过渡金属Co3O4/ZnO-ZIF氧还原催化剂Co/Zn-ZIF模板法制备及其产电性能

doi:10.16085/j.issn.1000-6613.2022-1534

化工进展 ›› 2023, Vol. 42 ›› Issue (6): 3066-3076.DOI: 10.16085/j.issn.1000-6613.2022-1534

过渡金属Co₃O₄/ZnO-ZIF氧还原催化剂Co/Zn-ZIF模板法制备及其产电性能

蒋博龙¹^,²(), 崔艳艳², 史顺杰², 常嘉城³, 姜楠¹, 谭伟强²

^1.青岛理工大学滨海人居环境学术创新中心，山东青岛 266000
^2.青岛理工大学环境与市政工程学院，山东青岛 266000
^3.中国石油管道局工程有限公司，河北廊坊 065000

收稿日期:2022-08-19 修回日期:2022-12-26 出版日期:2023-06-25 发布日期:2023-06-29
通讯作者: 蒋博龙
作者简介:蒋博龙（1988—），男，副教授，硕士生导师，研究方向为电化学。E-mail：jiangbolong@qut.edu.cn。
基金资助:
国家自然科学基金(22008134)

Synthesis of transition metal Co₃O₄/ZnO-ZIF oxygen reduction catalyst by Co/Zn-ZIF template method and its electricity generation performance

JIANG Bolong¹^,²(), CUI Yanyan², SHI Shunjie², CHANG Jiacheng³, JIANG Nan¹, TAN Weiqiang²

^1.Innovation Institute for Sustainable Maritime Architecture Research and Technology, Qingdao University of Technology, Qingdao 266000, Shandong, China
^2.Institute of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266000, Shandong, China
^3.China Petroleum Pipeline Engineering Co. , Ltd. , Langfang 065000, Hebei, China

Received:2022-08-19 Revised:2022-12-26 Online:2023-06-25 Published:2023-06-29
Contact: JIANG Bolong

摘要/Abstract

摘要：

开发高效、低成本的微生物燃料电池（MFC）阴极催化剂是目前最迫切需要的。本文选用晶体结构相似的ZIF-8与ZIF-67进行复合，制备了双金属叶片结构Co/Zn-ZIF前体材料，并以此为模板和N、C源，制备了Co₃O₄/ZnO(x)-ZIF阴极催化剂。研究了Co含量(x)对催化剂结构、氧还原（ORR）性能及MFC产电性能的影响。结果表明，在Co₃O₄/ZnO(x)-ZIF催化剂中，Co₃O₄/ZnO(2)-ZIF的性能最佳。各催化剂作为阴极的MFC输出电压大小依次为Pt/C（0.58V）>Co₃O₄/ZnO(2)-ZIF（0.52V）>Co₃O₄/ZnO(3)-ZIF（0.43V）> Co₃O₄/ZnO(1)-ZIF（0.39V）。以Co₃O₄/ZnO(2)-ZIF为阴极催化剂的MFC最大功率密度和化学需氧量（COD）去除率分别为741.1mW/m²和96.1%，接近商用Pt/C的最大功率密度（848.1mW/m²）和化学需氧量（COD）去除率（96.9%）的性能。这归因于其高的吡啶N含量和适宜的孔结构和Co/Zn比值。此外，Co₃O₄/ZnO(2)-ZIF遵循四电子转移路径，在30天的操作中其产电性能未见明显下降，表现出优异的稳定性。

关键词: 微生物燃料电池, 金属有机框架, 氮掺杂, 氧还原, Co₃O₄催化剂, 产电性能

Abstract:

The development of highly efficient and low-cost cathode catalysts for microbial fuel cell (MFC) cathode catalyst is the most urgently needed. In this study, the bimetallic blade structure Co/Zn-ZIF precursor material was prepared by combining the ZIF-8 and ZIF-67 with similar crystal structure. The Co₃O₄/ZnO(x)-ZIF cathode catalyst was prepared by using the Co/Zn-ZIF precursor as template, and N and C sources. The effects of Co content (x) on catalyst structure, oxygen reduction (ORR) performance and power generation performance of MFC were studied. The results showed that among the as prepared Co₃O₄/ZnO(x)-ZIF catalysts, Co₃O₄/ZnO(2)-ZIF possessed the best performance. The MFC output voltage decreased in the order of Pt/C (0.58V)>Co₃O₄/ZnO(2)-ZIF (0.52V)>Co₃O₄/ZnO(3)-ZIF (0.43V)>Co₃O₄/ZnO(1)-ZIF (0.39V). The maximum power density and COD removal rate of MFC using Co₃O₄/ZnO(2)-ZIF as cathode catalyst were 741.1mW/m² and 96.1%, respectively, which were close to those of commercial Pt/C (848.1mW/m² and 96.9%). This is attributed to its high pyridine N content and suitable pore structure and Co/Zn ratio. In addition, Co₃O₄/ZnO(2)-ZIF followed a 4-electron transfer path and exhibited no significant decrease in electrical performance within 30 days operation, showing excellent stability.

Key words: microbial fuel cells, metal organic framework, nitrogen doping, oxidation reduction reaction catalyst, Co₃O₄ catalyst, electricity generation performance

中图分类号:

O643.361

蒋博龙, 崔艳艳, 史顺杰, 常嘉城, 姜楠, 谭伟强. 过渡金属Co₃O₄/ZnO-ZIF氧还原催化剂Co/Zn-ZIF模板法制备及其产电性能[J]. 化工进展, 2023, 42(6): 3066-3076.

JIANG Bolong, CUI Yanyan, SHI Shunjie, CHANG Jiacheng, JIANG Nan, TAN Weiqiang. Synthesis of transition metal Co₃O₄/ZnO-ZIF oxygen reduction catalyst by Co/Zn-ZIF template method and its electricity generation performance[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3066-3076.

图/表 12

图1 微生物燃料电池阴极和阳极

图2 微生物燃料电池结构实物

图3 Co/Zn(2)-ZIF和Co3O4/ZnO(x)-ZIF的吸附性能曲线

图4 Co/Zn(x)-ZIF和Co3O4/ZnO(x)-ZIF的SEM图

图5 Co3O4/ZnO(x)-ZIF的XRD图

图6 Co3O4-ZIF-400 和Co3O4-ZIF/ZnO-400-X的XPS图

表1 Co3O4/ZnO(x)-ZIF催化剂表面元素物质的量分数（%）组成

样品名称	Co－N	吡啶型N	吡咯型N	Co 2p	Zn 2p
Co₃O₄/ZnO(1)-ZIF	35	30	35	9.7	17.4
Co₃O₄/ZnO(2)-ZIF	39	32	29	10.3	16.8
Co₃O₄/ZnO(3)-ZIF	43	29	28	12.6	14.2

图7 Co3O4/ZnO(2)-ZIF的TEM图

图8 Co3O4/ZnO(x)-ZIF的电化学测试结果

表2 Co3O4/ZnO(x)-ZIF催化剂的电化学性能

样品名称	开路电压 /V	功率密度 /mW·m^-2	起始电势 /V	还原峰电势 /V	R_ct/Ω
Co₃O₄/ZnO(1)-ZIF	0.61	598.5	0.020	-0.31	24.2
Co₃O₄/ZnO(2)-ZIF	0.67	741.1	0.086	-0.08	19.6
Co₃O₄/ZnO(3)-ZIF	0.66	656.9	0.082	-0.19	21.0
Pt/C （质量分数为10%）	0.68	848.1	0.146	—	21.6

图9 Co3O4/ZnO(x)-ZIF和Pt/C催化剂的产电性能测试

图10 Co3O4/ZnO(x)-ZIF和Pt/C催化剂的污水处理性能测试

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过渡金属Co₃O₄/ZnO-ZIF氧还原催化剂Co/Zn-ZIF模板法制备及其产电性能

Synthesis of transition metal Co₃O₄/ZnO-ZIF oxygen reduction catalyst by Co/Zn-ZIF template method and its electricity generation performance

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