3D-printed lab-in-a-syringe voltammetric cell based on a working electrode modified with a highly efficient Ca-MOF sorbent for the determination of Hg(II)

Christos Kokkinos; Anastasios Economou; Anastasia Pournara; Manolis Manos; Ioannis Spanopoulos; Mercouri Kanatzidis; Thomais Tziotzi; Valeri Petkov; Antigoni Margariti; Panagiotis Oikonomopoulos; Giannis S. Papaefstathiou

doi:10.1016/j.snb.2020.128508

3D-printed lab-in-a-syringe voltammetric cell based on a working electrode modified with a highly efficient Ca-MOF sorbent for the determination of Hg(II)

Christos Kokkinos^*, Anastasios Economou, Anastasia Pournara, Manolis Manos^*, Ioannis Spanopoulos, Mercouri Kanatzidis, Thomais Tziotzi, Valeri Petkov, Antigoni Margariti, Panagiotis Oikonomopoulos, Giannis S. Papaefstathiou

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

54 Scopus citations

Abstract

This work combines, for the first time, 3D-printing technology and a highly efficient metal organic framework (Ca-MOF) as an electrode modifier to produce a novel fully integrated lab-in-a-syringe device for the sensitive determination of Hg(II) by anodic stripping voltammetry. The specific Ca-MOF ([Ca(H₄L)(DMA)₂]·2DMA where H₆L is the N,N’-bis(2,4-dicarboxyphenyl)-oxalamide and DMA is the N,N-dimethylacetamide) shows an exceptional Hg(II) sorption capability over a wide pH range and its mechanism is elucidated via spectroscopic and X-ray diffraction studies. The voltammetric lab-in-a-syringe device is fabricated through a single-step process using a dual extruder 3D printer and is composed of a vessel integrating two thermoplastic conductive electrodes (serving as the counter and pseudo-reference electrodes) and of a small detachable 3D-printed syringe loaded with a graphite paste/Ca-MOF mixture (which serves as the working electrode). After optimization of the fabrication and operational variables, a limit of detection of 0.6 μg L⁻¹ Hg(II) was achieved, which is comparable or lower than that of existing sensors (plastic 3D-printed, gold and MOF-based electrodes). The adoption of 3D printing technology in combination with the highly efficient Ca-MOF enables the fabrication of a simple, low-cost and sensitive electrochemical sensor for Hg(II), which is suitable for on-site applications.

Original language	English (US)
Article number	128508
Journal	Sensors and Actuators, B: Chemical
Volume	321
DOIs	https://doi.org/10.1016/j.snb.2020.128508
State	Published - Oct 15 2020

Funding

This work was partially supported by the Special Account for Research Grants (SARG) of the National and Kapodistrian University of Athens (NKUA) . The Bodossaki Foundation is gratefully acknowledged for donating the TGA to NKUA. The research work, by A. D. Pournara and M. J. Manos, was supported by the Hellenic Foundation for Research and Innovation (H.F.R.I.) under the “First Call for H.F.R.I. Research Projects to support Faculty members and Researchers and the procurement of high-cost research equipment grant” (Project Number: 348). Metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center generously supported by NASA Ames Research Center NNA06CB93 G. MGK would like to acknowledge grant NSF DMR-1708254. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This work was partially supported by the Special Account for Research Grants (SARG) of the National and Kapodistrian University of Athens (NKUA). The Bodossaki Foundation is gratefully acknowledged for donating the TGA to NKUA. The research work, by A. D. Pournara and M. J. Manos, was supported by the Hellenic Foundation for Research and Innovation (H.F.R.I.) under the ?First Call for H.F.R.I. Research Projects to support Faculty members and Researchers and the procurement of high-cost research equipment grant? (Project Number: 348). Metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center generously supported by NASA Ames Research Center NNA06CB93 G. MGK would like to acknowledge grant NSF DMR-1708254. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Keywords

3D-printed electrode
Electrochemical sensing
Mercury
Metal-organic frameworks
Sorption

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Instrumentation
Condensed Matter Physics
Surfaces, Coatings and Films
Metals and Alloys
Electrical and Electronic Engineering
Materials Chemistry

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Kokkinos, C., Economou, A., Pournara, A., Manos, M., Spanopoulos, I., Kanatzidis, M., Tziotzi, T., Petkov, V., Margariti, A., Oikonomopoulos, P., & Papaefstathiou, G. S. (2020). 3D-printed lab-in-a-syringe voltammetric cell based on a working electrode modified with a highly efficient Ca-MOF sorbent for the determination of Hg(II). Sensors and Actuators, B: Chemical, 321, Article 128508. https://doi.org/10.1016/j.snb.2020.128508

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title = "3D-printed lab-in-a-syringe voltammetric cell based on a working electrode modified with a highly efficient Ca-MOF sorbent for the determination of Hg(II)",

abstract = "This work combines, for the first time, 3D-printing technology and a highly efficient metal organic framework (Ca-MOF) as an electrode modifier to produce a novel fully integrated lab-in-a-syringe device for the sensitive determination of Hg(II) by anodic stripping voltammetry. The specific Ca-MOF ([Ca(H4L)(DMA)2]·2DMA where H6L is the N,N{\textquoteright}-bis(2,4-dicarboxyphenyl)-oxalamide and DMA is the N,N-dimethylacetamide) shows an exceptional Hg(II) sorption capability over a wide pH range and its mechanism is elucidated via spectroscopic and X-ray diffraction studies. The voltammetric lab-in-a-syringe device is fabricated through a single-step process using a dual extruder 3D printer and is composed of a vessel integrating two thermoplastic conductive electrodes (serving as the counter and pseudo-reference electrodes) and of a small detachable 3D-printed syringe loaded with a graphite paste/Ca-MOF mixture (which serves as the working electrode). After optimization of the fabrication and operational variables, a limit of detection of 0.6 μg L−1 Hg(II) was achieved, which is comparable or lower than that of existing sensors (plastic 3D-printed, gold and MOF-based electrodes). The adoption of 3D printing technology in combination with the highly efficient Ca-MOF enables the fabrication of a simple, low-cost and sensitive electrochemical sensor for Hg(II), which is suitable for on-site applications.",

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author = "Christos Kokkinos and Anastasios Economou and Anastasia Pournara and Manolis Manos and Ioannis Spanopoulos and Mercouri Kanatzidis and Thomais Tziotzi and Valeri Petkov and Antigoni Margariti and Panagiotis Oikonomopoulos and Papaefstathiou, {Giannis S.}",

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Kokkinos, C, Economou, A, Pournara, A, Manos, M, Spanopoulos, I, Kanatzidis, M, Tziotzi, T, Petkov, V, Margariti, A, Oikonomopoulos, P & Papaefstathiou, GS 2020, '3D-printed lab-in-a-syringe voltammetric cell based on a working electrode modified with a highly efficient Ca-MOF sorbent for the determination of Hg(II)', Sensors and Actuators, B: Chemical, vol. 321, 128508. https://doi.org/10.1016/j.snb.2020.128508

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T1 - 3D-printed lab-in-a-syringe voltammetric cell based on a working electrode modified with a highly efficient Ca-MOF sorbent for the determination of Hg(II)

AU - Kokkinos, Christos

AU - Economou, Anastasios

AU - Pournara, Anastasia

AU - Manos, Manolis

AU - Spanopoulos, Ioannis

AU - Kanatzidis, Mercouri

AU - Tziotzi, Thomais

AU - Petkov, Valeri

AU - Margariti, Antigoni

AU - Oikonomopoulos, Panagiotis

AU - Papaefstathiou, Giannis S.

PY - 2020/10/15

Y1 - 2020/10/15

N2 - This work combines, for the first time, 3D-printing technology and a highly efficient metal organic framework (Ca-MOF) as an electrode modifier to produce a novel fully integrated lab-in-a-syringe device for the sensitive determination of Hg(II) by anodic stripping voltammetry. The specific Ca-MOF ([Ca(H4L)(DMA)2]·2DMA where H6L is the N,N’-bis(2,4-dicarboxyphenyl)-oxalamide and DMA is the N,N-dimethylacetamide) shows an exceptional Hg(II) sorption capability over a wide pH range and its mechanism is elucidated via spectroscopic and X-ray diffraction studies. The voltammetric lab-in-a-syringe device is fabricated through a single-step process using a dual extruder 3D printer and is composed of a vessel integrating two thermoplastic conductive electrodes (serving as the counter and pseudo-reference electrodes) and of a small detachable 3D-printed syringe loaded with a graphite paste/Ca-MOF mixture (which serves as the working electrode). After optimization of the fabrication and operational variables, a limit of detection of 0.6 μg L−1 Hg(II) was achieved, which is comparable or lower than that of existing sensors (plastic 3D-printed, gold and MOF-based electrodes). The adoption of 3D printing technology in combination with the highly efficient Ca-MOF enables the fabrication of a simple, low-cost and sensitive electrochemical sensor for Hg(II), which is suitable for on-site applications.

AB - This work combines, for the first time, 3D-printing technology and a highly efficient metal organic framework (Ca-MOF) as an electrode modifier to produce a novel fully integrated lab-in-a-syringe device for the sensitive determination of Hg(II) by anodic stripping voltammetry. The specific Ca-MOF ([Ca(H4L)(DMA)2]·2DMA where H6L is the N,N’-bis(2,4-dicarboxyphenyl)-oxalamide and DMA is the N,N-dimethylacetamide) shows an exceptional Hg(II) sorption capability over a wide pH range and its mechanism is elucidated via spectroscopic and X-ray diffraction studies. The voltammetric lab-in-a-syringe device is fabricated through a single-step process using a dual extruder 3D printer and is composed of a vessel integrating two thermoplastic conductive electrodes (serving as the counter and pseudo-reference electrodes) and of a small detachable 3D-printed syringe loaded with a graphite paste/Ca-MOF mixture (which serves as the working electrode). After optimization of the fabrication and operational variables, a limit of detection of 0.6 μg L−1 Hg(II) was achieved, which is comparable or lower than that of existing sensors (plastic 3D-printed, gold and MOF-based electrodes). The adoption of 3D printing technology in combination with the highly efficient Ca-MOF enables the fabrication of a simple, low-cost and sensitive electrochemical sensor for Hg(II), which is suitable for on-site applications.

KW - 3D-printed electrode

KW - Electrochemical sensing

KW - Mercury

KW - Metal-organic frameworks

KW - Sorption

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3D-printed lab-in-a-syringe voltammetric cell based on a working electrode modified with a highly efficient Ca-MOF sorbent for the determination of Hg(II)

Abstract

Funding

Keywords

ASJC Scopus subject areas

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