化工新型材料

化工新型材料 ›› 2021, Vol. 49 ›› Issue (2) : 140-143. DOI: 10.19817/j.cnki.issn 1006-3536.2021.02.032

科学研究

石墨烯负载四硫化三钴复合物氧还原催化剂的制备与性能

赵东江, 迟彩霞, 马松艳, 田喜强, 乔秀丽

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Preparation and property of graphene supported Co₃S₄ composite catalyst for oxygen reduction reaction

Zhao Dongjiang, Chi Caixia, Ma Songyan, Tian Xiqiang, Qiao Xiuli

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Received		Published
2019-10-31		2021-02-20
Issue Date	Revised Date
2021-03-03	2019-10-31

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摘要

选取二氯化钴和硫脲为钴源和硫源,以自制的还原氧化石墨烯(rGO)为载体,采用回流法在乙二醇溶剂中一步合成出Co₃S₄/rGO复合物。利用X射线衍射、扫描电镜和拉曼光谱(Raman)等手段对催化剂进行结构与形貌表征。结果表明:Co₃S₄/rGO样品中生成了具有立方结构的Co₃S₄细小晶粒,生长在rGO上的Co₃S₄晶粒发生聚集,具有较好的分散性。Co₃S₄/rGO的拉曼谱图的峰强比(I_D/I_G)为0.92,Co₃S₄对石墨烯结构无明显影响,石墨烯起到载体作用。在0.5mol/L H₂SO₄电解液中,线扫伏安测试表明,Co₃S₄/rGO催化剂具有良好的氧还原催化性能,氧还原起始电位为0.75V(vs.RHE),在动力学电位区,Tafel斜率和传递系数分别为119.5mV和0.49,氧分子在Co₃S₄/rGO催化剂上按四电子机理直接还原成水。

Abstract

The Co₃S₄/rGO composite was synthesized in ethylene glycol solvent by refluxing method using home-made reductive graphene oxide (rGO) as carrier,and choosing cobalt dichloride and thiourea as cobalt source and sulfur source,respectively.The structure and morphology of the catalyst were characterized by XRD and ramam technique.The results shown that the Co₃S₄ crystal particles with cubic structure were formed,the Co₃S₄ grains grown on rGO gathered and had good dispersibility.The I_D/I_G of raman spectra of the samples was 0.92,Co₃S₄ had no obvious effect on the structure of graphene and graphene acted as a carrier.In 0.5mol/L H₂SO₄ electrolyte,the linear sweep voltammetric test shown that the Co₃S₄/rGO catalyst had good catalytic performance for oxygen reduction,and the open-circuit potential was 0.75V (vs.NHE).In the kinetic potential region,the Tafel slope and transfer coefficient were 119.5mV and 0.49,respectively.Oxygen molecules were directly reduced to water on the Co₃S₄/rGO catalyst according to the four-electron mechanism.

关键词

氧还原反应 / 石墨烯 / 四硫化三钴化合物 / 非贵金属催化剂

Key words

oxygen reduction reaction / graphene / Co₃S₄ compound / non-precious metal catalyst

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石墨烯负载四硫化三钴复合物氧还原催化剂的制备与性能[J]. 化工新型材料, 2021, 49(2): 140-143 DOI:10.19817/j.cnki.issn 1006-3536.2021.02.032

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参考文献

原文顺序 | 出版日期 | 本文引用

[1] 钟国玉,王红娟,余皓,等.氧还原碳基非贵金属电催化剂研究进展[J].化学学报,2017,75(10):943-966.
[2] Borghei M,Lehtonen J,Liu L,et al.Advanced biomass-derived electrocatalysts for the oxygen reduction reaction[J].Adv Mater,2018,30(24):1703691.
[3] 司玉军,熊中平,李敏娇,等.氧化石墨制备氮掺杂氧还原反应电催化剂[J].电源技术,2018,42(1):58-60,64.
[4] Xu J J,Xiao C H,Ding S J.Red-blood-cell like nitrogen-doped carbons with highly catalytic activity towards oxygen reduction reaction[J].Chinese Chemical Letters,2017,28:748-754.
[5] Xue L,Li Y,Liu X,et al.Zigzag carbon as efficient and stable oxygen reduction electrocatalyst for proton exchange membrane fuel cells[J].Nature Communications,2018,9:3819.
[6] Chen Z,Higgins D,Yu A,et al.A review on non-precious metal electrocatalysts for PEM fuel cells[J].Energy Environ Sci,2011,4(9):3167-3192.
[7] Feng Y,Gago A S,Timperman L,et al.Chalcogenide metal centers for oxygen reduction reaction:activity and tolerance[J].Electrochim Acta,2011,56:1009-1022.
[8] Gao M R,Jiang J,Yu S H.Solution-based synthesis and design of late transition metal chalcogenide materials for oxygen reduction reaction[J].Small,2012,8:13-27.
[9] Brouzgou A,Song S,Liang Z X,et al.Non-precious electrocatalysts for oxygen reduction reaction in alkaline media:latest achievements on novel carbon materials[J].Catalysts,2016,6(10):159.
[10] Behret H,Sandstede G.Electrocatalytic oxygen reduction with thiospinels and other sulphides of transition metals[J].Electrochim Atca,1975,20:111-117.
[11] Feng Y,He T,Alonso-Vante N.In situ free surfactant synthesis and ORR electrochemistry of carbon-supported Co₃S₄ and CoSe₂ nanoparticles[J].Chem Mater,2008,20:26-28.
[12] Falkowski J M,Surendranath Y.Metal chalcogenide nano-films:platforms for mechanistic studies of electrocatalysis[J].ACS Catal,2015,5:3411-3416.
[13] Zhao D,Ma S,Yin G.A facile one-step synthesis of Co₉S₈ electrocatalyst for oxygen reduction reaction[J].Rare Metal Materials and Engineering,2017,46(12):3577-3582.
[14] Zhao C,Li D,Feng Y.Size-controlled hydrothermal synthesis and high electrocatalytic performance of CoS₂ nanocatalysts as non-precious metal cathode materials for fuel cells[J].J Mater Chem A,2013,1(18):5741-5746.
[15] Novoselov K,Geim A,Morozov S,et al.Electric field effect in atomically thin carbon films[J].Science,2004,306(5696):666-669.
[16] 陈亚玲,宋力,郭虎,等.水热合成二硫化钨/石墨烯复合材料及其氧还原性能[J].无机化学学报,2016,32(4):633-640.
[17] 程铭,史瑞娜,刘树森,等.微波溶剂热法制备掺氮石墨烯用于碱性氧还原反应[J].无机化学学报,2018,34(1):151-160.
[18] Wang H,Liang Y,Li Y,et al.Co_1-xS-graphene hybrid:a high-performance metal chalcogenide electrocatalyst for oxygen reduction[J].Angew Chem Int Ed,2011,50:10969-10972.
[19] Mahmood N,Zhang C,Jiang J,et al.Multifunctional Co₃S₄/grapheme composites for lithiumion batteries and oxygen reduction reaction[J].Chem Eur J,2013,19(16):5183-5190.
[20] 马松艳,田喜强,迟彩霞,等.CoSe₂/rGO复合物的水热法合成及其氧还原催化性能[J].炭素技术,2019,38(1):14-17,40.
[21] 李玲,张雪,李晶,等.碳纳米纤维负载Co₃S₄复合材料的合成及其在染料敏化太阳电池对电极的应用[J].无机化学学报,2017,33(4):607-614.
[22] 程铭史,瑞娜,刘树森,等.微波溶剂热法制备掺氮石墨烯用于碱性氧还原反应(英文)[J].无机化学学报,2018,34(1):151-160.
[23] 施旗,雷永鹏,王应德,等.氮掺杂石墨烯@碳纳米纤维的原位制备及其电催化氧还原性能[J].无机材料学报,2016,31(4):351-357.
[24] 邓玉潇,皇甫海新,唐水花,等.一步热解核黄素制备高性能氧还原反应电催化剂(英文)[J].催化学报,2017,38(10):1668-1679.
[25] Suarez-Alcantara K,Rodriguez-Castellanos A,Dante R,et al.Ru_xCr_ySe_z electrocatalyst for oxygen reduction in a polymer electrolyte membrane fuel cell[J].J Power Sources,2006,157(1):114-120.
[26] Li Y,Zhao Y,Cheng H,et al.Nitrogen-doped graphene quantum dots with oxygen-rich functional groups[J].J Am Chem Soc,2012,134:15-18.
[27] Hsueh K L,Chin D T,Srinivasan S.Electrode kinetics of oxygen reduction:a theoretical and experimental analysis of the rotating ring-disc electrode method[J].J Electroanal Chem,1983,153(1/2):79-95.
[28] 赵东江,马松艳,尹鸽平.CoSeO₃化合物的制备及对阴极氧还原的催化性能[J].无机材料学报,2013,28(6):644-648.