N和Co修饰的多孔碳催化剂的制备及电催化析氢性能研究
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摘要
首先利用溶剂热法制备出两种不同的金属有机框架MOFs,将两种不同的MOFs分别与石墨烯材料复合,得到ZnCo-MOF/Gr以及Co-MOF/Gr,经过高温热解后形成碳层包裹的钴纳米颗粒负载在N掺杂的多孔碳材料上(Co-N-C-T以及Co/N/C),通过XRD、XPS、SEM和TEM等手段对其进行了结构和形貌表征。结果表明所制备的Co-N-C-900继承了MOFs的高比表面积的特性,尺寸均一,其比表面积高达488.73m~2g~(-1)和具有多级孔结构、高浓度的催化活性位点(N和Co的原子含量为3.77%和1.26%)。并通过一系列电化学测试手段对材料的电催化析氢(HER)性能进行了评估。结果表明Co-N-C-900在酸性和碱性条件下都表现出优异的HER催化性能,在不同电解质中的起始电位最正,塔菲尔斜率最小,与Pt/C最为接近。在经历了1000次的循环伏安(CV)测试后,测得的线性伏安曲线(LSV)与初始LSV基本重合,表明Co-N-C-900具有较好的稳定性。
Two kinds of MOFs and graphene hybrid were prepared by solvothermal method then and were pyrolyzed at high temperature;cobalt nanoparticles encased in coated carbon layer supporting by N doped carbon(Co-N-C-T and Co/N/C) were prepared by pyrolyzing method. XRD,XPS,SEM and TEM were employed to characterize the morphology and structure of as-prepared catalysts. The results showed that the prepared Co-N-C-900 inherited the characteristics of high specific surface area of MOFs and its size was uniform. Its specific surface area was up to 488.73m~2g~(-1) and had multilevel pore structure,high concentration of catalytic activity sites(the atomic contents of N and Co are 3.77% and 1.26%). The electrocatalytic performance of the catalyst for HER was evaluated by a series of electrochemical methods. The results indicated that the Co-N-C-900 showed better activity and stability in both acidic and alkaline solution and attributed to larger specific surface area,hierarchical porosity and faster electron and mass transfer.After 1000 times of cyclic voltammetry(CV) measurements,the linear voltammetric curve(LSV) was basically coincident with the initial LSV,which indicated that Co-N-C-900 has good stability.
Two kinds of MOFs and graphene hybrid were prepared by solvothermal method then and were pyrolyzed at high temperature;cobalt nanoparticles encased in coated carbon layer supporting by N doped carbon(Co-N-C-T and Co/N/C) were prepared by pyrolyzing method. XRD,XPS,SEM and TEM were employed to characterize the morphology and structure of as-prepared catalysts. The results showed that the prepared Co-N-C-900 inherited the characteristics of high specific surface area of MOFs and its size was uniform. Its specific surface area was up to 488.73m~2g~(-1) and had multilevel pore structure,high concentration of catalytic activity sites(the atomic contents of N and Co are 3.77% and 1.26%). The electrocatalytic performance of the catalyst for HER was evaluated by a series of electrochemical methods. The results indicated that the Co-N-C-900 showed better activity and stability in both acidic and alkaline solution and attributed to larger specific surface area,hierarchical porosity and faster electron and mass transfer.After 1000 times of cyclic voltammetry(CV) measurements,the linear voltammetric curve(LSV) was basically coincident with the initial LSV,which indicated that Co-N-C-900 has good stability.
引文
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[3]Lu J,Xiong T,Zhou W,et al.Metal nickel foam as an efficient and stable electrode for hydrogen evolution reaction in acidic electrolyte under reasonable overpotentials[J].ACS Appl.Mater.Interfaces,2016,8(8):5065-5069.
[4]Deng J,Ren P,Deng D,et al.Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction[J].Energy Environ.Sci,2014,7(6):1919-1923.
[5]袁方莹,楚学影,李金华,等.形貌对ZnS微纳结构电化学电极特性影响及机制分析[J].长春理工大学学报:自然科学版,2017,9(2):33-36.
[6]Zou X,Huang X,Goswami A,et al.Cobalt-embedded nitrogen-rich carbon nanotubes efficiently catalyze hydrogen evolution reaction at all pH values[J].Angew.Chem.Int.Ed,2014,53(17):4372-4376.
[7]Wang T,Zhou Q,Wang X,et al.MOF-derived surface modified Ni nanoparticles as an efficient catalyst for the hydrogen evolution reaction[J].J.Mater.Chem.A,2015,3(32):16435-16439.
[8]Zhou W,Zhou Y,Yang L,et al.N-doped carbon-coated cobalt nanorod arrays supported on a titanium mesh as highly active electrocatalysts for the hydrogen evolution reaction[J].J.Mater.Chem.A,2015,3(5):1915-1919.
[9]Zhou W,Zhou J,Zhou Y,et al.N-doped carbon-wrapped cobalt nanoparticles on N-doped graphene nanosheets for high-efficiency hydrogen production[J].Chem.Mater,2015,27(6):2026-2032.
[10]Chen J,Zhou H F,Huang Y J,et al.A 3D Co-CNframework as high performance electrocatalyst for hydrogen evolution reaction[J].RSC Advances,2016,6(48):42014-42018.
[11]周贺,何兴权.介孔氮掺杂碳材料应用于氧还原催化剂.长春理工大学学报:自然科学版,2018,41(03):64-67.
[12]Odoh S O,Cramer C J,Thuhlar D G,Quantum-chemical characterization of the properties and reactivities of metal organic frameworks[J].Chem.Rev,2016,115(12):6051-6111.
[13]Ghosh S,Sahu R K,Raj C R.Shape-regulated high yield synthesis of electrocatalytically active branched Pt nanostructures for oxygen reduction and methanol oxidation reactions[J].Journal of Materials Chemistry,2011,21(32):11973-11980.
[14]Shen M X,Ruan C P,Chen Y,et al.Covalent entrapment of cobalt-iron sulfides in N-Doped mesoporous carbon:extraordinary bifunctional electrocatalysts for oxygen reduction and evolution reactions[J].ACS Appl.Mater.Interfaces,2014,7(2):1207-1218.
[15]Zhu Z,Yang Y,Guan Y,et al.Construction of a cobalt-embedded nitrogen doped carbon material with the desired porosity derived from the confined growth of MOFs within graphene aerogels as a superior catalyst towards HER and ORR[J].Journal of Materials Chemistry A,2016,4(40):15536-15545.
[16]Pimenta M A,Dresselhaus G,Dresselhaus M S,et al.Studying disorder in graphite-based systems by Raman spectroscopy[J].Physical Chemistry Chemical Physics Pccp,2007,9(11):1276-1291.
[17]Yang Z,Yao Z,Li G F,et al.Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction.ACS Nano[J].2012,6(1):205-211.
[18]Wang S Y,Iyyamperumal E,Roy A,et al.Vertically aligned BCN nanotubes as efficient metal-free electrocatalysts for the oxygen reduction reaction:a synergetic effect by co-doping with boron and nitrogen[J].Angew.Chem.Int.Ed.Engl,2011,50(49):11756-11760.
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[23]Yin J,Fan Q H,Li Y X,et al.Ni-C-Nnanosheets as catalyst for hydrogen evolution.Journal of American Chemical Society[J].Nano Research,2016,138(254):14546-14549.
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