Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media

Fluorescent carbon dots (CDs) have emerged as sensing systems for wastewater treatment and chemical sensing. Nowadays, different biomass-based materials, including the usage of starch, glucose, and cellulose have been widely employed for the production of CDs. In spite of their susta...

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Main Author: Issa Al-Badri, Mohammed Abdullah
Format: Thesis
Language:English
Published: 2019
Subjects:
Online Access:http://psasir.upm.edu.my/id/eprint/85575/
http://psasir.upm.edu.my/id/eprint/85575/1/FK%202020%2022%20-IR.pdf
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author Issa Al-Badri, Mohammed Abdullah
author_facet Issa Al-Badri, Mohammed Abdullah
author_sort Issa Al-Badri, Mohammed Abdullah
building UPM Institutional Repository
collection Online Access
description Fluorescent carbon dots (CDs) have emerged as sensing systems for wastewater treatment and chemical sensing. Nowadays, different biomass-based materials, including the usage of starch, glucose, and cellulose have been widely employed for the production of CDs. In spite of their sustainability, the fluorescent efficiency of the obtained CDs from these natural resources is still low. This motivates the researchers for doping CDs with various heteroatom species such as nitrogen doping agent. However, long-time synthesis process from 7-72 hr is normally required for obtaining a relatively low fluorescence quantum yield (QY). Additionally, a clear formation mechanism for nitrogen-doped CDs (N-CDs) synthesized hydrothermally from biomass and various heteroatom doping sources along with the origin of the photoluminescence (PL) emission are still under debate. In this work, one-step hydrothermal carbonization route has been used to produce N- CDs from carboxymethylcellulose (CMC) of oil palms empty fruit bunch in the presence of ethylenediamine (EDA-CDs) and linear-structured polyethyleneimine (LPEI-CDs) in an attempt to enhance the fluorescence quantum yield of CDs. At first, the optimum conditions for the hydrothermal route of N-CDs were identified by assessing the effect of different influential variables (reaction temperature, time, and N-weight). The statistical analysis results indicated that the production of LPEI-CDs not only was obtained in a considerably shorter time in comparison to EDA-CDs but also, they had significantly better fluorescent QY. Additionally, the characterization tests were carried out on the optimum N-CDs. The prepared N-CDs are reproducible, highly homogeneous and excellent PL properties with narrow emission bands. Furthermore, the N-CDs are nearly small (approx. 3-8 nm) with narrow size distributions; are stable over a long period of time (at least six months), and maintain their PL properties when re-dispersed in solution. Moreover, LPEI-CDs showed predominantly crystalline nature, and the functional groups from the LPEI have successfully tuned the PL properties of CDs in both the intrinsic and surface electronic structures, and hence improve the fluorescence QY up to 44%. It was concluded that the origin of light emission in N-CDs caused by the interplay between intrinsic state emission originates from graphitic core and extrinsic state emission due to the surface functional groups. Due to the significant interaction between Cu (II) and amino functional groups over the LPEI-CDs surface, the LPEI-CDs were further used as a fluorescent probe for the detection of Cu (II) in aqueous media. The linear relationship between the relative quenching rate and the concentration of Cu (II) (1–30 µM) with a detection limit of 0.93 µM were used. Considering the sustainable production of N-CDs, this PhD research project provides a guide for converting low-quality waste into value-added nanomaterials and applying for different functionalization processes and analytical applications.
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spelling upm-855752021-08-18T02:25:32Z http://psasir.upm.edu.my/id/eprint/85575/ Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media Issa Al-Badri, Mohammed Abdullah Fluorescent carbon dots (CDs) have emerged as sensing systems for wastewater treatment and chemical sensing. Nowadays, different biomass-based materials, including the usage of starch, glucose, and cellulose have been widely employed for the production of CDs. In spite of their sustainability, the fluorescent efficiency of the obtained CDs from these natural resources is still low. This motivates the researchers for doping CDs with various heteroatom species such as nitrogen doping agent. However, long-time synthesis process from 7-72 hr is normally required for obtaining a relatively low fluorescence quantum yield (QY). Additionally, a clear formation mechanism for nitrogen-doped CDs (N-CDs) synthesized hydrothermally from biomass and various heteroatom doping sources along with the origin of the photoluminescence (PL) emission are still under debate. In this work, one-step hydrothermal carbonization route has been used to produce N- CDs from carboxymethylcellulose (CMC) of oil palms empty fruit bunch in the presence of ethylenediamine (EDA-CDs) and linear-structured polyethyleneimine (LPEI-CDs) in an attempt to enhance the fluorescence quantum yield of CDs. At first, the optimum conditions for the hydrothermal route of N-CDs were identified by assessing the effect of different influential variables (reaction temperature, time, and N-weight). The statistical analysis results indicated that the production of LPEI-CDs not only was obtained in a considerably shorter time in comparison to EDA-CDs but also, they had significantly better fluorescent QY. Additionally, the characterization tests were carried out on the optimum N-CDs. The prepared N-CDs are reproducible, highly homogeneous and excellent PL properties with narrow emission bands. Furthermore, the N-CDs are nearly small (approx. 3-8 nm) with narrow size distributions; are stable over a long period of time (at least six months), and maintain their PL properties when re-dispersed in solution. Moreover, LPEI-CDs showed predominantly crystalline nature, and the functional groups from the LPEI have successfully tuned the PL properties of CDs in both the intrinsic and surface electronic structures, and hence improve the fluorescence QY up to 44%. It was concluded that the origin of light emission in N-CDs caused by the interplay between intrinsic state emission originates from graphitic core and extrinsic state emission due to the surface functional groups. Due to the significant interaction between Cu (II) and amino functional groups over the LPEI-CDs surface, the LPEI-CDs were further used as a fluorescent probe for the detection of Cu (II) in aqueous media. The linear relationship between the relative quenching rate and the concentration of Cu (II) (1–30 µM) with a detection limit of 0.93 µM were used. Considering the sustainable production of N-CDs, this PhD research project provides a guide for converting low-quality waste into value-added nanomaterials and applying for different functionalization processes and analytical applications. 2019-12 Thesis NonPeerReviewed text en http://psasir.upm.edu.my/id/eprint/85575/1/FK%202020%2022%20-IR.pdf Issa Al-Badri, Mohammed Abdullah (2019) Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media. Doctoral thesis, Universiti Putra Malaysia. Sewage - Purification Biomass chemicals
spellingShingle Sewage - Purification
Biomass chemicals
Issa Al-Badri, Mohammed Abdullah
Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media
title Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media
title_full Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media
title_fullStr Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media
title_full_unstemmed Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media
title_short Nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media
title_sort nitrogen-doped carbon dots from empty fruit bunch carboxymethylcellulose for selective detection of copper ions in aqueous media
topic Sewage - Purification
Biomass chemicals
url http://psasir.upm.edu.my/id/eprint/85575/
http://psasir.upm.edu.my/id/eprint/85575/1/FK%202020%2022%20-IR.pdf