一种含铜固体电极在新型无膜生物电化学系统中的应用研究

doi:10.13209/j.0479-8023.2016.109

北京大学学报自然科学版 ›› 2017, Vol. 53 ›› Issue (1): 135-141.DOI: 10.13209/j.0479-8023.2016.109

一种含铜固体电极在新型无膜生物电化学系统中的应用研究

陶虎春^†(), 于太安, 张晓, 石刚, 李金波

北京大学深圳研究生院环境与能源学院, 深圳市重金属污染控制与资源化重点实验室, 深圳 518055

收稿日期:2015-06-01 修回日期:2015-06-17 出版日期:2016-12-26 发布日期:2017-01-20
通讯作者: 陶虎春
基金资助:
深圳市基础研究项目(JCYJ20130329174424934)和深圳市重点实验室项目(CXB201111240110A)资助

Solid Electrodes with Cu(Ⅱ) Applied in Free-membrane Bioelectrochemical System

Huchun TAO^†(), Taian YU, Xiao ZHANG, Gang SHI, Jinbo LI

Shenzhen Key Laboratory for Heavy Metal Pollution Control and Reutilization, School of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen 518055

Received:2015-06-01 Revised:2015-06-17 Online:2016-12-26 Published:2017-01-20
Contact: Huchun TAO

摘要/Abstract

摘要：

采用壳聚糖修饰电极吸附溶液中 Cu(Ⅱ)制得含铜固体电极, 将其用做新型无膜生物电化学系统(MACMCB)阴极。研究固体电极 Cu(Ⅱ)质量和外阻对 MACMCB 电压的影响。结果表明, 系统电压与含铜固体电极 Cu(Ⅱ)质量及系统外阻正相关, 最大输出电压达 0.6346 V。该系统 Cu(Ⅱ)还原效率高于 92.75%, 表明 Cu(Ⅱ)做电子受体得电子能力强, Cu(Ⅱ)几乎被全部还原。MACMCB 与微生物燃料电池(MFC)的效率对比结果表明, 在一定时间内, MACMCB 在底物降解效率和产能输出方面明显优于 MFC, 推荐含铜固体电极更换时间为 10~30 小时。含铜固体电极中 Cu(Ⅱ)主要以 CuSO₄分子形式存在, 放电后 Cu(Ⅱ)的主要还原产物为单质Cu, 含少量Cu₂O, 另外掺杂部分Cu元素的磷化物和氯化物沉淀。

关键词: 含铜固体电极, 新型无膜生物电化学系统, Cu(Ⅱ)还原, 生物产电, 底物降解

Abstract:

A solid electrode with Cu(Ⅱ) was prepared by utilizing chitosan modified electrode to adsorb Cu(Ⅱ) in the solution, which was used as the cathode of microbial anode and chitosan modified cathode based battery (MACMCB). Different Cu(Ⅱ) masses and external loadings were tested to study the discharge property of MACMCB system. Results indicate that better discharge process relies on a larger amount of Cu(Ⅱ) or a higher external loading in this work. The highest cell voltage is 0.6346 V. The Cu(Ⅱ) reduction efficiency of MACMCB system is higher than 92.75%, indicating a nearly complete reduction of Cu(Ⅱ). The comparison between MACMCB and MFC indicates that MACMCB showes better performance than MFC on substrate consume and electricity output within a period of time. Changing the solid electrode within 10 - 30 hours is recommended. CuSO₄ is directly adsorbed inside the solid electrode. The major reduction product is copper, while the left included Cu₂O, phosphide of copper and chloride of copper.

Key words: solid electrode with Cu(Ⅱ), MACMCB, Cu(Ⅱ) reduction, electricity generation, substrate consume

中图分类号:

TM911
X703

陶虎春, 于太安, 张晓, 石刚, 李金波. 一种含铜固体电极在新型无膜生物电化学系统中的应用研究[J]. 北京大学学报自然科学版, 2017, 53(1): 135-141.

Huchun TAO, Taian YU, Xiao ZHANG, Gang SHI, Jinbo LI. Solid Electrodes with Cu(Ⅱ) Applied in Free-membrane Bioelectrochemical System[J]. Acta Scientiarum Naturalium Universitatis Pekinensis, 2017, 53(1): 135-141.

图/表 6

图1 MACMCB系统研究机理

Fig. 1 Schematic illustration of MACMCB system

图2 不同Cu(Ⅱ)质量条件下MACMCB系统电压随时间变化曲线

Fig. 2 Effect of Cu(Ⅱ) masses on the cell voltage of MACMCB system

图3 不同外阻条件下MACMCB系统电压随时间变化曲线

Fig. 3 Effect of external loadings on the cell voltage of MACMCB system

图4 MACMCB系统55小时内电荷累积曲线(系统外阻300 Ω)

Fig. 4 Electricity quantity accumulation (55 hours) of MACMCB system with an external loading of 300 Ω

图5 MACMCB系统与MFC系统对比

Fig. 5 Comparison between MACMCB and MFC system

图6 放电前后含铜固体电极表面分析(a) 放电前含铜固体电极SEM图; (b) 放电前含铜固体电极EDS元素分析((a)中白色标记长方形区域);(c) 放电后含铜固体电极SEM图; (d) 放电后含铜固体电极EDS元素分析((c)中黑色标记十字区域)

Fig. 6 Surface analysis of solid electrode with Cu(II) before and after discharge

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一种含铜固体电极在新型无膜生物电化学系统中的应用研究

Solid Electrodes with Cu(Ⅱ) Applied in Free-membrane Bioelectrochemical System

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