以硝酸钴、硝酸锌、尿素、氟化铵为原料,泡沫镍为基体,在水热法的基础上,利用两性金属的特点,通过引入Zn2+离子,并结合碱洗过程,在泡沫镍基体表面合成了高纯度独特的棱柱状Co3O4纳米团簇纤维。制备的Co3O4/Ni电极的形貌及成分通过扫描电子显微镜与X射线衍射进行了表征,电极的电化学性能利用循环伏安法与计时电流法测试,测试均在1mol/L KOH溶液中进行。结果表明:利用Zn2+诱导在泡沫镍表面制备的Co3O4呈现一种棱柱状纳米团簇纤维结构。这种结构的Co3O4纳米材料具有高的比表面积,在对葡萄糖检测过程中表现出优越的电化学性能,当其作为电极,表现出检测灵敏度高[23430μA/(mmol/L·cm2)],检出限低(1.547μmol/L)和线性检测范围宽(0～2.75mmol/L)的特点。抗干扰实验在+0.5V vs.SCE进行,结果显示制备的Co3O4/Ni电极对葡萄糖具有优异的选择性。因此可应用于无酶葡萄糖传感器的电极材料来改善现有无酶葡萄糖传感器材料响应范围小,灵敏度低等问题。
Co3O4 with high-purity and unique prismatic structure were synthesized on the surface of the nickel foam based on hydrothermal method with combination of alkali washing.Which used cobalt nitrate,zinc nitrate,urea and ammonium fluoride as raw materials,and nickel foam as matrix,meanwhile amphoteric Zn2+ ions were added.The composition and morphology of the Co3O4/Ni electrode was characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM),and the electrochemical properties of the fabricated Co3O4/Ni heterostructure-based glucose sensor were detected in 1M KOH solution by the cyclic voltammetry (CV) and chronoamperometry methods.The results showed that synthesized Co3O4 on the surface of nickel foam had prismatic nano-cluster fibrous structure.This nano-cluster Co3O4 based electrode had a high specific surface area,and showed excellent electrochemical performance in the process of glucose detection.As an electrode,the Co3O4/Ni heterostructure showed high detection sensitivity[23430μA/(mmol/L·cm2)],low detection limit(1.547μmol/L) and wide linear detection range(0～2.75mmol/L).Anti-interference tests showed that the prepared electrode had good selectivity to glucose at +0.5V vs.SCE.Therefore this Co3O4/Ni based electrode can be used as electrode material of non-enzyme glucose sensor,and solved the problem of low sensitivity and small response range existing in non-enzyme glucose sensor materials.
[1] Li M,Dong P,Zhang Y.Facile design and synthesis of ultrafine FeCo nanocrystallines coupled with porous carbon nanosheets as high efficiency non-enzymatic glucose sensor[J].Journal of Alloys and Compounds,2019,810:151927.
[2] 王永鹏,徐子勃,刘梦竹,等.多孔泡沫状CuO微纳米纤维的制备及用于无酶葡萄糖传感器[J].高等学校化学学报,2019,40(6):1310-1316.
[3] Meng S,Wu M,Wang Q,et al.Cobalt oxide nanosheets wrapped onto nickel foam for non-enzymatic detection of glucose[J].Nanotechnology,2016,27(34):344001-344001.
[4] Liu S,Liu B,Gong C,et al.A nanoporous Cu-Ag thin film at the Cu-Ag-Zn alloy surface by spontaneous dissolution of Zn and Cu in different degrees as a highly sensitive non-enzymatic glucose sensor[J].Electrochimica Acta,2019,320:134599.
[5] Bach L G,Thi M L N,Bui Q B,et al.Hierarchical cobalt nanorods shelled with nickel oxide vertically attached 3D architecture as non-binder and free-standing sensor for sensitive non-enzymatic glucose detection[J].Materials Research Bulletin,2019,118:110504.
[6] Xu L,Zou Y,Xiao Z,et al.Transforming Co3O4 nanosheets into porous N-doped CoO nanosheets with oxygen vacancies for the oxygen evolution reaction[J].Journal of Energy Chemistry,2019,35:24-29.
[7] 方璐,姚如富,薛燕.花状四氧化三钴的制备及其电性能研究[J].巢湖学院学报,2015,17(3):59-67.
[8] Mandal S,Rakibuddin M,Ananthakrishnan R.Strategic synthesis of SiO2-modified porous Co3O4 nano-octahedra through the nanocoordination polymer route for enhanced and selective sensing of H2 gas over NOx[J].ACS Omega,2018,3(1):648-661.
[9] Ren Y,Zhao S,Li H,et al.Facile fabrication of hierarchical porous Co3O4 nanoarrays as a free-standing cathode for lithium-oxygen batteries[J].Journal of Energy Chemistry,2019,30:63-70.
[10] Long H,Ren B,Li J,et al.3D hierarchical Co3O4:controlled preparation of coral-/urchin-like structures and application in photo-catalytic degradation[J].Journal of Alloys and Compounds,2017,720:437-444.
[11] 李济莘,胡亚鹏,赵晓丹,等.Co3O4超级电容器电极材料的制备及电化学性能研究[J].高师理科学刊,2019,39(8):48-53.
[12] 马麦霞,魏磊,张素玲,等.微纳米结构Co3O4陶瓷材料的合成及介电性能研究[J].陶瓷学报,2019,40(2):223-227.
[13] Zielinska B,Janus M,Kalenczuk R.Preparation,characterization and photocatalytic activity of Co3O4/LiNbO3 composite[J].Open Chemistry,2013,11(6).
[14] Li Y,Zhang Y,Gao M,et al.Preparation and catalytic effect of porous Co3O4 on the hydrogen storage properties of a Li-B-N-H system[J].Progress in Natural Science:Materials International,2017,27(1):132-138.
[15] Alali K T,Liu J,Chen R,et al.HFIP-Functionalized Co3O4 micro-nano octahedra/rGO as a double layer sensing material for chemical warfare agents[J].Chemistry,2019,25(51):11892-11902.
[16] Chai Y,Wang X,Yu Y,et al.Cooperation of Fe2O3@C and Co3O4/C subunits enhances the cyclic stability of Fe2O3@C/Co3O4 electrodes for lithium-ion batteries[J].International Journal of Energy Research,2019,43(11):6045-6055.
[17] Gao Z,Zhang L,Ma C,et al.TiO2 decorated Co3O4 acicular nanotube arrays and its application as a non-enzymatic glucose sensor[J].Biosensors and Bioelectronics,2016,80:511-518.
[18] Li X,Tian X,Yang T,et al.Hierarchically multiporous CNTs/Co3O4 composite as anode material for high performance lithium ion batteries[J].Chemistry,2018,24(54):14477-14483.
[19]Yin D,Huang G,Sun Q,et al.RGO/Co3O4 composites prepared using GO-MOFs as precursor for advanced lithium-ion batteries and supercapacitors electrodes[J].Electrochimica Acta,2016,215:410-419.
[20] Chen H,Lu S,Gong F,et al.Stepwise splitting growth and pseudocapacitive properties of hierarchical three-dimensional Co3O4 nanobooks[J].Nanomaterials,2017,7(4):81.
[21] Mahmoudian M R,Basirun W J,Woi P M,et al.Synthesis and characterization of Co3O4 ultra-nanosheets and Co3O4 ultra-nanosheet-Ni(OH)2 as non-enzymatic electrochemical sensors for glucose detection[J].Materials Science and Engineering:C,2016,59:500-508.
