorption.https://www.mdpi.com/2079-4991/13/22/2916metal–organic frameworkdiethyl sulfidesorptionDFTATR-FTIRkinetics |
| spellingShingle | Shaheed Ullah Michael L. McKee Alexander Samokhvalov Interaction of a Porphyrin Aluminum Metal–Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT Computations Nanomaterials metal–organic framework diethyl sulfide sorption DFT ATR-FTIR kinetics |
| title | Interaction of a Porphyrin Aluminum Metal–Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT Computations |
| title_full | Interaction of a Porphyrin Aluminum Metal–Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT Computations |
| title_fullStr | Interaction of a Porphyrin Aluminum Metal–Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT Computations |
| title_full_unstemmed | Interaction of a Porphyrin Aluminum Metal–Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT Computations |
| title_short | Interaction of a Porphyrin Aluminum Metal–Organic Framework with Volatile Organic Sulfur Compound Diethyl Sulfide Studied via In Situ and Ex Situ Experiments and DFT Computations |
| title_sort | interaction of a porphyrin aluminum metal organic framework with volatile organic sulfur compound diethyl sulfide studied via in situ and ex situ experiments and dft computations |
| topic | metal–organic framework diethyl sulfide sorption DFT ATR-FTIR kinetics |
| url | https://www.mdpi.com/2079-4991/13/22/2916 |
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