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 ID/IG 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.
[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.Co1-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.RuxCrySez 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.
