不同实验条件对锰矿法制备介孔纳米四氧化三锰性能的影响
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摘要
采用简单易行,成本低廉的锰矿法,以软锰矿焙烧熟料溶出液为原料,氨水为沉淀剂,空气为氧化剂,制备四氧化三锰。研究了不同实验条件对Mn_3O_4物相、形貌、比表面积的影响,采用XRD、SEM和BET对产物进行表征。结果表明,不同的实验条件对所得产物物相组成没有明显影响,经过超声处理的样品结晶度更好;不同的实验条件所得产物均为介孔结构的纳米级四氧化三锰,但对产物形貌和比表面积有较大影响。实验最佳条件为:不经过超声,未加任何添加剂,Mn_SO_4反加到NH_3·H_2O中的沉淀-氧化两步法。所得产物由球状颗粒和细棒状组成,球状颗粒的粒径最小,大部分小于50 nm,比表面积为35. 05 m~2/g。
Using leaching solution of pyrolusite sulfuric acid roasting clinker as raw material,aqueous ammonia as precipitant,and air as oxidant,Mn_3O_4 was prepared by the simple and economically feasible manganese ore method. The effects of different experimental conditions on the phase,morphology and specific surface area of Mn_3O_4 were studied,the products were characterized by X-ray diffraction,scanning electron microscope,and Brunauer-Emmett-Teller surface area analyzer. The results show that the products obtained under different experimental conditions are high purity Mn_3O_4,and the crystallinity of the samples with ultrasonic treatment is better. The products obtained are Nano Mn_3O_4 with mesoporous structure,however,the change of experimental conditions affects the morphology and specific surface area of the product. The optimum condition for preparation of Mn_3O_4 area precipitation-oxidation route,in which MnSO_4 is added to NH_3·H_2O without ultrasound and any additives. The morphology is the mixture of nanorods and small particles,the size of the spherical particles are less than 50 nm,and the specific surface area reaches 35. 05 m~2/g.
Using leaching solution of pyrolusite sulfuric acid roasting clinker as raw material,aqueous ammonia as precipitant,and air as oxidant,Mn_3O_4 was prepared by the simple and economically feasible manganese ore method. The effects of different experimental conditions on the phase,morphology and specific surface area of Mn_3O_4 were studied,the products were characterized by X-ray diffraction,scanning electron microscope,and Brunauer-Emmett-Teller surface area analyzer. The results show that the products obtained under different experimental conditions are high purity Mn_3O_4,and the crystallinity of the samples with ultrasonic treatment is better. The products obtained are Nano Mn_3O_4 with mesoporous structure,however,the change of experimental conditions affects the morphology and specific surface area of the product. The optimum condition for preparation of Mn_3O_4 area precipitation-oxidation route,in which MnSO_4 is added to NH_3·H_2O without ultrasound and any additives. The morphology is the mixture of nanorods and small particles,the size of the spherical particles are less than 50 nm,and the specific surface area reaches 35. 05 m~2/g.
引文
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[2]Konstantinov K,Tournayre Y,Liu H K.In-situ Fabrication and Characterization of Nanostructured Mn3O4Powders for Electronic and Electrochemical Applications[J].Materials Letters,2007,61(14-15):3189-3192.
[3]Gibot P,Laffont L.Hydrophilic and Hydrophobic Nano-sized Mn3O4Particles[J].Journal of Solid State Chemistry,2007(180):695-701.
[4]王新华.冶金研究[M].北京:冶金工业出版社,2003:291-295.
[5]董昌文,叶华,杨光辉.四氧化三锰的制备方法[J].广东化工,2016,43(12):92-93.
[6]何克杰,罗炎,皮露,等.硫酸锰溶液碱化沉淀-焙烧法制备Mn3O4[J].湿法冶金,2015,34(3):213-217.
[7]李长安,陈上,刘伟.从硫酸锰两步法制备的四氧化三锰中除硫[J].中国有色金属学报,2013,23(3):1783-1788.
[8]Han Y F,Chen F X,Zhong Z Y,et al.Synthesis and Characterization of Mn3O4and Mn2O3Nanocrystals on SBA-15:Novel Combustion Catalysts at Low Reaction Temperatures[J].Catalysis Communications,2006(7):739-744.
[9]Liu L G,Lin C C,Yang Y J.Formation of Diamond by Decarbonation of MnCO3[J].Solid State Communications,2001,118(4):195-198.
[10]Wang J S,Sun J Q,Bao Y,et al.Preparation of Manganese Oxide Nanobelts[J].Journal of Materials Science&Technology,2003,19(5):489-491.
[11]Al Sagheer F A,Hasan M A,Pasupulety L,et al.Low-temperature Synthesis of Hausmannite Mn3O4[J].Journal of Materials Science Letters,1999,18(3):209-211.
[12]聂建中,毋兴.以原生锰矿制取四氧化三锰的方法:中国,CN200410012578.5[P],2005-04-06.
[13]杨志超,冯雅丽,李浩然,等.石灰乳法制备四氧化三锰[J].中国有色金属学报,2013,23(11):1004-0609.
[14]何秋星,陈启权.磁性材料的制备[J].韶关学院学报:自然科学版,2002,23(9):57-60.
[15]王红太.国内四氧化三锰的生产工艺现状及发展方向[J].山西化工,2006,26(3):55-57.
[16]Zhen M M,Zhang Z,Ren Q T,et al.Room-temperature Synthesis of Ultrathin Mn3O4Nanosheets as Anode Materials for Lithium-ion Batteries[J].Materials Letters,2016(177):21-24.
[17]胡文立,耿萌,陈梦琴,等.几种表面活性剂对Mn3O4生成形貌的影响[J].湿法冶金,2016,35(3):225-230.
[18]Hu Y Y,Wen Z Y,Jin J.Rapid Low-cost Synthesis And Enhanced Electrochemical Properties of Mesoporous Mn3O4Nanorods[J].Journal of Inorganic Materials,2013,28(9):1045-1050.
[19]Wan C Y,Cheng M,Zhang Q S,et al.Preparation of MnO2Nanostructures by Controlled Crystal Growth and Its Pseudocapacitive Properties[J].Powder Technology,2013,235:706-711.
[20]李文艳.微波辅助制备高比表面积四氧化三锰的研究[D].重庆:重庆大学,2009.