基于纳米CdS对尿酸的光催化氧化和铜(Ⅱ)配合物对氧的电催化还原的燃料电池性能

doi:10.7503/cjcu20150469

摘要/Abstract

摘要：

以纳米硫化镉薄膜修饰的铟锡氧化物电极(CdS/ITO)作光阳极, 铜(Ⅱ)配合物[Cu(phen)(L-Trp)·(H₂O)]⁺(phen=1,10-菲啰啉, L-Trp=L-色氨酸)修饰单壁碳纳米管(SWCNTs)电极作阴极, 构建了光催化尿酸(UA)燃料电池, 并研究了其性能及热处理温度的影响. 结果表明, 在40 ℃以下获得的纳米CdS修饰电极在320~550 nm波长区间显现明显的吸收和光伏响应, 在可见光辐射下能光催化氧化UA; 较高温度的热处理(200~300 ℃)却降低了纳米CdS对UA的光催化氧化活性. [Cu(phen)(L-Trp)(H₂O)]⁺/SWCNTs电极在-0.131 V电位下呈现一对准可逆的氧化还原峰, 并能电催化还原O₂和H₂O₂. 此外, 基于UA在CdS/ITO电极上的光催化氧化及O₂在[Cu(phen)(L-Trp)(H₂O)]⁺/SWCNTs电极上的电催化还原, 组装了UA(0.2 mmol/L)燃料电池, 其在可见光照射(0.18 mW/cm²)下产生0.52 V开路电压, 13.08 μA/cm²短路光电流, 在0.41 V下呈现的最大功率密度为4.10 μW/cm².

关键词: 尿酸, 燃料电池, 光催化氧化, 硫化镉, 电催化还原, 铜(Ⅱ)配合物

Abstract:

A novel visible light-driven uric acid(UA) fuel cell was preprared by employing CdS nanoparticles modified indium-tin oxide photoanode(CdS/ITO) and [Cu(phen)(L-Trp)(H₂O)]⁺(phen=1,10-phenanthrothine and L-Trp=L-tryptophan) modified single-walled nanotubes(SWCNTs) cathode. The CdS nanoparticles obtained after thermal treatment at 40 ℃ show obvious absorption and open-circuit photovoltage responses between 320 and 550 nm. The CdS/ITO electrode exhibits good photocatalytic activity towards the oxidation of uric acid(UA) upon visible light irradiation. The CdS nanoparticles prepared at high temperatures between 200 and 300 ℃ show smaller photocatalytic activities than those obtained at 40 ℃. The [Cu(phen)(L-Trp)·(H₂O)]⁺/SWCNTs electrode exhibits a pair of quasi-reversible redox peaks at the formal potential of -0.131 V, indicating the electrocatalytic activity towards the reduction of both O₂ and H₂O₂. Furthermore, on the basis of photocatalysis of CdS nanoparticles and electrocatalysis of [Cu(phen)(L-Trp)(H₂O)]⁺, a photocatalytic UA(0.2 mmol/L) fuel cell was elaborately assembled, which showed an open-circuit photovoltage of 0.52 V, a short-circuit photocurrent of 13.08 μA/cm² and a maximum power density of 13.08 μW/cm² at 0.41 V upon the visible light irradiation of 0.18 mW/cm².

Key words: Uric acid, Fuel cell, Photocatalytic oxidation, Cadmium sulfate, Electrocatalytic reduction, Cu(Ⅱ) complex

中图分类号:

O646

TrendMD:

骆金苑, 陈琳琳, 王奕, 李红. 基于纳米CdS对尿酸的光催化氧化和铜(Ⅱ)配合物对氧的电催化还原的燃料电池性能. 高等学校化学学报, 2015, 36(12): 2468.

LUO Jinyuan, CHEN Linlin, WANG Yi, LI Hong. Fabrication and Performance of a Novel Visible Light-driven Fuel Cell Based on Photocatalytic Oxidation of Uric Acid by CdS Nanoparticles and Electrocatalytic Reduction of Oxygen by a Copper(Ⅱ) Complex^†. Chem. J. Chinese Universities, 2015, 36(12): 2468.

图/表 10

Fig.1 Structure of the Cu(Ⅱ) complex(A) and schematic configuration and electron transfer processes of a photocatalytic UA/O2 fuel cell using CdS/ITO anode and Cu(Ⅱ)/SWCNTs cathode(B)

Fig.2 SEM images of CdS/ITO electrodes generated from the thermal treatment at 40 ℃(A) and 300 ℃(B), and [Cu(phen)(L-Trp)(H2O)]+/SWCNTs electrode(C)

Fig.3 Effects of visible light(off or on) on open circuit potential(EOC) of CdS/ITO anodes at different UA concentrations c(UA)/(mmol·L-1): a. 0; b. 0.017; c. 0.033; d. 0.057; e. 0.088; f. 0.125; g. 0.189. Inset shows the photovoltage(ΔEOC)-c(UA) plot.

Fig.4 Electronic absorption spectrum(a) and photovoltage(b) as a function of wavelength for CdS/ITO electrode in buffer solutions

Fig.5 Effects of drying temperature on the photovoltage of CdS/ITO electrode at different UA concentrations c(UA)/(mmol·L-1): a. 0.020; b. 0.041; c. 0.062; d. 0.083; e. 0.123; f. 0.164.

Fig.6 Cyclic voltammograms of Cu(Ⅱ)/SWCNTs electrode in nitrogen-saturated buffer solutions at different scan rates(A), relation of cathodic peak currents with scan rate(B) and change of cathodic peak potentials with natural logarithm of scan rate(C) Scan rate/(V·s-1): a. 0.05; b. 0.10; c. 0.15; d. 0.20; e. 0.25; f. 0.30.

Fig.7 Differential pulse voltammograms of SWCNTs(a) and Cu(Ⅱ)/SWCNTs(b) electrodes in buffer solutions containing saturated O2(A) or 0.2 mmol/L H2O2(B) and of Cu(Ⅱ)/SWCNTs electrode in N2-saturated buffer solutions(c)

Fig.8 Effects of Cu(Ⅱ) concentration on open-circuit potential of CdS/ITO electrode in the absence and presence of visible light Cu(Ⅱ) concentration/(mmol·L-1): a. 0; b. 0.005; c. 0.010; d. 0.016; e. 0.021; f. 0.026; g. 0.031. Inset shows photovoltage vs. Cu(Ⅱ) concentration plot.

Fig.9 Effects of visible light(a) and UV light(b) on open-circuit voltage of 0.2 mmol/L UA/O2 fuel cells employing CdS/ITO anode and Cu(Ⅱ)/SWCNTs cathode

Fig.10 Cell current(a) and power output(b) from 0.2 mmol/L UA/O2 fuel cells using CdS/ITO anode and Cu(Ⅱ)/SWCNTs cathode under the excitation of visible light(A) and UV light(B) by altering the external load from 1000 Ω to 100000 Ω

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