氮掺杂碳原位锚定铜纳米颗粒用于高效氧还原反应催化剂

doi:10.13208/j.electrochem.200724

电化学（中英文） ›› 2021, Vol. 27 ›› Issue (6): 671-680. doi: 10.13208/j.electrochem.200724

氮掺杂碳原位锚定铜纳米颗粒用于高效氧还原反应催化剂

袁会芳¹, 张越¹, 翟兴吾², 胡立兵¹, 葛桂贤², 王刚¹, 于锋¹^,³^,^*(), 代斌¹^,^*()

1.石河子大学化学化工学院,新疆兵团绿色化工过程重点实验室,新疆石河子 832003
2.石河子大学理学院,新疆石河子 832003
3.石河子大学兵团工业技术研究院,清洁能源转化与储存研究组,新疆石河子 832003

收稿日期:2020-07-24 修回日期:2021-02-18 出版日期:2021-12-28 发布日期:2021-02-22
通讯作者: 于锋,代斌 E-mail:yufeng05@mail.ipc.ac.cn;db_tea@shzu.edu.cn
作者简介:第一联系人：
#两位作者对此文章贡献相同。
基金资助:
国家自然科学基金项目(21865025);国家自然科学基金项目(51962032)

Copper Nanoparticles In-Situ Anchored on Nitrogen-Doped Carbon for High-Efficiency Oxygen Reduction Reaction Electrocatalyst

Hui-Fang Yuan¹, Yue Zhang¹, Xing-Wu Zhai², Li-Bing Hu¹, Gui-Xian Ge², Gang Wang¹, Feng Yu¹^,³^,^*(), Bin Dai¹^,^*()

1. Key Laboratory of Green Chemical Process of Xinjiang Corps, College of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, Xinjiang, China
2. School of Science, Shihezi University, Shihezi 832003, Xinjiang, China
3. Shihezi University Bingtuan Industrial Technology Research Institute Clean Energy Conversion and Storage Research Group, Shihezi 832003, Xinjiang, China

Received:2020-07-24 Revised:2021-02-18 Published:2021-12-28 Online:2021-02-22
Contact: Feng Yu,Bin Dai E-mail:yufeng05@mail.ipc.ac.cn;db_tea@shzu.edu.cn

摘要/Abstract

摘要：

与贵金属铂基电化学氧还原反应（ORR）催化剂相比,廉价的非贵金属催化剂引起了广泛的关注。本文以壳聚糖作为一种富含氮和碳元素的生物质资源,利用碳浴法成功制备了氮掺杂碳原位负载铜纳米颗粒（Cu/N-C）催化剂。纯壳聚糖碳化得到的样品N-C的比表面积为67.5 m²·g^-1、平均孔径0.14 nm、平均孔体积8.00 m²·g^-1,与之相比,Cu/N-C比表面积可达607.3 m²·g^-1、平均孔径为2.5 nm、平均孔体积为0.40 cm³·g^-1。通过密度泛函理论（DFT）进行计算表明,Cu(111)/N-C的自由能值低于N-C,更有利于氧还原催化进行。在0.1 mol·L^-1 KOH的介质中,Cu/N-C不仅表现出优异的起始和半波电势（分别为0.96 V和0.84 V）,而且还表现出了优异的抗甲醇性能和稳定性,并且Cu元素掺杂量达到1.67wt.%。

关键词: Cu/N-C, 壳聚糖, 生物质资源, 催化剂, 氧还原反应, 碳浴法

Abstract:

Compared with noble metal platinum (Pt)-based catalysts, inexpensive non-noble metal electrocatalysts have attracted extensive attention for oxygen reduction reaction (ORR). Herein, chitosan as a kind of biomass resource rich in nitrogen and carbon was used to prepare nitrogen-doped carbon (N-C) and N-C in-situ anchored by copper nanoparticles (Cu/N-C). The as-obtained N-C and Cu/N-C nanoparticles were successfully used as non-noble eletrocatalysts tested for ORR. Compared with the N-C, the Cu/N-C showed the high surface area of 607.3 m ²·g^-1 with the mean pore size of 2.5 nm and the pore volume of 0.40 cm³·g^-1. The most positive Gibbs free energy change was the rate determining step for ORR process with the 4e mechanism, where the value of the Cu(111)/N-C(-0.39 eV) was lower than that of the N-C(-0.26 eV). The Cu/N-C exhibited superior onset and half-wave potentials (0.96 V and 0.84 V, respectively) in alkaline media(0.1 mol·L^-1 KOH), all of which are much better than those measured for N-C and commercial Pt/C. Furthermore, the Cu/N-C showed superior methanol crossover avoidance and oxygen reduction stability.

Key words: Cu/N-C, chitosan, biomass resource, electrochemical catalyst, oxygen reduction reaction, carbon-bath method

袁会芳, 张越, 翟兴吾, 胡立兵, 葛桂贤, 王刚, 于锋, 代斌. 氮掺杂碳原位锚定铜纳米颗粒用于高效氧还原反应催化剂[J]. 电化学（中英文）, 2021, 27(6): 671-680.

Hui-Fang Yuan, Yue Zhang, Xing-Wu Zhai, Li-Bing Hu, Gui-Xian Ge, Gang Wang, Feng Yu, Bin Dai. Copper Nanoparticles In-Situ Anchored on Nitrogen-Doped Carbon for High-Efficiency Oxygen Reduction Reaction Electrocatalyst[J]. Journal of Electrochemistry, 2021, 27(6): 671-680.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200724

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I6/671

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Catalyst	Surface area/ (m²·g^-1)	Electrolyte	Onset potential/ V(vs. RHE)	Half-wave potential/ V(vs. RHE)	Ref.
PtNi/C	489	Alkaline	-	0.88	[12]
PtFe alloy	-	Alkaline	0.95	0.88	[13]
Fe_0.3Co_0.7/NC	52	Alkaline	0.98	0.88	[18]
CoFe alloy	745	Alkaline	--	0.89	[19]
FeCo@NC-750	42	Alkaline	0.94	0.80	[16]
FeNi@NCNTs	104	Alkaline	0.95	0.77	[17]
DBD- FeCo@NC	-	Alkaline	0.96	0.88	[21]
FeCo@PCNF-800	304.98	Alkaline/acidic	0.94/0.84	0.85/0.74	[20]
FeNi-NC	1864	Alkaline	0.98	0.83	[23]
Cu/N-C	607.3	Alkaline	0.96	0.84	This work

氮掺杂碳原位锚定铜纳米颗粒用于高效氧还原反应催化剂

Copper Nanoparticles In-Situ Anchored on Nitrogen-Doped Carbon for High-Efficiency Oxygen Reduction Reaction Electrocatalyst

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Sample	Surface area/(m²·g^-1)	Pore volume/(cm³·g^-1)	Pore size/nm
N-C	67.5	0.14	8.00
Cu/N-C	607.3	0.40	2.60