CIESC Journal ›› 2019, Vol. 70 ›› Issue (1): 319-326.doi: 10.11949/j.issn.0438-1157.20180717

• Material science and engineering, nanotechnology • Previous Articles     Next Articles

Controllable preparation of Co-Fe-Pd nanoparticles and their catalytic activities toward oxygen reduction

Channa WANG1(),Ling LIU1,Huihua WANG1,2(),Tianpeng QU1,Jun TIAN1,Deyong WANG1,Zhenhui KANG2   

  1. 1. Shagang School of Iron and Steel, Soochow University, Suzhou 215021, Jiangsu, China
    2. Institute of Functional Nano and Soft Materials FUNSOM, Soochow University, Suzhou 215021, Jiangsu, China
  • Received:2018-07-02 Revised:2018-09-07 Online:2019-01-05 Published:2018-11-06
  • Contact: Huihua WANG;


Co(FeOH)2, FeCl3 and PdCl2 were used as raw materials, citric acid was used as stabilizer, and ethanol was used as accelerator. Ultrasonic-assisted preparation of Co-Fe-Pd metal nanoparticles was carried out, and the oxygen reduction reaction (ORR) electrocatalytic performance was evaluated. The results show that the average size of Co-Fe-Pd nanoparticles prepared by ultrasonic method is about 3—5 nm, and only Pd diffraction peaks are detected for the Co-Pd,Fe-Pd and Co-Fe-Pd nanoparticles because of the dissolution of Co and Fe into the Pd lattice. Compared to Co, Co-Fe Fe-Pd and Co-Pd nanoparticles, the lattice contraction of Co-Fe-Pd nanoparticles exhibited as the wide peaks is remarkable, which leads to increasing lattice defects and subsequent enhanced catalytic activities. The onset potential of oxygen reduction and the slop of Tafel for the Co-Fe-Pd nanoparticles are 1.03 V(vs RHE) and -87 mV/dec, respectively. The values obtained here are comparable to those of commercial Pt/C catalyst. The transferred electron-number of Co-Fe-Pd nanoparticles is 3.80±0.04 during the oxygen reduction, which is dominated by a four-electron pathway. Furthermore, the peroxide percentage (H2O2) is about 10% from the results of RRDE.

Key words: nanoparticles, catalyst, radiation, electrochemistry, transferred electron-number

CLC Number: 

  • TM 911


Different magnification TEM images and electron diffraction pattern of selected area marked by red rectangle for Co5Fe2Pd1 nanoparticles synthesized in solution with [citric acid] = 0.05 mol/L and V(alcohol) =20 ml"


XRD patterns of synthesized Co5Fe1, Co5Pd1, Fe2Pd1 and Co5Fe2Pd1 nanoparticles (JCPD-05727,JCPD-894897)"


XPS full spectrum and high resolution spectra of Co 2p, Fe 2p and Pd 3d for Co5Fe2Pd1 nanoparticle"

Table 1

XPS analysis of Co-Fe-Pd nanoparticles"

NanoparticleComponentAfter ultrasonicProduct compositon


Curves of LSV and Tafel slops for the Co-Fe-Pd nanoparticles (rotating speed=1600 r/min)"


Curves of RRDE, transferred electron-numbers and yields of H2O2 for nanoparticles"


LSV curves of Co5Fe2Pd1 nanoparticles before and after 1000 cycles in 0.1mol/L KOH solution"


XPS high resolution of Co, Co-Fe, Co-Pd, Fe-Pd andCo-Fe-Pd nanoparticles"

1 王瀛, 张丽敏, 胡天军. 金属空气电池阴极氧还原催化剂研究进展[J]. 化学学报, 2015, 73(4): 316-325.
WangY, ZhangL M, HunT J. Progress in oxygen reduction reaction electro catalysts for metal-air batteries[J]. Acta Chimica Sinica, 2015, 73(4): 316-325.
2 朱明骏, 袁振善, 桑林, 等. 金属/空气电池的研究进展[J]. 电源技术, 2012, 36(12): 1953-1958.
ZhuM J, YuanZ P, SangL, et al. Research progresses of metal/air batteries[J]. Chinese Journal of Power Sources, 2012, 36(12): 1953-1958.
3 李彦龙, 王为. 金属-空气电池中空气电极的研究进展[J].电源技术, 2015,5(9):1106-1109.
LiY L, WangW. Research progress of air electrode for metal-air battery[J]. Chinese Journal of Power Sources, 2015, 5(9): 1106-1109
4 周宇, 王宇新. 杂原子掺杂碳基氧还原反应电催化剂研究进展[J]. 化工学报, 2017, 68(2): 520-534.
ZhouY, WangY X. Recent progress on electrocatalysts towards oxygen reduction reaction based on heteroatoms-doped carbon[J]. CIESC Journal, 2017, 68(2): 520-534.
5 FofanaD, NatarajanS K, HamelinJ, et al. Low platinum, high limiting current density of the PEMFC (proton exchange membrane fuel cell) based on multilayer cathode catalyst approach[J]. Energy, 2014, 64: 398-403.
6 DemarconnayL, CoutanceauC, LégerJ M. Electroreduction of dioxygen (ORR) in alkaline medium on Ag/C and Pt/C nanostructured catalysts—effect of the presence of methanol[J]. Electrochimica Acta, 2004, 49(25): 4513-4521.
7 金燕仙, 施梅勤, 刘委明, 等. Pt/WC-CNTs催化剂的制备及其对氧还原的电催化性能[J]. 化工学报, 2014, 65(10): 4015-4024.
JinY X, ShiM Q, LiuW M, et al. Pt/WC-CNTs electro catalyst for oxygen reduction reaction[J]. CIESC Journal, 2014, 65(10): 4015-4024.
8 NieY, LiL, WeiZ. Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction[J]. Chemical Society Reviews, 2015, 44(8): 2168-2201.
9 ZhuC, LiH, FuS, et al. Highly efficient nonprecious metal catalysts towards oxygen reduction reaction based on three dimensional porous carbon nanostructures[J]. Chemical Society Reviews, 2016, 45(3): 517-531.
10 ZhouM, WangH L, GuoS. Towards high-efficiency nanoelectrocatalysts for oxygen reduction through engineering advanced carbon nanomaterials[J]. Chemical Society Reviews, 2016,45(5): 1273-1307.
11 聂瑶, 丁炜, 魏子栋. 质子交换膜燃料电池非铂电催化剂研究进展[J]. 化工学报, 2015, 66(9): 3305-3318.
NieY, DingW, WeiZ D. Recent advancements of Pt-free catalysts for polymer electrolyte membrane fuel cells[J]. CIESC Journal , 2015, 66(9): 3305-3318.
12 SaY J, ParkC, JeongY, et al. Carbon nanotubes/heteroatom-doped carbo core-sheath nanostructures as highly active, metal-free oxygen reduction electrocatalysts for alkaline fuel cells[J]. Angewandte Chemie International Edition, 2014, 53(16): 4102-4106.
13 HuC, WangL, ZhaoY, et al. Designing nitrogen-enriched echinus-like carbon capsules for highly efficient oxygen reduction reaction and lithium ion storage[J]. Nanoscale, 2014, 6(14): 8002-8009.
14 邹志君, 郑龙珍, 熊乐艳, 等. 一种新型的Fe-N/C氧还原反应电催化剂的制备及其性能研究[J]. 化工学报, 2014, 42(11): 60-62.
ZouZ J, ZhengL Z, XiongL Y, et al. Preparation and performance of a new type of Fe-N/C catalyst for oxygen reduction reaction[J]. CIESC Journal, 2014, 42(11): 60-62.
15 FofanaD, NatarajanS K, HamelinJ, et al. Low platinum, high limiting current density of the PEMFC (proton exchange membrane fuel cell) based on multilayer cathode catalyst approach[J]. Energy, 2014, 64(64): 398-403.
16 KimJ, MommaT, OsakaT. Cell performance of Pd–Sn catalyst in passive direct methanol alkaline fuel cell using anion exchange membrane[J]. Journal of Power Sources, 2009, 189(2): 999-1002.
17 VinodgopalK, HeY, AshokkumarM, et al. Sonochemically prepared platinum-ruthenium bimetallic nanoparticles[J]. Journal of Physical Chemistry B, 2006, 110(9): 3849-52.
18 NakanishiM, TakataniH, KobayashiY, et al. Characterization of binary gold/platinum nanoparticles prepared by sonochemistry technique[J]. Applied Surface Science, 2005, 241(1): 209-212.
19 魏建红, 官建国, 袁润章. 金属纳米粒子的制备与应用[J]. 武汉理工大学学报, 2001, 23(3): 1-4.
WeiJ H, GuanJ G, YuanR Z. Preparation and application of metal nano particles[J]. Journal of Wuhan University of Technology, 2001, 23(3): 1-4.
20 KimJ, MommaT, OsakaT. Synthesis of carbon-supported Pd-Sn catalyst by ultrasonic irradiation for oxygen reduction reaction[J]. Journal of Power Sources, 2009, 189 (2): 909-914.
21 WuY, WangC, ZouL, et al. Incorporation of cobalt into Pd2Sn intermetallic nanoparticles as durable oxygen reduction electrocatalyst[J]. Journal of Electroanalytical Chemistry, 2017, 789: 167-171.
22 VinodgopalK, HeY, AshokkumarM, et al. Sonochemically prepared platinum-ruthenium bimetallic nanoparticles[J]. Journal Physical Chemistry B, 2006, 110(9): 3849-3853.
23 OxleyJ D, MdleleniM M, SuslickK S. Hydrodehalogenation with sonochemically prepared Mo2C and W2C[J]. Catalyst Today, 2004, 88(3/4): 139-146.
24 MizukoshiY, TsuruY, TominagaA, et al. Sonochemical immobilization of noble metal nanoparticles on the surface of maghemite: mechanism and morphological control of the products[J]. Ultrasonics Sonochemistry, 2008, 15(5): 875-80.
25 KimJ, ParkJ E, MommaT, et al. Synthesis of Pd-Sn nanoparticles by ultrasonic irradiation and their electrocatalytic activity for oxygen reduction[J]. Electrochimica Acta, 2009, 54(12): 3412-3418.
26 YuJ C, YuJ, HoW, et al. Preparation of highly photocatalytic active nano-sized TiO2 particles via ultrasonic irradiation[J]. Chemical Communications, 2001, (19): 1942-1943.
27 KimJ, MommaT, OsakaT. Synthesis of carbon-supported Pd-Sn catalyst by ultrasonic irradiation for oxygen reduction reaction[J]. Journal Power Sources, 2009, 189(2): 909-914.
28 BirryL, ZagalJ H, DodeletJ P. Does CO poison Fe-based catalysts for ORR[J]. Electrochemistry Communications, 2010, 12(5): 628-631.
29 VenarussoL B, BooneC V, BettiniJ, et al. Carbon-supported metal nanodendrites as efficient, stable catalysts for the oxygen reduction reaction[J]. Journal of Material Chemistry A, 2018, 6 (4): 1714-1726.
30 LuG L, ZhuY L, LuL, et al. Iron-rich nanoparticle encapsulated, nitrogen doped porous carbon materials as efficient cathode electrocatalyst for microbial fuel cells[J]. Journal of Power Sources, 2016, 315: 302-307.
31 WangX P, KariukiN, VaugheyJ T. Bimetallic Pd-Cu oxygen reduction electrocatalystsfuel cells and energy conversion[J]. Journal of the Electrochemistry Society, 2018, 155(6): B602-B609.
[1] Ning QIN, Qing MIN, Kaiyuan SHAO, Wenxiang HU. Synthesis of 3-methyl-benzidine hydrochloride [J]. CIESC Journal, 2019, 70(S1): 242-247.
[2] Hui SHANG, Yu DING, Wenhui ZHANG. Research progress of microwave assisted biodiesel production [J]. CIESC Journal, 2019, 70(S1): 15-22.
[3] Fanrui MENG, Boyang LI, Xianchun LI, Shuang QIU. Catalysis effects of K2CO3 for gasification of semi-coke [J]. CIESC Journal, 2019, 70(S1): 99-109.
[4] Qiang YU, Yuanwei LU, Xiaopan ZHANG, Yuting WU. Effect of nanoparticles on thermal properties of molten salt composite heat storage materials [J]. CIESC Journal, 2019, 70(S1): 217-225.
[5] Yucai ZENG, Xiaoling LIU, Qifeng LIANG, Jianquan LYU. One-pot synthesis of 2-amino-4-aryl-3-cyano-4H-benzochromene derivatives catalyzed by K2CO3 under microwave irradiation [J]. CIESC Journal, 2019, 70(S1): 110-114.
[6] Chaoqian WANG, Wenlong WANG, Zhe LI, Jing SUN, Zhanlong SONG, Xiqiang ZHAO, Yanpeng MAO. Energy consumption analysis of novel pyrolysis method of sewage sludge based on microwave-induced target-oriented heating [J]. CIESC Journal, 2019, 70(S1): 168-176.
[7] Lianxia HOU, Zhaoping YUAN, Hongchang QIAO, Jinghong ZHOU, Xinggui ZHOU. Mechanistic study on catalytic conversion of glucose into low carbon glycols over nickel promoted tungsten carbide catalyst [J]. CIESC Journal, 2019, 70(4): 1390-1400.
[8] Haibin YU, Qiang LIU, Likun ZHOU, Zan CHEN, Chao LUO, Guanyan ZHANG, Jianjie QIAO Lina WANG. Preparation of MnO x /ZrO2 catalyst and catalytic ozonation degradation of methylorange [J]. CIESC Journal, 2019, 70(4): 1436-1445.
[9] Qiang GAO, Hong LYU, Fan XIONG, Fei CHEN, Zeheng YANG, Weixin ZHANG. Preparation of LiFePO4/C plate cathode materials and their electrochemical properties [J]. CIESC Journal, 2019, 70(4): 1628-1634.
[10] Yucong SONG, Xiaoshu DING, Yahui YAN, Shufang WANG, Yanji WANG. Catalytic performance of graphene oxide composite metal catalyst in dimethyl carbonate synthesis [J]. CIESC Journal, 2019, 70(4): 1401-1408.
[11] Wensheng LIANG, Jiangtao LIU, Yue ZHAO, Wei HUANG, Zhijun ZUO. Theoretical calculation of effect of NiO and Ni catalysts for benzoic acid pyrolysis [J]. CIESC Journal, 2019, 70(4): 1429-1435.
[12] Fengteng HU, Jianlong YAO, Xiaoqing LI, Sihan LI, Xinhuan YAN. Properties of Sr modified Cu-based catalysts for hydrogenation of fructose to mannitol [J]. CIESC Journal, 2019, 70(4): 1420-1428.
[13] Shuai HE, Feng GUO, Guojun KANG, Jian YU, Xuefeng REN, Guangwen XU. Preparation of palladium-based catalysts by complexing-solvothermal method and catalytic oxidation of m-xylene [J]. CIESC Journal, 2019, 70(3): 937-943.
[14] Quan TANG, Yanglong GUO, Wangcheng ZHAN, Yun GUO, Li WANG, Yunsong WANG. Catalytic combustion of propane over PdxPty-ZSM-5/Cordierite monolithic catalyst [J]. CIESC Journal, 2019, 70(3): 944-950.
[15] Chao WANG, Changming LI, Lin HUANGFU, Ping LI, Yunquan YANG, Shiqiu GAO, Jian YU, Guangwen XU. Preparation of red mud-based catalyst and performance for trace ammonia in simulative tail gas [J]. CIESC Journal, 2019, 70(3): 1056-1064.
Full text



[1] LING Lixia, ZHANG Riguang, WANG Baojun, XIE Kechang. Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory[J]. , 2009, 17(5): 805 -813 .
[2] LEI Zhigang, LONG Aibin, JIA Meiru, LIU Xueyi. Experimental and Kinetic Study of Selective Catalytic Reduction of NO with NH3 over CuO/Al2O3/Cordierite Catalyst[J]. , 2010, 18(5): 721 -729 .
[3] SU Haifeng, LIU Huaikun, WANG Fan, LÜXiaoyan, WEN Yanxuan. Kinetics of Reductive Leaching of Low-grade Pyrolusite with Molasses Alcohol Wastewater in H2SO4[J]. , 2010, 18(5): 730 -735 .
[4] WANG Jianlin, XUE Yaoyu, YU Tao, ZHAO Liqiang. Run-to-run Optimization for Fed-batch Fermentation Process with Swarm Energy Conservation Particle Swarm Optimization Algorithm[J]. , 2010, 18(5): 787 -794 .
[5] SUN Fubao, MAO Zhonggui, ZHANG Jianhua, ZHANG Hongjian, TANG Lei, ZHANG Chengming, ZHANG Jing, ZHAI Fangfang. Water-recycled Cassava Bioethanol Production Integrated with Two-stage UASB Treatment[J]. , 2010, 18(5): 837 -842 .
[6] Gao Ruichang, Song Baodong and Yuan Xiaojing( Chemical Engineering Research Center, Tianjin University, Tianjin 300072). LIQUID FLOW DISTRIBUTION IN GAS - LIQUID COUNTER - CONTACTING PACKED COLUMN[J]. , 1999, 50(1): 94 -100 .
[7] Su Yaxin, Luo Zhongyang and Cen Kefa( Institute of Thermal Power Engineering , Zhejiang University , Hangzhou 310027). A STUDY ON THE FINS OF HEAT EXCHANGERS FROM OPTIMIZATION OF ENTROPY GENERATION[J]. , 1999, 50(1): 118 -124 .
[8] Luo Xiaoping(Department of Industrial Equipment and Control Engineering , South China University of Technology, Guangzhou 510641)Deng Xianhe and Deng Songjiu( Research Institute of Chemical Engineering, South China University of Technology, Guangzhou 5106. RESEARCH ON FLOW RESISTANCE OF RING SUPPORT HEAT EXCHANGER WITH LONGITUDINAL FLUID FLOW ON SHELL SIDE[J]. , 1999, 50(1): 130 -135 .
[9] Jin Wenzheng , Gao Guangtu , Qu Yixin and Wang Wenchuan ( College of Chemical Engineering, Beijing Univercity of Chemical Technology, Beijing 100029). MONTE CARLO SIMULATION OF HENRY CONSTANT OF METHANE OR BENZENE IN INFINITE DILUTE AQUEOUS SOLUTIONS[J]. , 1999, 50(2): 174 -184 .

LI Qingzhao;ZHAO Changsui;CHEN Xiaoping;WU Weifang;LI Yingjie


Combustion of pulverized coal in O2/CO2 mixtures and its pore structure development

[J]. , 2008, 59(11): 2891 -2897 .