NiO@rGO负载钯、银纳米粒子用作氧还原催化剂

doi:10.13208/j.electrochem.190125

摘要/Abstract

摘要：

为了促进燃料电池的广泛应用,必须研发一种高效、经济的氧还原（ORR）催化剂材料替代目前使用的昂贵的Pt基催化剂. 本文合成了NiO@rGO、Pd-NiO@rGO和Ag-NiO@rGO三种催化剂材料,并对其ORR催化性能进行了比较研究. 结果表明,三种材料均具有催化ORR的能力,但与NiO@rGO相比,Pd-NiO@rGO和Ag-NiO@rGO展示了更加优异的性能,主要表现在其4电子转移ORR过程、起始电位增加,中间产物的产率降低和稳定性提高. 其中,Pd-NiO@rGO作为ORR催化剂的性能最好.

关键词: 氧还原, 催化剂, 氧化镍, 还原氧化石墨烯, 表面修饰

Abstract:

For pervasive applications of fuel cells, highly efficient and economical materials are required to replace Pt-based catalysts for oxygen reduction reaction (ORR). In this study, the NiO@rGO, Pd-NiO@rGO and Ag-NiO@rGO nanoparticles were synthesized, and their catalytic performances toward ORR were investigated. The results revealed that all the three materials were capable of catalyzing ORR, but both the Pd-NiO@rGO and Ag-NiO@rGO showed the better performances compared with the NiO@rGO in terms of the reaction pathway being 4-electron process, the increases of the onset potential and the intermediate yielding rate, as well as the extended stability. Moreover, the effect of Pd modification was superior to that of Ag.

Key words: oxygen reduction reaction, catalyst, nickel oxide, reduced graphene oxide, surface modification

中图分类号:

O646

姚硕, 黄太仲, RizwanHaider, 房恒义, 于洁玫, 姜占坤, 梁栋, 孙玥, 原鲜霞. NiO@rGO负载钯、银纳米粒子用作氧还原催化剂[J]. 电化学（中英文）, 2020, 26(2): 270-280.

YAO Shuo, HUANG Tai-zhong, HAIDER Rizwan, FANG Heng-yi, YU Jie-mei, JIANG Zhan-kun, LIANG Dong, SUN Yue, YUAN Xian-xia. NiO@rGO Supported Palladium and Silver Nanoparticles as Electrocatalysts for Oxygen Reduction Reaction[J]. Journal of Electrochemistry, 2020, 26(2): 270-280.

图/表 6

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Fig. 4

Tab. 1

Fig. 5

参考文献 47

[1]	Liu Q, Zhang J Y . Graphene supported Co-g-C₃N₄ as a novel metal-macrocyclic electrocatalyst for the oxygen reduction reaction in fuel cells[J]. Langmuir, 2013,29(11):3821-3828.
[2]	Zhao Y, Ding Y, Qiao B , et al. Interfacial proton enrichment enhances proton-coupled electrocatalytic reactions[J]. Journal of Materials Chemistry A, 2018,6(36):17771-17777.
[3]	Xue Q, Bai J, Han C C , et al. Au nanowires@Pd-polyethy-lenimine nanohybrids as highly active and methanol-tolerant electrocatalysts toward oxygen reduction reaction in alkaline media[J]. ACS Catalysis, 2018,8(12):11287-11295. doi: 10.1021/acscatal.8b03447 URL
[4]	Jayasayee K, Van Veen JAR, Manivasagam T G , et al. Oxygen reduction reaction (ORR) activity and durability of carbon supported PtM (Co, Ni, Cu) alloys: Influence of particle size and non-noble metals[J]. Applied Catalysis B: Environmental, 2012,111:515-526.
[5]	Jennings P C, Pollet B G, Johnston R L . Theoretical studies of Pt-Ti nanoparticles for potential use as PEMFC electrocatalysts[J]. Physical Chemistry Chemical Physics, 2012,14(9):3134-3139. doi: 10.1039/c2cp23430k URL
[6]	Xu G R, Han C C, Zhu Y Y , et al. PdCo alloy nanonetworks-polyallylamine inorganic-organic nanohybrids toward the oxygen reduction reaction[J]. Advanced Materials Interfaces, 2018,5(4):1701322. doi: 10.1002/admi.v5.4 URL
[7]	Dong Y Y, Deng Y J, Zeng J H , et al. A high-performance composite ORR catalyst based on the synergy between binary transition metal nitride and nitrogen-doped reduced graphene oxide[J]. Journal of Materials Chemistry A, 2017,5(12):5829-5837. doi: 10.1039/C6TA10496G URL
[8]	Xue Q, Xu G R, Mao R D , et al. Polyethyleneimine modified AuPd@PdAu alloy nanocrystals as advanced electrocatalysts towards the oxygen reduction reaction[J]. Journal of Energy Chemistry, 2017,26(6):1153-1159. doi: 10.1016/j.jechem.2017.06.007 URL
[9]	Roche I, Chaînet E, Chatenet M , et al. Carbon-supported manganese oxide nanoparticles as electrocatalysts for the oxygen reduction reaction (ORR) in alkaline medium: Physical characterizations and ORR mechanism[J]. The Journal of Physical Chemistry C, 2007,111(3):1434-1443. doi: 10.1021/jp0647986 URL
[10]	Zhou J, Xiao H, Zhou B W , et al. Hierarchical MoS₂-rGO nanosheets with high MoS₂ loading with enhanced electro-catalytic performance[J]. Applied Surface Science, 2015,358:152-158.
[11]	Wu X Y, Gao X P, Xu L P , et al. Mn₂O₃ doping induced the improvement of catalytic performance for oxygen reduction of MnO[J]. International Journal of Hydrogen Energy, 2016,41(36):16087-16093.
[12]	Xiao M L, Zhu J B, Ma L , et al. Microporous framework induced synjournal of single-atom dispersed Fe-N-C acidic ORR catalyst and its in situ reduced Fe-N₄ active site identification revealed by X-ray absorption spectroscopy[J]. ACS Catalysis, 2018,8(4):2824-2832. doi: 10.1021/acscatal.8b00138 URL
[13]	Cai P W, Peng X X, Huang J H , et al. Covalent organic frameworks derived hollow structured N-doped noble carbon for asymmetric-electrolyte Zn-air battery[J]. Science China Chemistry, 2019,62(3):385-392.
[14]	Lin Y, Chai G L, Wen Z H . Zn-MOF-74 derived N-doped mesoporous carbon as pH-universal electrocatalyst for oxygen reduction reaction[J]. Advanced Functional Materials, 2017,27(14):1606190.
[15]	Xia W, Qu C, Liang Z B , et al. High-performance energy storage and conversion materials derived from a single metal-organic framework/graphene aerogel composite[J]. Nano Letters, 2017,17(5):2788-2795.
[16]	Song P( 宋平), Ruan M B( 阮明波), Liu J( 刘京 ), et al. Recent research for non-Pt-based oxygen reduction reaction electrocatalysts in fuel cell[J]. Journal of Electrochemistry( 电化学), 2015,21(2):130-137.
[17]	Cai P W, Li Y, Wang G X , et al. Alkaline-acid Zn-H₂O fuel cell for simultaneous generation of hydrogen and electricity[J]. Angewandte Chemie International Edition, 2018,57(15):3910-3915.
[18]	Osgood H, Devaguptapu S V, Xu H , et al. Transition metal (Fe, Co, Ni, and Mn) oxides for oxygen reduction and evolution bifunctional catalysts in alkaline media[J]. Nano Today, 2016,11(5):601-625.
[19]	Kalantar-Zadeh K, Ou J Z, Daeneke T , et al. Two dimensional and layered transition metal oxides[J]. Applied Materials Today, 2016,5:73-89.
[20]	Wang D C, Huang N B, Sun Y , et al. GO clad Co₃O₄ (Co₃O₄@GO) as ORR catalyst of anion exchange membrane fuel cell[J]. International Journal of Hydrogen Energy, 2017,42(31):20216-20223.
[21]	Kumar K, Canaff C, Rousseau J , et al. Effect of the oxide-carbon heterointerface on the activity of Co₃O₄/NRGO nanocomposites towards ORR and OER[J]. Journal of Physical Chemistry C, 2016,120(15):7949-7958.
[22]	Amin R S, Hameed R M A, El-Khatib K M , et al. Pt-NiO/C anode electrocatalysts for direct methanol fuel cells[J]. Electrochimica Acta, 2012,59:499-508.
[23]	Tong S F, Zheng M B, Lu Y , et al. Mesoporous NiO with a single-crystalline structure utilized as a noble metal-free catalyst for non-aqueous Li-O₂ batteries[J]. Journal of Materials Chemistry A, 2015,3(31):16177-16182.
[24]	Xu X B, Liu Z H, Zuo Z X , et al. Hole selective NiO contact for efficient perovskite solar cells with carbon electrode[J]. Nano Letters, 2015,15(4):2402-2408.
[25]	Zhao J, Yu H, Liu Z S , et al. Supercritical deposition route of preparing Pt/graphene composites and their catalytic performance toward methanol electrooxidation[J]. Journal of Physical Chemistry C, 2014,118(2):1182-1190.
[26]	Geng D, Ding N, Hor T S A , et al. Potential of metal-free “graphene alloy” as electrocatalysts for oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2015,3(5):1795-1810.
[27]	Higgins D, Zamani P, Yu A , et al. The application of graphene and its composites in oxygen reduction electrocatalysis: a perspective and review of recent progress[J]. Energy & Environmental Science, 2016,9(2):357-390.
[28]	Sun M, Liu H J, Liu Y , et al. Graphene-based transition metal oxide nanocomposites for the oxygen reduction reaction[J]. Nanoscale, 2015,7(4):1250-1269.
[29]	Xiu L Y( 修陆洋), Yu M Z( 于梦舟), Yang P J( 杨鹏举 ), et al. Caging porous Co-N-C nanocomposites in 3D graphene as active and aggregation-resistant electrocatalyst for oxygen reduction reaction[J]. Journal of Electrochemistry( 电化学), 2018,24(6):715-725.
[30]	Li X J, Fan L l, Li X F , et al. Enhanced anode performance of flower-like NiO/RGO nanocomposites for lithium-ion batteries[J]. Materials Chemistry and Physics, 2018,217:547-552.
[31]	Yu S P, Liu Q B, Yang W S , et al. Graphene-CeO₂ hybrid support for Pt nanoparticles as potential electrocatalyst for direct methanol fuel cells[J]. Electrochimica Acta, 2013,94:245-251.
[32]	Ji Z Y, Shen X P, Yang J L , et al. A novel reduced grap-hene oxide/Ag/CeO₂ ternary nanocomposite: Green synjournal and catalytic properties[J]. Applied Catalysis B: Environmental, 2014,144:454-461. doi: 10.1016/j.apcatb.2013.07.052 URL
[33]	Hummers W S, Offeman R E . Preparation of graphitic oxide[J]. Journal of the American Chemical Society, 1958,80(6):1339.
[34]	Chang K, Chen W X . L-cysteine-assisted synjournal of layered MoS₂/graphene composites with excellent electrochemical performances for lithium ion batteries[J]. ACS Nano, 2011,5(6):4720-4728.
[35]	Wen M, Sun B L, Zhou B , et al. Controllable assembly of Ag/C/Ni magnetic nanocables and its low activation energy dehydrogenation catalysis[J]. Journal of Materials Chemistry, 2012,22(24):11988-11993.
[36]	Wanger C D, Riggs W M, Davis L E , et al. Handbook of X-ray photoelectron spectroscopy[M]. Minnesota: Perkin-Elmer Corp., Physical Electronics Division, 1979.
[37]	Zhang J, Liu H L, Wang B , et al. Preparation of Pd/GO/Ti electrode and its electrochemical degradation for 2,4-dich-lorophenol[J]. Materials & Design, 2015,86(Supplement C):664-669.
[38]	Kahri H, Sevim M . Enhanced catalytic activity of mono-dispersed AgPd alloy nanoparticles assembled on mesoporous graphitic carbon nitride for the hydrolytic dehydrogenation of ammonia borane under sunlight[J]. Nano Research, 2017,10(5):1627-1640. doi: 10.1007/s12274-016-1345-x URL
[39]	Zhao X H, Liu X . A novel magnetic NiFe₂O₄@graphene-Pd multifunctional nanocomposite for practical catalytic application[J]. RSC Advances, 2015,5(97):79548-79555. doi: 10.1039/C5RA12720C URL
[40]	Yang L, Luo W, Cheng G Z . Graphene-supported ag-based core-shell nanoparticles for hydrogen generation in hydrolysis of ammonia borane and methylamine borane[J]. ACS Applied Materials & Interfaces, 2013,5(16):8231-8240.
[41]	Gong K P, Du F, Xia Z H , et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction[J]. Science, 2009,323(5915):760-764.
[42]	Wei Y C, Liu C W, Wang K W . Improvement of oxygen reduction reaction and methanol tolerance characteristics for PdCo electrocatalysts by Au alloying and CO treatment[J]. Chemical Communications, 2011,47(43):11927-11929.
[43]	Alexiadis A, Cornell A, Dudukovic M P . Comparison between CFD calculations of the flow in a rotating disk cell and the Cochran/Levich equations[J]. Journal of Electroanalytical Chemistry, 2012,669(1):55-66.
[44]	Gu W L, Hu L Y, Hong W , et al. Noble-metal-free Co₃S₄-S/G porous hybrids as an efficient electrocatalyst for oxygen reduction reaction[J]. Chemical Science, 2016,7(7):4167-4173. doi: 10.1039/C6SC00357E URL
[45]	Nakabayashi S, Yagi I, Sugiyama N , et al. Reaction pathway of four-electron oxidation of formaldehyde on platinum electrode as observed by in situ optical spectroscopy[J]. Surface Science, 1997,386(1/3):82-88. doi: 10.1016/S0039-6028(97)00329-4 URL
[46]	Chang H C, Han C K, Yook S , et al. Hydrogen peroxide synjournal via enhanced two-electron oxygen reduction pathway on carbon-coated Pt surface[J]. Journal of Physical Chemistry C, 2014,118(51):30063-30070. doi: 10.1021/jp5113894 URL
[47]	Yin Z, Zhang Y N, Chen K , et al. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation[J]. Scientific Reports, 2014,4:4288.

Catalyst	b/(V·dec^-1)	α	i₀/(A·cm^-2)	n
Pd-NiO@rGO	0.078	0.0625	8.9×10^-7	3.89
Ag-NiO@rGO	0.220	0.0612	7.1×10^-7	3.71
NiO@rGO	0.105	0.0298	1.5×10^-7	2.36