基于PtAu阳极催化剂的柔性生物燃料电池的性能研究

doi:10.6023/A24060196

摘要/Abstract

葡萄糖生物燃料电池(GFC)是一种能够将葡萄糖燃料中的化学能转换为电能的装置, 在自供电可穿戴医疗设备领域有着广泛的应用. 本工作采用一种简单的超声辅助法制备了PtAu纳米颗粒催化剂, 在中性环境下作为柔性GFC的阳极催化剂用于催化葡萄糖. PtAu催化剂对葡萄糖催化具有较高的活性和稳定性. 此外, 本工作还引入了消耗性固态二氧化锰(MnO₂)电极替代O₂还原阴极, 避免溶液中低氧溶解度和缓慢的O₂还原动力学等问题. 通过采用PtAu催化剂修饰的碳布(PtAu/CC)阳极和MnO₂/CC阴极制备的无膜柔性GFC的最大功率密度(P_max)为22.61 μW•cm⁻², 开路电压(E^OCV)为0.439 V, 这为可穿戴设备领域的研究提供了新思路.

关键词: PtAu催化剂, 固态二氧化锰电极, 柔性葡萄糖生物燃料电池, 葡萄糖电催化氧化

The rapid growth of flexible electronics has led to various wearable sensors, circuit, and storage devices. The glucose biofuel cell (GFC) is a device capable of converting the chemical energy from glucose fuel into electrical energy, with a wide range of applications in self-powered wearable medical devices. In this study, a PtAu nanoparticle catalyst was synthesized for the catalysis of glucose in a neutral environment through an ultrasound-assisted method. This method offers the advantages of simple operation, short reaction time, and environmental friendliness. In the synthesis of PtAu catalyst, drying is unnecessary, but the catalyst concentration must be carefully controlled to maintain its catalytic effectiveness. The morphology and structure of the PtAu catalysts were analyzed using transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrum (XPS). The PtAu catalysts were immobilized on a carbon cloth (CC) to construct the anode of flexible GFC. The study investigated the impact of electrochemically active area, varying sweep rates, and pH values on the catalytic performance, demonstrating the PtAu catalyst’s commendable activity and durability for glucose catalysis. Furthermore, a solid manganese dioxide (MnO₂) material was synthesized through a simple hydrothermal method. The morphology and structure MnO₂ were characterized using scanning electron microscopy (SEM) and XRD. The prepared solid MnO₂ material was applied to the CC as the cathode of flexible GFC to address issues such as low oxygen solubility and slow O₂ reduction kinetics in solution. Linear scanning voltammetry (LSV) was employed to examine the influence of glucose on MnO₂. In addition, the effects of various mechanical deformations on the anode and cathode were studied, demonstrating their strong mechanical strain capacity. A membrane-less flexible GFC prepared using a PtAu/CC anode and a MnO₂/CC cathode achieved a maximum power density (P_max) of 22.61 μW•cm⁻² and an open circuit voltage (E^OCV) of 0.439 V, surpassing previous reports in the literature, demonstrating its potential for wearable applications. Notably, the flexible GFC maintains consistent power density and E^OCV even after repeated bending, highlighting its stability.

Key words: PtAu catalyst, solid manganese dioxide electrode, flexible glucose biofuel cell, glucose electrocatalytic oxidation

引用此文

许廷强. 基于PtAu阳极催化剂的柔性生物燃料电池的性能研究[J]. 化学学报, 2024, 82(10): 1022-1030.

Tingqiang Xu. Performance Study of Flexible Biofuel Cell Based on PtAu Anode Catalysts[J]. Acta Chimica Sinica, 2024, 82(10): 1022-1030.

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图/表 11

图1. 柔性GFC组成示意图

Figure 1. Schematic diagram of flexible GFC composition

图2. PtAu催化剂的合成示意图(A)和TEM图(B), XRD谱图(C)以及Au 4f (D)和Pt 4f (E)的XPS图

Figure 2. Schematic diagram the synthetic procedure for PtAu catalyst (A); TEM image (B), XRD pattern (C) of PtAu; XPS spectrum of Au 4f (D) and Pt 4f (E)

图3. MnO2的SEM图(A)和XRD谱图(B)

Figure 3. SEM image and XRD pattern of MnO2

图4. CC电极(a)和PtAu/CC (b)的EIS图

Figure 4. EIS curves of CC (a) and PtAu/CC (b)

图5. PtAu/CC电极(A)在饱和氩气的0.5 mol?L?1 H2SO4溶液中的CV图(扫速: 50 mV?s?1); (B)在含有10 mmol?L?1葡萄糖或不含葡萄糖的0.2 mol?L?1 PBS (pH 7.0)溶液中的CV图(扫速: 20 mV?s?1); (C)在含有10 mmol?L?1葡萄糖的0.2 mol?L?1 PBS (pH 7.0)溶液中不同扫速下的CV图(扫速: 10、20、40、60、80和100 mV?s?1); (D)氧化还原峰电流密度与扫速之间的线性关系, 底液0.2 mol?L?1 PBS (pH 7.0); (E) 在含有10 mmol?L?1葡萄糖的0.2 mol?L?1 PBS溶液中不同pH值的CV图(pH=6、7、8、9和10); (F)在含有10 mmol?L?1葡萄糖的0.2 mol?L?1 PBS (pH 7.0)溶液中连续100次扫描的CV图(扫速: 50 mV?s?1)

Figure 5. (A) CV curve of PtAu/CC in the 0.5 mol?L?1 H2SO4 solution with saturated Ar (scan rate: 50 mV?s?1); (B) CV curves of PtAu/CC in the 0.2 mol?L?1 PBS (pH 7.0) solution with or without 10 mmol?L?1 glucose (scan rate: 20 mV?s?1); (C) CV curves of PtAu/CC in the 0.2 mol?L?1 PBS (pH 7.0) solution with 10 mmol?L?1 glucose at different scan rates (scan rates: 10, 20, 40, 60, 80, and 100 mV?s?1); (D) linear relationship between redox peak current density and scan rate, bottom solution 0.2 mol?L?1 PBS (pH 7.0); (E) CV curves of PtAu/CC in the 0.2 mol?L?1 PBS solution with 10 mmol?L?1 glucose at different pH values (pH=6, 7, 8, 9 and 10); (F) CV curves of PtAu/CC in the 0.2 mol?L?1 PBS (pH 7.0) solution with 10 mmol?L?1 glucose at 100 consecutive scan cycles (scan rate: 50 mV?s?1)

图6. PtAu催化剂在0.2 mol?L?1 PBS (pH 7.0)中催化葡萄糖氧化的机制示意图: (A)氢区; (B)双电层区; (C)氧化区

Figure 6. Schematic diagram for the mechanism of glucose oxidation catalyzed by the PtAu catalyst in the 0.2 mol?L?1 PBS (pH 7.0) solution: (A) hydrogen region; (B) double layer region; (C) oxidation region

图7. (A) CC电极(a)和MnO2/CC (b)的EIS图; (B) MnO2/CC电极在含有和不含有30 mmol?L?1葡萄糖的0.2 mol?L?1 PBS (pH 7.0)溶液中的LSV曲线

Figure 7. (A) EIS curves of CC (a) and MnO2/CC (b); (B) LSV curves of MnO2/CC in the 0.2 mol?L?1 PBS (pH 7.0) solution with and without 30 mmol?L?1 glucose

图8. (A) 电极不同弯曲状态(凸、凹和扭曲)的照片; (B) 电极形变后的EIS图; (C) 形变前后的PtAu/CC在含有30 mmol?L?1葡萄糖的0.2 mol?L?1 PBS (pH 7.0)溶液中的CV图(扫速: 50 mV?s?1); (D) 形变前后的MnO2/CC在0.2 mol?L?1 PBS (pH 7.0)溶液中的LSV图

Figure 8. (A) Photographic images of electrodes in different bending states (convex, concave, and twisted); (B) EIS image after electrode deformation; (C) CV curves of PtAu/CC before and after in the 0.2 mol?L?1 PBS (pH 7.0) solution with 30 mmol?L?1 glucose (scan rate: 50 mV?s?1); (D) LSV curves of MnO2/CC before and after in the 0.2 mol?L?1 PBS (pH 7.0) solution

图9. (A) MnO2/CC柔性阴极(a)和PtAu/CC柔性阳极(b)在0.2 mol?L?1 PBS (pH 7.0)溶液中的EOCV; (B)柔性PtAu||MnO2生物燃料电池的极化曲线(a)及功率密度(b)对EOCV作图, 底液: 含有30 mmol?L?1葡萄糖的0.2 mol?L?1 PBS (pH 7.0)溶液; (C)不同的弯曲状态对于柔性GFC性能的影响; (D)弯曲(凸)程度对于柔性GFC性能的影响

Figure 9. (A) EOCV of MnO2/CC flexible cathode (a) and PtAu/CC flexible anode (b) in the 0.2 mol?L?1 PBS (pH 7.0) solution; (B) the polarization curve (a) and power density (b) for the EOCV, bottom liquid: 0.2 mol?L?1 PBS (pH 7.0) solution containing 30 mmol?L?1 glucose; (C) the influence of different bending states on the performance of flexible GFC; (D) the influence of bending (convex) cycle on the performance of flexible GFC

阳极材料	阴极材料	葡萄糖浓度/ (mmol•L⁻¹)	E^OCV/V	P_max/ (μW•cm⁻²)	参考文献
Raney-Pt	Porous-Pt	8	—	4.4	[31]
PtPd	Pt/C	500	0.616	27.6	[16]
Pt₇₀Ni₃₀	Pt₇₀Ni₃₀	3	0.460	7.2	[32]
Au	Graphene	500	0.82	10.7	[33]
PtAu	MnO₂	30	0.439	22.61	本工作

表1. 本工作与文献报道的GFC的性能比较

Table 1. Performance comparison of this work with GFC reported in the literature

图10. CC (A, B), PtAu/CC (C, D)和MnO2/CC (E, F)的SEM图

Figure 10. SEM images of CC (A, B), PtAu/CC (C, D) and MnO2/CC (E, F)

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