碳基<strong>Pt@Co</strong>多层次复合催化阴极海水介质电催化氧还原行为研究

doi:10.11901/1005.3093.2023.552

材料研究学报

2024, Vol. 38

Issue (8): 632-640 DOI: 10.11901/1005.3093.2023.552

研究论文

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碳基Pt@Co多层次复合催化阴极海水介质电催化氧还原行为研究

张恒宇¹^,², 黄照单³, 段体岗²(

), 温青¹(

), 李若灿¹^,², 吴厚燃², 马力², 张海兵²

^1.哈尔滨工程大学材料科学与化学工程学院哈尔滨 150001
^2.洛阳船舶材料研究所海洋腐蚀与防护全国重点实验室青岛 266237
^3.山东电力建设第三工程有限公司咨询院青岛 266200

Electrocatalytic Oxygen Reduction of Carbon-based Hierarchical Pt@Co Composite Catalytic Cathode in Natural Seawater

ZHANG Hengyu¹^,², HUANG Zhaodan³, DUAN Tigang²(

), WEN Qing¹(

), LI Ruocan¹^,², WU Houran², MA Li², ZHANG Haibing²

^1.College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
^2.National Key Laboratory of Marine Corrosion and Protection, Luoyang Ship Material Research Institute, Qingdao 266237, China
^3.Sepco III Electric Power Construction Co., LTD, Qingdao 266200, China

引用本文:

张恒宇, 黄照单, 段体岗, 温青, 李若灿, 吴厚燃, 马力, 张海兵. 碳基Pt@Co多层次复合催化阴极海水介质电催化氧还原行为研究[J]. 材料研究学报, 2024, 38(8): 632-640.
Hengyu ZHANG, Zhaodan HUANG, Tigang DUAN, Qing WEN, Ruocan LI, Houran WU, Li MA, Haibing ZHANG. Electrocatalytic Oxygen Reduction of Carbon-based Hierarchical Pt@Co Composite Catalytic Cathode in Natural Seawater[J]. Chinese Journal of Materials Research, 2024, 38(8): 632-640.

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摘要:

以碳布为基体将室温原位生长、高温碳化处理与电沉积方法相结合，制备出具有高活性的铂@钴@氮碳(Pt@Co-N-C@CC)复合材料，研究了这种多层级复合催化阴极材料在海水介质中的电催化氧还原性能。结果表明，这种复合材料具有底层微孔Co-N-C、表层Pt纳米簇的多层次包覆结构，其中ZIF8/ZIF67混合碳化底层提供铂负载位点，有利于Pt纳米颗粒的附着生长，提高了Pt纳米颗粒的分散性。与商业Pt/C催化剂(-0.028 V和-0.401 V vs. Ag/AgCl)相比，Pt@Co-N-C@CC复合材料的氧还原性能较高，其氧还原起始电位和半波电位分别0.075 V和-0.156 V (vs. Ag/AgCl)；与Mg组装的电池，Pt@Co-N-C@CC在5 mA/cm²下的恒流放电电压高于0.8 V，最大功率密度达到7.6 mW/cm²。这种金属有机骨架ZIF8/67衍生的Co-N-C结构与纳米Pt复合，有利于提高Pt的催化活性和抗Cl^-毒化。

关键词 ：复合材料, 碳基Pt@Co多层次电极, 氧还原反应, 海水溶解氧电池

Abstract：

Aiming at the problem of low chloride-poisoning resistance capacity and low electrocatalytic activity for the catalytic material of oxygen reduction, hierarchical composite material was synthesized and its oxygen reduction process was studied in the natural seawater. Herein, A highly active material of hierarchical Pt@Co@-N-C composite coating on carbon cloth was prepared via a combined technique composed of in-situ growth method, high-temperature carbonization treatment and electrodeposition. Characterization results indicate that the as-synthesized composite displays a multi-layered core-shell encapsulation structure with carbon fibers serving as the core matrix, ZIF8/ZIF67-deriving microporous Co-N-C as the bottom coating and the electrodeposited Pt nanoclusters as the apparent catalytic coating. Whereinto, the Co-N-C coating provides lots of depositing sites for improving the dispersibility of Pt nanoparticles, expediting the uniform growth of Pt nanoclusters. Electrochemical results show that in comparison to the commercial Pt/C catalyst, Pt@Co-N-C@CC possesses better electrocatalytic oxygen reduction performance, i.e.which presents onset potential 0.075 V and half-wave potential -0.156 V all much more positive than those of the commercial ones -0.028 V and -0.401 V (vs. Ag/AgCl) respectively. The seawater battery assembling Pt@Co-N-C@CC and Mg shows higher cell voltage of above 0.8 V and maximum power density of 7.6 mW/cm², in contrary, below 0.5 V and 3.9 mW/cm² respectively for the assembling Pt/C and Mg. These prove that the high-efficiency recombination of ZIF8/ZIF67-deriving Co-N-C and Pt nanoclusters benefits to enhance the catalytic activity and improve the chloride-poisoning resistance.

Key words： composite carbon-base Pt@Co hierarchical electrode oxygen reduction reaction seawater dissolved oxygen battery

收稿日期: 2023-11-22

ZTFLH:

TQ152

通讯作者: 段体岗，高级工程师，duantigang@sunrui.net，研究方向为海洋腐蚀与防护、化学能源
温青，教授，wenqing@hrbeu.edu.cn，研究方向为微生物燃料电池、电催化

Corresponding author: DUAN Tigang, Tel: 15725237618, E-mail: duantigang@sunrui.net
WEN Qing, Tel: (0451)82518596, E-mail: wenqing@hrbeu.edu.cn

作者简介: 张恒宇，男，1998年生，硕士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2023.552 或 https://www.cjmr.org/CN/Y2024/V38/I8/632

图1 ZIF8/67@CC和Co-N-C@CC的SEM照片、Pt@Co-N-C@CC的SEM照片以及Pt@Co-N-C@CC的TEM照片

图2 Pt@Co-N-C@CC的HRTEM图像

图3 Pt@N-C@CC与Pt@Co-N-C@CC的XPS总谱图、Pt@Co-N-C@CC的Pt，Co，N的精细谱图以及Pt@N-C@CC的Pt，N精细谱

图4 Pt@Co-N-C@CC, Pt@N-C@CC，Co-N-C@CC的拉曼图像以及Pt@Co-N-C@CC和Pt@N-C@CC的XRD谱

图5 Pt@Co-N-C@CC，Pt@N-C@CC, Co-N-C@CC在不同扫速下的CV图像、拟合所得的Cdl值以及Pt@Co-N-C@CC，Pt@N-C@CC与Pt/C-20%在饱和O2与饱和N2下的CV图像

图6 Pt@Co-N-C@CC在不同扫速下的LSV、不同催化材料在1600 r/min下的LSV图像、不同催化材料的氧还原起始电位与半波电位、催化材料拟合所得的的Tafel斜率、Pt@Co-N-C@CC的稳定性测试以及Pt@Co-N-C@CC和Pt/C-20%@CC的恒电流极化测试

图7 Pt/C-20%@CC和Pt@Co-N-C@CC的功率密度曲线

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