2D-titanium carbide (MXene) based selective electrochemical sensor for simultaneous detection of ascorbic acid, dopamine and uric acid

doi:10.1016/j.jmst.2020.07.037

Abstract

Abstract:

Two-dimensional (2D) titanium carbide (MXene) nanosheets exhibited excellent conductivity, flexibility, high volumetric capacity, hydrophilic surface, thermal stability, etc. So, it has been exploited in various applications. Herein, we report synthesis of mixed phase 2D MXene as a catalytic material for simultaneous detection of important biomolecules such as ascorbic acid (AA), dopamine (DA) and uric acid (UA). Crystalline structure, surface morphology and elemental composition of mixed phase titanium carbide (Ti-C-T_x) MXene (T_x = -F, -OH, or -O) nanosheets were confirmed by X-ray diffraction (XRD), Raman spectroscopy, high-resolution transmission electron microscopy (HR-TEM), high-resolution scanning electron microscopy (HR-SEM) and Energy-dispersive X-ray spectroscopy (EDS) mapping analysis. Furthermore, Ti-C-T_x modified glassy carbon electrode (GCE) was prepared and its electrochemical properties are studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). It was found that Ti-C-T_x modified GCE (Ti-C-T_x/GCE) showed excellent electrocatalytic activity and separated oxidation peaks of important biomolecules such as AA (at 0.01 V), DA (at 0.21 V) and UA (at 0.33 V). Also, Ti-C-T_x/GCE sensor is enabled their simultaneous detection in physiological pH from 100 to 1000 μM for AA, 0.5-50 μM for DA and 0.5-4 μM & 100-1500 μM for UA. The limit of detection’s (LOD) was estimated as 4.6 μM, 0.06 μM and 0.075 μM for AA, DA and UA, respectively. Moreover, real sample analysis indicated that spiked AA, DA and UA can be determined accurately by Ti-C-T_x/GCE with the recovery ratio in the range between 100.5%-103% in human urine samples. The proposed Ti-C-T_x modified electrode exhibited good stability, selectivity and reproducibility as an electrochemical sensor for the detection of AA, DA and UA molecules.

Key words: Titanium carbide, Dopamine, Uric acid, Ascorbic acid, Electrochemical sensor

Nagaraj Murugan, Rajendran Jerome, Murugan Preethika, Anandhakumar Sundaramurthy, Ashok K. Sundramoorthy. 2D-titanium carbide (MXene) based selective electrochemical sensor for simultaneous detection of ascorbic acid, dopamine and uric acid[J]. J. Mater. Sci. Technol., 2021, 72: 122-131.

Figures/Tables 13

Scheme 1. Schematic illustration for the preparation of Ti-C-Tx powders.

Fig. 1. (A, B) HR-SEM images of the mixed phase Ti-C-Tx (MXene) layered materials and (C) EDS mapping of Ti, C, O and Al.

Fig. 2. (A, B) TEM images of the Ti-C-Tx nanosheets with different magnifications, (C) HR-TEM images of Ti-C-Tx layers and (D) SAED pattern of Ti-C-Tx layers.

Fig. 3. (A) XRD pattern and (B) Raman spectrum of mixed phase Ti-C-Tx) (MXene) layered material (532 nm laser was used).

Fig. 4. Cyclic voltammograms (CVs) recorded using a bare GCE (red), and Ti-C-Tx/GCE (black) in (A) 1 mM AA, (B) 1 mM DA, (C) 1 mM UA and (D) mixture of 1 mM of (AA, DA and UA) + 0.1 M PBS (pH 7.4).

Fig. 5. The electro-oxidation reaction mechanisms of AA, DA and UA at Ti-C-Tx/GCE.

Fig. 6. The CVs of Ti-C-Tx/GCE electrode recorded in (A) 1 mM AA, (B) 1 mM DA, (C) 1 mM UA at different scan rates in the range from 10 to 150 mV s-1, respectively. (D-F) The linear plots of AA, DA and UA obtained from their oxidation peak current vs. square-root of the scan rates.

Fig. 7. (A, B, C) DPVs recorded for different individual concentrations of AA, DA and UA at the Ti-C-Tx/GCE in 0.1 M PBS (pH 7.4) upon successive additions of different concentrations from 100 to 1000 μM for AA, 5 to 50 μM for DA and 100 to 1500 μM for UA, respectively. (D, E, F) The calibration curves made for AA, DA and UA using their concentrations vs. oxidation peak currents.

Fig. 8. (A) DPVs recorded for different concentrations of DA and UA at the Ti-C-Tx/GCE in 0.1 M PBS (pH 7.4) with successive additions from 0.5 to 4 μM for DA and 0.5 to 4 μM for UA, respectively. (B, C) The calibration curves made from the oxidation peaks currents against concentration of DA and UA, respectively.

Fig. 9. (A) DPVs recorded for different concentrations of AA, DA and UA at the Ti-C-Tx/GCE in 0.1 M PBS (pH 7.4) upon successive additions from 100 to 600 μM for AA, 0.5 to 3 μM for DA and 0.5 to 3 μM for UA, respectively. (B-D) The calibration curves made for AA, DA and UA from their oxidation peak currents vs. concentrations.

Table 1 Analytical data comparison between proposed method and other reported sensors for electrochemical simultaneous detection of AA, DA and UA.

Electrode materials	Linear range (μM)			Limit of detection (LOD) (μM)			Refs.
	AA	DA	UA	AA	DA	UA
AC/GCE	30-95	1-65	2-230	4.96	0.06	0.75	[71]
Fe₃O₄/Co₃O₄/mC@g-C₃N₄/GCE	500-8000	1-70	5-100	12.55	0.21	0.18	[72]
HNP-PtTi	200-1000	4-500	100-1000	24.2	3.2	5.3	[73]
GO/MWNT	5.0-300	5.0-500	3.0-60	1.0	1.5	1.0	[50]
MWCNT-PEDOT/GCE	100-2000	10-330	10-250	100	10	10	[74]
PEDOT-modified Ni/Si MCP	20-1400	12-48	36-216	10	1.5	2.7	[75]
PG/GCE	9-2314	5-710	6-1330	6.45	2.00	4.82	[76]
CILE	50-7400	2-1500	2-220	20	1.00	1.00	[77]
ERGO/GCE	500-2000	0.5-60	0.5-60	250	0.5	0.5	[78]
Ti-C-T_x/GCE	100-1000	0.5 - 50	0.5 - 4; 100 - 1500	4.64	0.06	0.075	This work

Table 2 DPV analysis of spiked AA, DA and UA in diluted human urine samples using Ti-C-Tx modified GCE as a sensor (n = 3).

Sample	Analyte	Concentration added (μM)	Found (μM)^a	Recovery (%)
Urine	AA	100	102 ± 1.1	101
	DA	20	20.1 ± 0.6	100.5
	UA	100	103 ± 1.3	103

Fig. 10. (A) Histogram represents peak currents obtained from DPV using three different Ti-C-Tx modified electrodes at fixed concentrations of AA, DA and UA (each 1 mM) in PBS. (B) CVs of Ti-C-Tx/GCE in 0.1 M PBS (pH 7.4) containing AA, DA and UA (1 mM) after several days of storage. (C) DPV responses were recorded using of Ti-C-Tx/GCE in 0.1 M PBS containing AA (300 μM), DA (1.5 μM), UA (1.5 μM) with the presence of 10 fold concentrated interferent molecules. (D) Histogram representing the variation of peak current responses with the addition of interferent molecules such as (b) urea (c) nicotine, (d) l-cysteine, (e) paracetamol, (f) Cd2+ and (g) Pb2+ in the presence of (a) AA, DA and UA.

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