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

doi:10.11901/1005.3093.2023.552

Chinese Journal of Materials Research

2024, Vol. 38

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

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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

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ZHANG Hengyu, HUANG Zhaodan, DUAN Tigang, WEN Qing, LI Ruocan, WU Houran, MA Li, ZHANG Haibing. Electrocatalytic Oxygen Reduction of Carbon-based Hierarchical Pt@Co Composite Catalytic Cathode in Natural Seawater. Chinese Journal of Materials Research, 2024, 38(8): 632-640.

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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

Received: 22 November 2023

ZTFLH:

TQ152

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

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	ZHANG Hengyu
	HUANG Zhaodan
	DUAN Tigang
	WEN Qing
	LI Ruocan
	WU Houran
	MA Li
	ZHANG Haibing

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https://www.cjmr.org/EN/10.11901/1005.3093.2023.552 OR https://www.cjmr.org/EN/Y2024/V38/I8/632

Fig.1 SEM images of different composite materials (a) ZIF8/67 grown on carbon cloth; (b) ZIF8/67@CC after calcination, (c, d) electrodeposited Pt nanoclusters and (e, f)TEM images of Pt@Co-N-C@CC

Fig.2 HRTEM images of Pt@Co-N-C@CC

Fig.3 XPS full spectrum of Pt@N-C@CC and Pt@Co-N-C@CC (a); XPS fine spectra of Pt 4f, Co 2p and N 1s for Pt@Co-N-C@CC (b~d); XPS fine spectra of Pt 4f for Pt@N-C@CC (e) and XPS fine spectra of N 1s for Pt@N-C@CC (f)

Fig.4 Raman spectra of Pt@Co-N-C@CC, Pt@Co-N-C@CC, Co-N-C@CC (a) and XRD patterns of Pt@Co-N-C@CC and Pt@N-C@CC (b)

Fig.5 CV plots of Pt@Co-N-C@CC, Pt@N-C@CC and Co-N-C@CC with different scanning speeds (a~c); double-layer capacitance values for the three materials (d) and CV plots of Pt@Co-N-C@CC, Pt@N-C@CC and Pt/C-20% in saturated oxygen and saturated nitrogen environments (e, f)

Fig.6 LSV plots of Pt@Co-N-C@CC at different speeds (a); LSV plots of four kinds of catalytic cathodes at 1600 r/min (b); onset potential and half-wave potential of catalytic cathode (c); Tafel slopes calculated from LSV of four catalytic cathodes (d); stability tests of Pt@Co-N-C@CC (e) and constant current polarization curves of Pt@Co-N-C@CC and Pt/C-20%@CC (f)

Fig.7 Power density of seawater battery assembled with Pt/C-20%@CC as cathode (a) and power density (b) of seawater battery assembled with Pt@Co-N-C@CC as cathode

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