以高锰酸钾、草酸锰、石墨烯为原料，采用化学共沉淀法制备MnO2@graphene 复合材料，用X射线衍射、红外光谱、拉曼光谱、扫描电镜、比表面测定等对其进行表征。以MnO2@graphene为MFC阴极氧还原反应催化剂，采用循环伏安法和电化学阻抗法研究MnO2@graphene催化电极对氧还原反应的催化活性。结果表明：粒度为400 nm 左右的 MnO2颗粒通过静电相互作用均匀而牢固地分散在纸片状 graphene 表面，形成MnO2@graphene复合材料。循环伏安测试结果表明：当扫描速率为5 mV/s时，虽然MnO2@graphene催化电极在pH为7.0的磷酸盐缓冲体系(PBS)的氧还原反应起峰电位比Pt/C催化电极负0.048V，但其峰电位(?0.440 V)与Pt/C催化电极的起峰电位(?0.434 V)接近。随着循环次数的增加，MnO2@graphene催化电极的起峰电位稍有下降，但峰电流密度下降很小，表明MnO2@graphene催化剂具有更好的氧还原催化活性和更优秀的循环稳定性。电化学阻抗实验发现：MnO2@graphene催化电极的电荷转移阻抗为12.6Ω，比同条件下Pt/C催化电极和MnO2催化电极的低，表明由于graphene增加MnO2的导电性，降低催化电极电荷转移阻抗，加快电子的转移速率，促进阴极氧还原反应。
MnO2@graphene composites were prepared by a chemical co-precipitation method using KMnO4, MnC2O4·2H2O and graphene as raw materials.The microstructure, morphology of the prepared composites were analyzed using X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectrum, Raman spectroscopy, X-ray photoelectron spectroscopy(XPS), scanning electron microscopy (SEM) and specific area measurements. The electrochemical performances of MnO2@graphene composites as catalysts for cathodic oxygen reduction reaction in microbial fuel cell were analyzed using cyclic voltammetry, electrochemical impedance spectrometry (EIS). The results show that spherical MnO2 with uniform particle size of 400 nm is tightly formed on the surface of paper-like graphene by electrostatic interaction. Moreover, the peak potential of MnO2@graphene electrode (?0.440 V) is very close to that for Pt/C electrode (?0.434 V), though the initial peak potential of MnO2@graphene electrode is 0.048 V negative than that for Pt/C electrode. With the increase of cycling times, the initial peak potential of MnO2@graphene electrode decreases, while there is only a small decline for the peak current density of MnO2@graphene electrode, indicating that the MnO2@graphene composites have better catalytic activity and cycling stability for cathodic oxygen reduction reaction in microbial fuel cell than that for Pt/C catalysts. EIS results show that the electron-transfer resistance of MnO2@graphene is only 12.6 Ω, which is smaller than that for Pt/C catalysts and MnO2 catalysts, suggesting MnO2@graphene catalysts promote the cathodic oxygen reduction reaction by decareasing the electron-transfer resistance and accelerating the charge transfer due the introduction of the excellent conductive graphene.
参考文献
| [1] | BRUCE E. LOGAN;JOHN M. REGAN.MICROBIAL FUEL CELLS-CHALLENGES AND APPLICATIONS[J].Environmental Science & Technology: ES&T,200617(17):5172-5180. |
| [2] | Logan BE;Hamelers B;Rozendal R;Schrorder U;Keller J;Freguia S;Aelterman P;Verstraete W;Rabaey K.Microbial fuel cells: Methodology and technology[J].Environmental Science & Technology: ES&T,200617(17):5181-5192. |
| [3] | Shijie You;Qingliang Zhao;Jinna Zhang.A microbial fuel cell using permanganate as the cathodic electron acceptor[J].Journal of Power Sources,20062(2):1409-1415. |
| [4] | 袁浩然;邓丽芳;黄宏宇;小林敬幸;陈勇.MnO2为阴极催化剂的微生物燃料电池处理城市垃圾渗滤液研究[J].太阳能学报,2014(9):1715-1722. |
| [5] | Li, Y.;Lu, A.;Ding, H.;Wang, X.;Wang, C.;Zeng, C.;Yan, Y..Microbial fuel cells using natural pyrrhotite as the cathodic heterogeneous Fenton catalyst towards the degradation of biorefractory organics in landfill leachate[J].Electrochemistry communications,20107(7):944-947. |
| [6] | 费讲驰 .高效产电菌的筛选及其在微生物燃料电池中的应用研究[D].吉首大学,2014. |
| [7] | 范平;支银芳;吴夏芫;周楚新.微生物燃料电池中阳极产电微生物的研究进展[J].生物学通报,2011(10):6-9. |
| [8] | 尤世界;赵庆良;姜珺秋.电极构型对空气阴极生物燃料电池发电性能的影响[J].环境科学,2006(11):2159-2163. |
| [9] | Sebastià Puig;Marc Serra;Marta Coma;MarinaCabré;M. Dolors Balaguer;Jesús Colprim.Microbial fuel cell application in landfill leachate treatment[J].Journal of hazardous materials,20112/3(2/3):763-767. |
| [10] | Pham The Hai;Jae Kyung Jang;In Seop Chang;Byung Hong Kim.Improvement of Cathode Reaction of a Mediatorless Microbial Fuel Cell[J].Journal of microbiology and biotechnology,20042(2):324-329. |
| [11] | Yuan, Y.;Zhao, B.;Jeon, Y.;Zhong, S.;Zhou, S.;Kim, S..Iron phthalocyanine supported on amino-functionalized multi-walled carbon nanotube as an alternative cathodic oxygen catalyst in microbial fuel cells[J].Bioresource Technology: Biomass, Bioenergy, Biowastes, Conversion Technologies, Biotransformations, Production Technologies,201110(10):5849-5854. |
| [12] | Kim, J.R.;Kim, J.-Y.;Han, S.-B.;Park, K.-W.;Saratale, G.D.;Oh, S.-E..Application of Co-naphthalocyanine (CoNPc) as alternative cathode catalyst and support structure for microbial fuel cells[J].Bioresource Technology: Biomass, Bioenergy, Biowastes, Conversion Technologies, Biotransformations, Production Technologies,20111(1):342-347. |
| [13] | Manganese dioxide as a new cathode catalyst in microbial fuel cells[J].Journal of Power Sources,20109(9):2586. |
| [14] | I. Roche;K. Scott.Carbon-supported manganese oxide nanoparticles as electrocatalysts for oxygen reduction reaction (orr) in neutral solution[J].Journal of Applied Electrochemistry,20092(2):197-204. |
| [15] | Fischer AE;Pettigrew KA;Rolison DR;Stroud RM;Long JW.Incorporation of homogeneous, nanoscale MnO2 within ultraporous carbon structures via self-limiting electroless deposition: Implications for electrochemical capacitors[J].Nano letters,20072(2):281-286. |
| [16] | Qing Wen;Shaoyun Wang;Jun Yan;Lijie Cong;Zhongcheng Pan;Yueming Ren;Zhuangjun Fan.MnO_2-graphene hybrid as an alternative cathodic catalyst to platinum in microbial fuel cells[J].Journal of Power Sources,2012Oct.15(Oct.15):187-191. |
| [17] | 钱晓峰;褚有群;李照华;马淳安.MnOx/CNT的制备及其对氧还原反应的电催化性能研究[J].浙江工业大学学报,2012(4):365-368. |
| [18] | Sang-Bok Ma;Young-Ho Lee;Kyun-Young Ahn.Spontaneously Deposited Manganese Oxide on Acetylene Black in an Aqueous Potassium Permanganate Solution[J].Journal of the Electrochemical Society,20061(1):C27-C32. |
| [19] | Xingkang Huang;Hongjun Yue;Adel Attia.Preparation and Properties of Manganese Oxide/Carbon Composites by Reduction of potassium Permanganate with Acetylene Black[J].Journal of the Electrochemical Society,20071(1):A26-A33. |
| [20] | 曾双双;郑明森;董全峰.直接还原高锰酸钾制备CNT/MnO2复合材料[J].电池,2010(3):121-123. |
| [21] | Yaping Zhang;Yongyou Hu;Sizhe Li;Jian Sun;Bin Hou.Manganese dioxide-coated carbon nanotubes as an improved cathodic catalyst for oxygen reduction in a microbial fuel cell[J].Journal of Power Sources,201122(22):9284-9289. |
| [22] | 赵东江.石墨烯在氧还原反应催化剂中应用的研究进展[J].绥化学院学报,2013(09):153-160. |
| [23] | 彭三;郭慧林;亢晓峰.氮掺杂石墨烯的制备及其对氧还原反应的电催化性能[J].物理化学学报,2014(9):1778-1786. |
| [24] | 许学飞 .高分散性Pt/C催化剂的制备与研究[D].浙江理工大学,2012. |
| [25] | 陈仲;李建玲;陈宇.微波水热法制备二氧化锰/石墨烯复合材料[J].电池,2013(1):15-17. |
| [26] | 徐晓;田艳红;张学军.石墨烯/二氧化锰复合材料的电化学性能[J].硅酸盐学报,2013(1):38-43. |
| [27] | Y. L. Cao;H. X. Yang;X. P. Ai;L. F. Xiao.The mechanism of oxygen reduction on MnO_2-catalyzed air cathode in alkaline solution[J].Journal of Electroanalytical Chemistry: An International Journal Devoted to All Aspects of Electrode Kinetics, Interfacial Structure, Properties of Electrolytes, Colloid and Biological Electrochemistry,20030(0):127-134. |
| [28] | 邹琼;宰建陶;刘萍;钱雪峰.中空Fe203/G-NS纳米复合材料的制备和储锂性能[J].高等学校化学学报,2011(3):630-634. |
| [29] | 姚振华;胡茂从.二氧化锰/石墨烯臭氧催化氧化甲苯反应性能[J].广州化工,2015(2):34-36. |
| [30] | Tao Gao;Marianne Glerup;Frank Krumeich.Microstructures and Spectroscopic Properties of Cryptomelane-type Manganese Dioxide Nanofibers[J].The journal of physical chemistry, C. Nanomaterials and interfaces,200834(34):13134-13140. |
| [31] | Mathieu Toupin;Thierry Brousse;Daniel Belanger.Charge Storage Mechanism of MnO_2 Electrode Used in Aqueous Electrochemical Capacitor[J].Chemistry of Materials,200416(16):3184-3190. |
| [32] | Yan Gu;Jianwei Cai;Mingze He;Liping Kang;Zhibin Lei;Zong-Huai Liu.Preparation and capacitance behavior of manganese oxide hollow structures with different morphologies via template-engaged redox etching[J].Journal of Power Sources,2013Oct.1(Oct.1):347-355. |
| [33] | Chigane M.;Ishikawa M..Manganese Oxide Thin Film Preparation by Potentiostatic Electrolyses and Electrochromism[J].Journal of the Electrochemical Society,20006(6):2246-2251. |
| [34] | Toupin M.;Brousse T.;Belanger D..Influence of microstucture on the charge storage properties of chemically synthesized manganese dioxide[J].Chemistry of Materials,20029(9):3946-3952. |
| [35] | Jiajia Wu;Dun Zhang;Yi Wang;Yi Wan.Manganese oxide-graphene composite as an efficient catalyst for 4-electron reduction of oxygen in alkaline media[J].Electrochimica Acta,2012:305-310. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%