Enzyme-MXene Nanosheets: Fabrication and Application in Electrochemical Detection of H2O2

doi:10.15541/jim20190139

Abstract

Abstract:

Two-dimensional MXene nanosheets with vertical junction structure was employed for easy immobilization of horse radish peroxidase enzymes to fabricate the electrochemical hydrogen peroxide (H₂O₂) biosensor. The synthesized MXene nanosheets exhibited large specific area, excellent electronic conductivity and good dispersion in aqueous phase. Horse Radish Peroxidase (HRP) enzymes molecules immobilized on MXene/chitosan/GCE electrode demonstrated good electrocatalytic activity toward reduction of H₂O₂. The fabricated HRP@MXene/chitosan/GCE biosensor exhibited a wide linear range from 5 to 1650 μmol?L ^-1, a limit of detection of 0.74 μmol?L ^-1 and good operation stability. The fabricated biosensor was successfully employed for detection of trace level of H₂O₂ in both solid and liquid food.

Key words: horse radish peroxidase, MXene nanosheets, biosensor, hydrogen peroxide

CLC Number:

TS207

MA Bao-Kai, LI Mian, CHEONG Ling-Zhi, WENG Xin-Chu, SHEN Cai, HUANG Qing. Enzyme-MXene Nanosheets: Fabrication and Application in Electrochemical Detection of H₂O₂[J]. Journal of Inorganic Materials, 2020, 35(1): 131-138.

Figures/Tables 11

Fig. 1 Schematic illustration for fabrication of HRP@MXene (Graphite/TiC/Ti3C2)/chitosan/GCE and H2O2 sensing principle of HRP@MXene/chitosan/GCE

Fig. 2 XRD patterns of G/TiC/Ti3AlC2 and G/TiC/Ti3C2 (A); FT-IR spectra of the MXene, HRP and HRP@MXene (B); SEM images of the MXene G/TiC (C) and Ti3C2 (D)

Fig. S1 EIS of various electrodes in 0.1 mol?L-1 KCL aqueous solution containing 5 mmol?L-1 [Fe(CN)6]3-/4-: Chit (pH 5.0)/GCE (curve b, red line), Chit (pH 6.0)/GCE (curve c, blue line) , Chit (pH 6.5)/GCE (curve d, green line), Chit (pH 7.0)/GCE (curve e, pink line) (A); CV curves of Chit (pH 5.0)/GCE (curve b, red line), Chit (pH 6.0)/GCE (curve c, blue line) , Chit (pH 6.5)/GCE (curve d, green line) , Chit (pH 7.0)/GCE (curve e, pink line) electrodes cycled in 0.1 mol?L-1 KCL aqueous solution containing 5 mmol?L-1 [Fe(CN)6]3-/4-: (potential window: -0.1-0.5 V vs. SCE) (B)

Fig. 3 EIS of Chit(chitosan)/GCE(a), MXene/Chit/GCE(b), HRP@MXene/Chit/GCE (c) electrodes cycled in 0.1 mol?L-1 KCL aqueous solution containing 5 mmol?L-1 [Fe(CN)6]3-/4- (A); CV curves of Chit/GCE (a), MXene/Chit/GCE (b), HRP@MXene/Chit/GCE (c) electrodes cycled in 0.1 mol?L-1 KCL aqueous solution containing 5 mmol?L-1 [Fe(CN)6]3-/4-: (potential window: -0.1-0.5 V vs. SCE) (B)

Fig. 4 CV curves of Chit/GCE (curve a, black line), MXene/ Chit/GCE (curve b, red line), HRP/Chit/GCE (curve c, pink line), HRP@MXene/Chit/GCE (curve d, blue line) electrodes cycled in N2-saturated 0.1 mol?L-1 PBS (pH 7.5) containing 1.0 mmol?L-1 HQ and 2.0 mmol?L-1 H2O2 at a scanning rate of 50 mV?s-1 (potential window: -0.8-0.8 V vs. SCE).

Fig. S2 CV curves of HRP@MXene/Chit/GCE electrodes cycled in N2-saturated 0.1 mol?L-1 PBS (pH 7.5) containing 1.0 mmol?L-1 HQ and 2.0 mmol?L-1 H2O2 at a different scanning rates (20-500 mV?s-1) (A); Plot of cathodic and anodic peak current for HRP@MXene/Chit/GCE versus scanning rate (B); Inset: Plots of anodic peak potential and cathodic peak potential for HRP@MXene/Chit/GCE electrode versus the logarithm of scan rate

Fig.S3 Effects of PBS buffer’s pH (A) and concentration of MXene (B) on the cathodic peak current of enzyme biosensor cycled in N2-saturated 0.1 mol?L-1 PBS ( pH 7.5) containing 1.0 mmol?L-1 HQ and 2.0 mmol?L-1 H2O2; Effects of PBS buffer’s pH (C) and concentration of MXene (D) on the DPV response of enzyme biosensor cycledin N2-saturated 0.1 mol?L-1 PBS (pH 7.5) containing 1.0 mmol?L-1 HQ and 2.0 mmol?L-1 H2O2

Fig. 5 Amperometric responses of HRP@MXene/Chit/ GCE at -0.1 V upon successive additions of H2O2 in astirred 0.1 mol?L-1 PBS (pH 7.5) (A); Calibration curve of amperometric responses at different H2O2 concentrations (B); Amperometric responses of HRP@MXene/Chit/ GCE at -0.1 V upon successive additions of solutions extracted from milk sample (C) and dried scallop (D) spiked with different H2O2 under stirred 0.1 mol?L-1 PBS (pH 7.5)

Electrode	Linear range/(mmol?L^-1)	LOD/(mmol?L^-1)	Ref.
HRP-CTAB-Au/GCE	0.50-105	0.23	[1]
HRP/GO/GCE	0.002-0.5	1.6	[2]
HRP/TB/CCB	0.429-455	0.17	[3]
HRP-BMIM·BF4/SWCNTs	0.49 to 10.2	0.13	[4]
HRP/PGN/GCE	2.77-835	2.67 ×10^-4	[5]
Hb-MXene-GO/Au foil	2-1×10³	1.95	[6]
MXene/GCE	-	0.7×10^-3	[7]
Hb-naf-MXene/GCE	0.1-260	0.02	[8]
TiO₂-Hb-naf-MXene/GCE	0.1-380	1.4×10^-2	[9]
HRP@MXene/Chitosan/GCE	5-1.65×10³	0.74	This work

Sample	Added H₂O₂/ (mmol?L^-1)	Found H₂O₂/ (mmol?L^-1)	Recovery /%	RSD /%
Milk	12.5	13.037	104.30	5.88
Milk	50	52.57	105.14	1.12
Milk	125	136.5	109.20	3.33
Dried scallop	0	66.56	-	-
Dried scallop	12.5	77.84	90.24	6.97
Dried scallop	50	120.08	107.04	1.46
Dried scallop	125	189.11	98.04	8.39

Fig.S4 Amperometric response of HRP@MXene/Chit/GCE in 0.1 mol?L-1 pH 7.5 PBS containing 100 mmol?L-1 of ascorbic acid, glucose, uric acid and H2O2 (Applied potential: -0.1 V) (A); Reduction peak currents of HRP@MXene/Chit/GCE stored in 50 mmol?L-1 PBS (pH 7.5) at 4 for 10 d (B)

References 33

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Enzyme-MXene Nanosheets: Fabrication and Application in Electrochemical Detection of H₂O₂

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