Amine-Functionalized Metal-Organic Frameworks and Covalent Organic Polymers as Potential Sorbents for Removal of Formaldehyde in Aqueous Phase: Experimental Versus Theoretical Study

Kowsalya Vellingiri, Ya Xin Deng, Ki-Hyun Kim, Jheng Jie Jiang, Taejin Kim, Jin Shang, Wha Seung Ahn, Deepak Kukkar, Danil W. Boukhvalov

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3 Citations (Scopus)

Abstract

Porous materials have been identified as efficient sorbent media to remove volatile organic compounds. To evaluate their potential as adsorbents, the adsorptive removal of formaldehyde (FA) in aqueous environments was investigated using four materials, two water-stable metal-organic frameworks (MOFs) of UiO-66 (U6) and U6-NH 2 (U6N) and two covalent organic polymers (COPs) with amine-functionality, CBAP-1-EDA (CE) and CBAP-1-DETA (CD). U6N exhibited the highest removal capacity of 93% (0.56 mg g -1 ) of the tested materials [e.g., CE (81.1%, 0.53 mg g -1 ) > CD (67.2%, 0.43 mg g -1 ) > U6 (66.9%, 0.42 mg g -1 )], which was 2 times higher than that of the reference sorbent, activated carbon (AC: 50%, 0.30 mg g -1 ). The results of Fourier transform infrared and powder X-ray diffraction analyses confirmed the interactions between FA molecules and the amine components of the materials (U6N, CD, and CE). According to density functional theory calculations, the formation of hydrogen bonds between FA molecules and amine components was apparent and was further verified by FA/amine distance (CD: 2.83, CE: 2.88, and U6N: 2.66 Å) along with enthalpy values (CD: ?32.4, CE: ?45.5, and U6N: ?272 kJ mol -1 ). In case of U6, the major interactions occurred in the metal-clusters (?19.3 kJ mol -1 ) via electrostatic interactions (distance: 5.49 Å). Furthermore, the sorption by amine-functionalized materials such as U6N is suggested to be dominated by hydrogen bonding which ultimately led to the formation of imine. If the performance of the tested materials is evaluated in terms of partition coefficient, U6N (1153 mg g -1 mM -1 ) is found as the outperformer in all tested subjects. Regeneration of spent MOFs/COPs was also plausible in the presence of ethanol to maintain their structural integrity even after 10 adsorption-desorption cycles. Overall, the selected MOFs/COPs were seen to have very high removal capacity for hazardous FA molecules in aqueous phase.

Original languageEnglish
Pages (from-to)1426-1439
Number of pages14
JournalACS Applied Materials and Interfaces
Volume11
Issue number1
DOIs
StatePublished - 2019 Jan 9

Fingerprint

DEET
Organic polymers
Sorbents
Formaldehyde
Amines
Metals
Molecules
Hydrogen bonds
Volatile Organic Compounds
Imines
Structural integrity
Coulomb interactions
Volatile organic compounds
Activated carbon
X ray powder diffraction
Adsorbents
Density functional theory
Porous materials
Sorption
Enthalpy

Keywords

  • COPs
  • HPLC
  • MOFs
  • adsorption
  • formaldehyde

Cite this

Vellingiri, Kowsalya ; Deng, Ya Xin ; Kim, Ki-Hyun ; Jiang, Jheng Jie ; Kim, Taejin ; Shang, Jin ; Ahn, Wha Seung ; Kukkar, Deepak ; Boukhvalov, Danil W. / Amine-Functionalized Metal-Organic Frameworks and Covalent Organic Polymers as Potential Sorbents for Removal of Formaldehyde in Aqueous Phase : Experimental Versus Theoretical Study. In: ACS Applied Materials and Interfaces. 2019 ; Vol. 11, No. 1. pp. 1426-1439.
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abstract = "Porous materials have been identified as efficient sorbent media to remove volatile organic compounds. To evaluate their potential as adsorbents, the adsorptive removal of formaldehyde (FA) in aqueous environments was investigated using four materials, two water-stable metal-organic frameworks (MOFs) of UiO-66 (U6) and U6-NH 2 (U6N) and two covalent organic polymers (COPs) with amine-functionality, CBAP-1-EDA (CE) and CBAP-1-DETA (CD). U6N exhibited the highest removal capacity of 93{\%} (0.56 mg g -1 ) of the tested materials [e.g., CE (81.1{\%}, 0.53 mg g -1 ) > CD (67.2{\%}, 0.43 mg g -1 ) > U6 (66.9{\%}, 0.42 mg g -1 )], which was 2 times higher than that of the reference sorbent, activated carbon (AC: 50{\%}, 0.30 mg g -1 ). The results of Fourier transform infrared and powder X-ray diffraction analyses confirmed the interactions between FA molecules and the amine components of the materials (U6N, CD, and CE). According to density functional theory calculations, the formation of hydrogen bonds between FA molecules and amine components was apparent and was further verified by FA/amine distance (CD: 2.83, CE: 2.88, and U6N: 2.66 {\AA}) along with enthalpy values (CD: ?32.4, CE: ?45.5, and U6N: ?272 kJ mol -1 ). In case of U6, the major interactions occurred in the metal-clusters (?19.3 kJ mol -1 ) via electrostatic interactions (distance: 5.49 {\AA}). Furthermore, the sorption by amine-functionalized materials such as U6N is suggested to be dominated by hydrogen bonding which ultimately led to the formation of imine. If the performance of the tested materials is evaluated in terms of partition coefficient, U6N (1153 mg g -1 mM -1 ) is found as the outperformer in all tested subjects. Regeneration of spent MOFs/COPs was also plausible in the presence of ethanol to maintain their structural integrity even after 10 adsorption-desorption cycles. Overall, the selected MOFs/COPs were seen to have very high removal capacity for hazardous FA molecules in aqueous phase.",
keywords = "COPs, HPLC, MOFs, adsorption, formaldehyde",
author = "Kowsalya Vellingiri and Deng, {Ya Xin} and Ki-Hyun Kim and Jiang, {Jheng Jie} and Taejin Kim and Jin Shang and Ahn, {Wha Seung} and Deepak Kukkar and Boukhvalov, {Danil W.}",
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Amine-Functionalized Metal-Organic Frameworks and Covalent Organic Polymers as Potential Sorbents for Removal of Formaldehyde in Aqueous Phase : Experimental Versus Theoretical Study. / Vellingiri, Kowsalya; Deng, Ya Xin; Kim, Ki-Hyun; Jiang, Jheng Jie; Kim, Taejin; Shang, Jin; Ahn, Wha Seung; Kukkar, Deepak; Boukhvalov, Danil W.

In: ACS Applied Materials and Interfaces, Vol. 11, No. 1, 09.01.2019, p. 1426-1439.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Amine-Functionalized Metal-Organic Frameworks and Covalent Organic Polymers as Potential Sorbents for Removal of Formaldehyde in Aqueous Phase

T2 - Experimental Versus Theoretical Study

AU - Vellingiri, Kowsalya

AU - Deng, Ya Xin

AU - Kim, Ki-Hyun

AU - Jiang, Jheng Jie

AU - Kim, Taejin

AU - Shang, Jin

AU - Ahn, Wha Seung

AU - Kukkar, Deepak

AU - Boukhvalov, Danil W.

PY - 2019/1/9

Y1 - 2019/1/9

N2 - Porous materials have been identified as efficient sorbent media to remove volatile organic compounds. To evaluate their potential as adsorbents, the adsorptive removal of formaldehyde (FA) in aqueous environments was investigated using four materials, two water-stable metal-organic frameworks (MOFs) of UiO-66 (U6) and U6-NH 2 (U6N) and two covalent organic polymers (COPs) with amine-functionality, CBAP-1-EDA (CE) and CBAP-1-DETA (CD). U6N exhibited the highest removal capacity of 93% (0.56 mg g -1 ) of the tested materials [e.g., CE (81.1%, 0.53 mg g -1 ) > CD (67.2%, 0.43 mg g -1 ) > U6 (66.9%, 0.42 mg g -1 )], which was 2 times higher than that of the reference sorbent, activated carbon (AC: 50%, 0.30 mg g -1 ). The results of Fourier transform infrared and powder X-ray diffraction analyses confirmed the interactions between FA molecules and the amine components of the materials (U6N, CD, and CE). According to density functional theory calculations, the formation of hydrogen bonds between FA molecules and amine components was apparent and was further verified by FA/amine distance (CD: 2.83, CE: 2.88, and U6N: 2.66 Å) along with enthalpy values (CD: ?32.4, CE: ?45.5, and U6N: ?272 kJ mol -1 ). In case of U6, the major interactions occurred in the metal-clusters (?19.3 kJ mol -1 ) via electrostatic interactions (distance: 5.49 Å). Furthermore, the sorption by amine-functionalized materials such as U6N is suggested to be dominated by hydrogen bonding which ultimately led to the formation of imine. If the performance of the tested materials is evaluated in terms of partition coefficient, U6N (1153 mg g -1 mM -1 ) is found as the outperformer in all tested subjects. Regeneration of spent MOFs/COPs was also plausible in the presence of ethanol to maintain their structural integrity even after 10 adsorption-desorption cycles. Overall, the selected MOFs/COPs were seen to have very high removal capacity for hazardous FA molecules in aqueous phase.

AB - Porous materials have been identified as efficient sorbent media to remove volatile organic compounds. To evaluate their potential as adsorbents, the adsorptive removal of formaldehyde (FA) in aqueous environments was investigated using four materials, two water-stable metal-organic frameworks (MOFs) of UiO-66 (U6) and U6-NH 2 (U6N) and two covalent organic polymers (COPs) with amine-functionality, CBAP-1-EDA (CE) and CBAP-1-DETA (CD). U6N exhibited the highest removal capacity of 93% (0.56 mg g -1 ) of the tested materials [e.g., CE (81.1%, 0.53 mg g -1 ) > CD (67.2%, 0.43 mg g -1 ) > U6 (66.9%, 0.42 mg g -1 )], which was 2 times higher than that of the reference sorbent, activated carbon (AC: 50%, 0.30 mg g -1 ). The results of Fourier transform infrared and powder X-ray diffraction analyses confirmed the interactions between FA molecules and the amine components of the materials (U6N, CD, and CE). According to density functional theory calculations, the formation of hydrogen bonds between FA molecules and amine components was apparent and was further verified by FA/amine distance (CD: 2.83, CE: 2.88, and U6N: 2.66 Å) along with enthalpy values (CD: ?32.4, CE: ?45.5, and U6N: ?272 kJ mol -1 ). In case of U6, the major interactions occurred in the metal-clusters (?19.3 kJ mol -1 ) via electrostatic interactions (distance: 5.49 Å). Furthermore, the sorption by amine-functionalized materials such as U6N is suggested to be dominated by hydrogen bonding which ultimately led to the formation of imine. If the performance of the tested materials is evaluated in terms of partition coefficient, U6N (1153 mg g -1 mM -1 ) is found as the outperformer in all tested subjects. Regeneration of spent MOFs/COPs was also plausible in the presence of ethanol to maintain their structural integrity even after 10 adsorption-desorption cycles. Overall, the selected MOFs/COPs were seen to have very high removal capacity for hazardous FA molecules in aqueous phase.

KW - COPs

KW - HPLC

KW - MOFs

KW - adsorption

KW - formaldehyde

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DO - 10.1021/acsami.8b17479

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JF - ACS Applied Materials and Interfaces

SN - 1944-8244

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