基于铂、钯负载的MoS2纳米片构建生物传感器及应用

doi:10.16085/j.issn.1000-6613.2020-1901

摘要/Abstract

摘要：

制备了Pt和Pd纳米颗粒修饰的单层MoS₂纳米片（Pt-Pd/MoS₂），通过扫描电镜（SEM）、透射电镜（TEM）和X射线光电子能谱（XPS）对Pt-Pd/MoS₂外部形貌、内部结构和组成进行表征分析，并基于Pt-Pd/MoS₂修饰玻碳电极，并于表面固定乙酰胆碱酯酶（AChE），制备AChE生物传感器。对比了Pt和Pd双金属纳米颗粒、商品化Pt/C及Pt-Pd/MoS₂的电化学性能，结果发现，Pt-Pd/MoS₂的电化学性能明显优于其他两种。测定电极表面酶催化反应的动力学参数K_m为883μmol/L；以马拉硫磷和甲基对硫磷为代表，考察制备电极的检测性能以及制备电极对有机磷农药的检测性能，马拉硫磷的检测范围是1×10^-14～1×10^-5mol/L，检测限为4.69×10^-14mol/L；甲基对硫磷的检测范围是1×10^-15～1×10^-5mol/L，检测限为5.23×10^-15mol/L（S/N=3）；并应用于真实样品检测OPs的回收率为91.4%～103%，显示出良好的回收率和准确性，可应用于实际样品的分析。Pt-Pd/MoS₂为二维纳米材料构建高效生物传感器提供了新思路。

关键词: 贵金属, 有机磷农药, 二硫化钼, 乙酰胆碱酯酶, 生物传感器

Abstract:

Pd and Pt nanoparticle-decorated MoS₂nanocomposites (Pt-Pd/MoS₂) were synthesized and applied to prepare acetylcholinesterase (AChE) biosensors for organophosphorus pesticide detection. The nanoparticles were characterized by SEM, TEM and XPS. The AChE biosensor showed high affinity to acetylthiocholine chloride (ATCl) with K_m of 883μmol/L. The prepared biosensors exhibited high sensitivity towards malathion and parathion methyl, with a linear range of 1×10^-14mol/L to 1× 10^-5mol/L and a detection limit of 4.69×10^-14mol/L (S/N=3) and a linear range of 1×10^-15mol/L to 1×10^-5mol/L and a detection limit of 5.23×10^-15mol/L (S/N=3), respectively. Moreover, the AChE/Pt-Pd/MoS₂/GCE was used to detect OPs in real samples with the recovery of 91.4%—103%. Due to the synergistic effect of the highly dispersed bimetallic nanoparticles and the MoS₂ nanosheets, the Pt-Pd/MoS₂ nanocomposites provide a potential electrode material for biosensor fabrication.

Key words: noble metal, organophosphate pesticide, molybdenum disulfide (MoS₂), acetylcholinesterase, biosensor

中图分类号:

TQ31

周丽亚, 周栖桐, 赵聪俐, 姜艳军, 马丽, 贺莹. 基于铂、钯负载的MoS₂纳米片构建生物传感器及应用[J]. 化工进展, 2021, 40(8): 4371-4380.

ZHOU Liya, ZHOU Xitong, ZHAO Congli, JIANG Yanjun, MA Li, He Ying. Synthesis and utilization of Pt and Pd nanoparticle-decorated MoS₂nanocomposites for fabrication of electrochemical biosensor[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4371-4380.

图/表 11

参考文献 27

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构建电极	检测范围/mol·L^-1	检测限/mol·L^-1	参考文献
AChE/PEDOT-MWCNTs/FTO	1×10^-11~1×10^-9	1×10^-11	［20］
AChE-CS/Pd-Cu NWs/GCE	1.5×10^-13~3×10^-9 和1.5×10^-9~9×10^-9	4.5×10^-9	［21］
AChE-Ag	1×10^-11~1×10^-8	4.0 ×10^-12	［22］
AChE-CS/3DG-CuO NFs/GCE	3×10^-12~4.7×10^-8	9.2×10^-13	［23］
AChE-CS/Pd@Au NRs/GCE	3.6×10^-12~1×10^-7	3.6×10^-12	［24］
AChE/AuNPs/DAR/P-ABSA/GCE	1×10^-8~1×10^-12	5.12×10^-13	［25］
AChE/CS-Ti₃C₂T_x/GCE	1×10^-14~1×10^-8	0.3×10^-14	［26］
AChE/MPtPdN/GCE	1×10^-12~4.7×10^-6	2.6×10^-13	［27］
AChE/ Pt-Pd/MoS₂/GCE	1×10^-14~1×10^-5	5.23×10^-15	本文

构建电极	检测范围/mol·L^-1	检测限/mol·L^-1	参考文献
AChE/PEDOT-MWCNTs/FTO	1×10^-11~1×10^-9	1×10^-11	［20］
AChE-CS/Pd-Cu NWs/GCE	1.5×10^-13~3×10^-9 和1.5×10^-9~9×10^-9	4.5×10^-9	［21］
AChE-Ag	1×10^-11~1×10^-8	4.0 ×10^-12	［22］
AChE-CS/3DG-CuO NFs/GCE	3×10^-12~4.7×10^-8	9.2×10^-13	［23］
AChE-CS/Pd@Au NRs/GCE	3.6×10^-12~1×10^-7	3.6×10^-12	［24］
AChE/AuNPs/DAR/P-ABSA/GCE	1×10^-8~1×10^-12	5.12×10^-13	［25］
AChE/CS-Ti₃C₂T_x/GCE	1×10^-14~1×10^-8	0.3×10^-14	［26］
AChE/MPtPdN/GCE	1×10^-12~4.7×10^-6	2.6×10^-13	［27］
AChE/ Pt-Pd/MoS₂/GCE	1×10^-14~1×10^-5	5.23×10^-15	本文

样品	加入量 /mol·L^-1	检出量 /mol·L^-1	回收率 /%	相对标准偏差 /%
马拉硫磷
1^#	1.00×10^-9	0.932×10^-9	93.2	2.1
2^#	1.00×10^-10	0.943×10^-10	94.3	1.9
3^#	1.00×10^-11	0.999×10^-11	99.9	4.1
甲基对硫磷
1^#	1.00×10^-9	0.914×10^-9	91.4	4.5
2^#	1.00×10^-10	0.962×10^-10	96.2	3.3
3^#	1.00×10^-11	1.03×10^-11	103	4.2

样品	加入量 /mol·L^-1	检出量 /mol·L^-1	回收率 /%	相对标准偏差 /%
马拉硫磷
1^#	1.00×10^-9	0.932×10^-9	93.2	2.1
2^#	1.00×10^-10	0.943×10^-10	94.3	1.9
3^#	1.00×10^-11	0.999×10^-11	99.9	4.1
甲基对硫磷
1^#	1.00×10^-9	0.914×10^-9	91.4	4.5
2^#	1.00×10^-10	0.962×10^-10	96.2	3.3
3^#	1.00×10^-11	1.03×10^-11	103	4.2

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基于铂、钯负载的MoS₂纳米片构建生物传感器及应用

Synthesis and utilization of Pt and Pd nanoparticle-decorated MoS₂nanocomposites for fabrication of electrochemical biosensor

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