Sains Malaysiana 51(4)(2022): 1197-1212

http://doi.org/10.17576/jsm-2022-5104-20

 

Microwave Synthesis of Blue Emissive N-Doped Carbon Quantum Dots as a Fluorescent Probe for Free Chlorine Detection

(Sintesis Gelombang Mikro N-Terdop Titik Kuantum Karbon Pancaran Biru sebagai Prob Pendarfluor untuk Pengesanan Klorin Bebas)

 

MELISSA ASHA LARSSON1, PRAVENA RAMACHANDRAN1, PURIM JARUJAMRUS2,3 & HOOI LING LEE1*

 

1Nanomaterials Research Group, School of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia

2Department of Chemistry and Centre of Excellence for Innovation in Chemistry, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, Thailand

3Nanomaterials Science, Sensors & Catalysis for Problem-Based Projects, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani, Thailand

 

Received: 8 June 2021/Accepted: 8 September 2021

 

Abstract

Blue emissive N-doped carbon quantum dots (N-CQDs) were prepared through a convenient and sustainable microwave synthesis method using citric acid monohydrate (CA) and urea as carbon and nitrogen sources, respectively, with an optimum molar ratio of 1:3 (CA:Urea). The surface functional groups, morphology, and hydrodynamic characteristics of N-CQDs were analysed with Fourier-transform infrared (FTIR) spectroscopy, high-resolution transmission electron microscopy (HRTEM) and dynamic light scattering (DLS), respectively. The as-synthesised N-CQDs with a quantum yield of 14.8%, exhibited excitation-independent fluorescence emission at 443 nm due to surface-state-induced fluorescence, with an optimum excitation wavelength at 360 nm. The N-CQDs were spherical, with an average particle size of 7.29 ± 3.91 nm based on HRTEM analysis. However, DLS analysis showed that the hydrodynamic size (293.0 ± 110.8 nm) was larger than the average particle size due to the presence of hydrophilic polymer chains and abundant surface groups on the N-CQDs. The free chorine-induced fluorescence quenching of N-CQDs at pH 9 denotes the sensitivity of N-CQDs towards detection of free chlorine in the form of hypochlorite (ClO-) ion, providing the limit of detection (LOD) of 0.4 mM and limit of quantification (LOQ) of 1.2 mM. The fluorescence quenching effect in the N-CQDs caused by the quencher (ClO-) is attributed to the dynamic quenching mechanism, via an intersystem crossing. The low selectivity of N-CQDs towards various ions justified N-CQDs' selectivity as a free chlorine fluorescent probe that can be used for wastewater testing due to its high range sensitivity.

 

Keywords: Fluorescent probe; free chlorine detection; microwave synthesis; N-doped carbon quantum dots (N-CQDs)

 


 

Abstrak

Pancaran biru titik kuantum karbon terdop N (N-CQDs) telah disediakan melalui kaedah gelombang mikro yang mudah dan lestari dengan menggunakan asid sitrik monohidrat (CA) dan urea masing-masing sebagai sumber karbon dan nitrogen dengan nisbah molar optimum 1:3 (CA:Urea). Kumpulan berfungsi permukaan, morfologi dan ciri hidrodinamik N-CQDs telah dianalisis dengan spektroskopi transformasi Fourier inframerah (FTIR), mikroskop pancaran elektron resolusi tinggi (HRTEM) dan penyerakan cahaya dinamik (DLS), masing-masing. N-CQDs yang disintesis dengan 14.8% hasil kuantum telah mengeluarkan pelepasan pendarfluor pengujaan-bebas pada 443 nm disebabkan pendarfluor teraruh keadaan permukaan dengan gelombang pengujaan optimum pada 360 nm. N-CQDs adalah berbentuk sfera dengan purata saiz zarah 7.29 ± 3.91 nm berdasarkan analisis HRTEM. Namun, analisis DLS telah menunjukkan bahawa saiz hidrodinamik (293.0 ± 110.8 nm) adalah lebih besar daripada purata saiz zarah disebabkan kehadiran rantaian polimer hidrofil dan banyak kumpulan berfungsi permukaan pada N-CQDs. Lindapan pendarfluor N-CQDs teraruh klorin bebas pada pH 9 menunjukkan kepekaan N-CQDs terhadap pengesanan klorin bebas dalam bentuk ion hipoklorit (ClO-), yang memberi had pengesanan (LOD) 0.4 mM dan had pengkuantitian (LOQ) 1.2 mM. Kesan lindapan pendarfluor di N-CQDs yang disebabkan oleh pelindap (ClO-) adalah dikaitkan dengan mekanisme lindapan dinamik, melalui lintasan antara sistem. Kepekaan N-CQDs yang rendah terhadap beberapa ion mewajarkan keterpilihan N-CQDs sebagai prob pendarfluor klorin bebas yang boleh digunakan bagi pengujian air sisa disebabkan julat kepekaan yang tinggi.

 

Kata kunci: Pengesanan klorin bebas; prob pendarfluor; sintesis gelombang mikro; titik kuantum karbon terdop N (N-CQDs)

 

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*Corresponding author; email: hllee@usm.my

 

 

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