碱化插层二维过渡金属碳化物的制备及其对铀酰离子的电化学检测

doi:10.15541/jim20180232

摘要/Abstract

摘要：

二维过渡金属碳化物(MXenes)具有良好的电化学性能与辐照稳定性, 其在放射性核素电化学检测领域有潜在应用价值。本研究通过碱活化的方式处理碳化钛型MXene(Ti₃C₂T_x), 随后将钾插层的Ti₃C₂T_x(K-Ti₃C₂T_x)负载到玻碳电极(GCE)上得到K-Ti₃C₂T_x/GCE修饰电极。采用XRD、SEM、XPS等手段分别对Ti₃C₂T_x和K-Ti₃C₂T_x进行分析表征, 并进一步研究了K-Ti₃C₂T_x/GCE对痕量铀酰离子(UO₂²⁺)的电化学检测性能。循环伏安(CV)实验结果表明, 相比于GCE电极, K-Ti₃C₂T_x/GCE修饰电极对UO₂²⁺的电化学响应显著增强。进一步使用差分脉冲伏安法(DPV)扫描, 发现pH=4.0时, K-Ti₃C₂T_x/GCE修饰电极对UO₂²⁺在铀浓度0.5~10 mg/L范围内呈现良好的线性检测关系, 本方法的检测限为0.083 mg/L(S/N=3), 稳定性和重复性好。

关键词: 铀酰离子, 碱化Ti₃C₂T_x, 电化学检测

Abstract:

Given the good electrochemical performance and excellent irradiation stability of two dimensional transition metal carbides (MXenes), the development of MXene-based electrode materials for radionuclide detection is very promising. In this work, Ti₃C₂T_x MXene was activated via an alkalization strategy to form K⁺ intercalated Ti₃C₂T_x (K-Ti₃C₂T_x). Then the modified electrode of K-Ti₃C₂T_x/GCE was prepared on glassy carbon electrode (GCE). Ti₃C₂T_x and K-Ti₃C₂T_x were characterized by XRD, SEM and XPS techniques, and the electrochemical detection performance of K-Ti₃C₂T_x/GCE for trace uranyl ion (UO₂²⁺) was further investigated. Cyclic voltammetry (CV) experiments showed that the electrochemical response of K-Ti₃C₂T_x/GCE modified electrode to UO₂²⁺ increased significantly. Under the differential pulse voltammetry (DPV) scanning at pH 4.0, the K-Ti₃C₂T_x/GCE modified electrode presented a good linear detection relationship for UO₂²⁺ in the uranium concentration range of 0.5-10mg/L. The detection limit of this method is 0.083 mg/L (S/N = 3), with decent stability and repeatability.

Key words: uranyl ion, alkalization of Ti₃C₂T_x, electrochemical detection

中图分类号:

TQ174

樊懋, 王琳, 裴承新, 石伟群. 碱化插层二维过渡金属碳化物的制备及其对铀酰离子的电化学检测[J]. 无机材料学报, 2019, 34(1): 85-90.

FAN Mao, WANG Lin, PEI Cheng-Xin, SHI Wei-Qun. Alkalization Intercalation of MXene for Electrochemical Detection of Uranyl Ion[J]. Journal of Inorganic Materials, 2019, 34(1): 85-90.

图/表 9

图1 Ti3AlC2、Ti3C2Tx、K-Ti3C2Tx三种材料的XRD图谱

Fig. 1 XRD patterns of the synthesized Ti3AlC2、Ti3C2Tx and K-Ti3C2Tx

图2 三种材料的SEM照片

Fig. 2 SEM images of Ti3AlC2, Ti3C2Tx and K-Ti3C2Tx (a) Ti3AlC2; (b) Ti3C2Tx; (c) Enlarged view of Ti3C2Tx; (d) K-Ti3C2Tx

图3 (a) Ti3C2Tx和K-Ti3C2Tx的XPS光谱图, (b)Ti3C2Tx和K-Ti3C2Tx的Ti2p高分辨图, (c)Ti3C2Tx和K-Ti3C2Tx的O1s高分辨图

Fig. 3 (a) XPS spectra of Ti3C2Tx and K-Ti3C2Tx, (b) high- resolution Ti2p spectra of MXene Ti3C2Tx and K-Ti3C2Tx, (c) high- resolution O1s spectra of MXene Ti3C2Tx and K-Ti3C2Tx

图4 UO22+在不同电极上的循环伏安(CV)响应

Fig. 4 Cyclic voltammetry (CV) results of UO22+ in different electrodes (A) (a) K- Ti3C2Tx/GCE, [U]=0 mg/L, (b) GCE, [U]= 50 mg/L, (c) K Ti3C2Tx/GCE, [U]=50 mg/L; (B) Ti3C2Tx/GCE, [U]= 50 mg/L

图5 pH对K- Ti3C2Tx /GCE检测UO22+的影响

Fig. 5 The effect of pH on UO22+/(K-Ti3C2Tx/GCE)

图6 K-Ti3C2Tx GCE于0.01 mol/L pH=4.0的NaCl中对UO22+的循环伏安扫描结果, 扫描速度为10~100 mV/s, [U]=50 mg/L

Fig. 6 Cyclic voltammetry results of UO22+/(K-Ti3C2Tx/ GCE), pH 4.0, 10-100 mV/s, [U]=50 mg/L (a) CV curves; (b) Plots of peak currents vs scan speed

图7 K-Ti3C2Tx/GCE对UO22+的DPV扫描结果, pH=4.0, [U]=0.5~10 mg/L

Fig 7 Differential pulse voltammetry (DPV) results of UO22+/ (K-Ti3C2Tx/GCE), pH =4.0, [U]=0.5-10 mg/L (a) DPV curves; (b) Plots of peak currents vs concentration of uranium

表1 自来水中样品的分析结果

Table 1 Sample analysis results of uranium content in tap-water

Samples	number	Detected /(mg·L^-1)	Found /(mg·L^-1)	Average /(mg·L^-1)	RSD/%
Tap-water	1	5.00	5.36	5.30	1.34
	2	5.00	5.22
	3	5.00	5.31

表2 K-Ti3C2Tx/GCE电极对U(VI)的回收率结果

Table 2 Determination of U(VI) in the recovery experiments

Samples	Detected /(mg·L^-1)	Added /(mg·L^-1)	Found /(mg·L^-1)	Recovery /%	RSD/%
1	1.0	1.0	1.93	93.00	1.95
2	1.0	2.0	3.06	103.00	1.54
3	1.0	3.0	3.95	98.00	1.12
4	1.0	4.0	5.11	102.75	1.23

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