CN109110825B - 一种具有三级孔结构的氧化镍中空微球及其制备方法 - Google Patents
一种具有三级孔结构的氧化镍中空微球及其制备方法 Download PDFInfo
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- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
本发明涉及一种氧化镍微球,为内部中空的球形结构,球壳由各氧化镍纳米片组装而成,氧化镍纳米片所处的平面与氧化镍中空微球的球壳厚度方向保持一致,球壳上有孔隙,孔隙由相邻纳米片之间围合的区域构成,孔隙的孔截面为多边形,孔隙的孔截面尺寸随着方向a逐渐增大,方向a为球壳内侧指向球壳外侧的方向,氧化镍纳米片的表面为介孔结构。上述氧化镍微球具有独特的三级孔结构,具有高的比表面积和孔隙率。
Description
技术领域
本发明涉及半导体材料的制备领域,具体涉及一种具有三级孔结构的氧化镍中空微球及其制备方法。
背景技术
纳米材料是指在三维空间中至少有一维处在纳米尺度范围(1~100nm)或由他们作为基本单元构成的材料。因其特有的性质,如表面与界面效应、小尺寸效应、量子尺寸效应和宏观量子隧道效应,在光、电、磁等诸多领域都有着重要的功能和作用。纳米材料的物理化学性能与其晶体结构、形态学结构以及粒子大小等密切相关,具有独特形貌结构的微纳米材料通常显示优越的物理化学性能,越来越受到人们高度重视。其中,中空多孔分级微纳米结构的材料因具有较大的比表面积、较低的密度、优良的渗透性和独特的光电及表面性能,是纳米材料科学研究热点之一。
氧化镍的晶体结构为立方晶系,与氯化钠类似,即岩盐结构,其中每个Ni周围有六个最近距离的O,氧原子形成正八面体,镍原子处于其中心。氧化镍是一类重要的p型宽禁带半导体材料,在气敏元件、吸附剂、电极材料、电致变色和燃料电池等方面都有着广泛的应用。氧化镍纳米材料的形貌结构非常丰富,通过各种各样的制备方法已制备出各种形态结构的氧化镍微纳米材料,如纳米颗粒、纳米纤维,纳米管、花状、海胆状微球等等,并广泛应用于吸附剂、气敏器件、超级电容器、锂离子电池等。
其中,具有分级结构的氧化镍中空微球也有诸多的制备方法予以大量报道,就文献调研,涉及的物理化学制备方法可概括为以下两种工艺:一,引入结构修饰剂或矿化剂制备氢氧化镍前体,然后经热处理得到氧化镍中空结构。如Wang等使用甘氨酸为结构导向剂,通过水热合成技术先制得β-Ni(OH)2中空微球,再经600℃热分解得到由50-100nm片组装而成的氧化镍中空微球(Yong Wang,Qingshan Zhu,Huigang Zhang,Fabrication ofβ-Ni(OH)2and NiO hollow spheres by a facile template free process,Chem.Commun.,2005,5231-5233);随后,Cao等利用乙二醇(EG)为结构导向剂和微波加热技术、Al-Hazmi等采用四丁基胺(TBAB)为结构导向剂和超声化学技术,Liu采用丙三醇和Feng等采用三乙二醇(TEG)为结构导向剂和水热合成技术,并经热处理工艺合成得到了分级结构氧化镍纳米空心球(Chang-Yan Cao,Wei Guo,Zhi-Min Cui,Wei-Guo Song,Wei Cai,Microwave-assisted gas/liquid interfacial synthesis of flowerlike NiO hollow nanosphereprecursors and their application as supercapacitor electrodes,J.Mater.Chem.,2011,21,3204-3209;F.Al-Hazmi,T.Al-Harbi,Waleed E.Mahmoud,Synthesis andcharacterization of thin shell hollow sphere NiO nanopowder via ultrasonictechnique,Mater.Lett.,86(2012),28-30;Sen Liu,Bo Yu,Tong Zhang,A novel non-enzymatic glucose sensor based on NiO hollow spheres,Electrochimica Acta,102(2013),104-107;Fan Feng,Shiqiang Zhao,Rui Liu,Zewen Yang,Qiang Shen,NiOFlowerlike porous hollow nanostructures with an enhanced interfacial storagecapability for battery-to-pseudocapacitor transition,Electrochimica Acta,222(2016),1160-1168);Xie等采用草酸根为结构导向剂,通过超声技术合成草酸镍前体,然后经空气中热处理得到多孔的氧化镍中空微球(Dong Xie,Weiwei Yuan,Zimin Dong,Qingmei Su,Jun Zhang,Gaohui Du,Facile synthesis of porous NiO hollowmicrospheres and its electrochemical lithium-storage performance,Electrochimica Acta,92(2013),87-92);Yan等采用硫酸镍、过硫酸钾和氨水的混合溶液经化学浴沉积得到氢氧化镍前体,再经300℃热处理得到由纳米片交错组装的多晶性的氧化镍空心球(Xiaoyan Yan,Xili Tong,Jian Wang,Changwei Gong,Mingang Zhang,LipingLiang,Rational synthesis of hierarchically porous NiO hollow spheres andtheir supercapacitor application,Mater.Lett.,95(2013),1-4)。最近,Kuang采用尿素为矿化剂,通过水热合成技术和退火工艺制得了由纳米带组装的氧化镍开口空心球(Chengwei Kuang,Wen Zeng,Hong Yeb,Yanqiong Li,A novel approach forfabricating NiO hollow spheres for gas sensors,Physica E:Low-dimensionalSystems and Nanostructures,97(2018),314-316)。二,引入模板剂(表面活性剂为软模板,高分子聚合物、碳球等为硬模板)制得含镍前体,再经其他工艺得到氧化镍空心微球。如Liu等和Ci等采用十二烷基磺酸钠(SDS)为软模板通过溶剂热技术分别制得了纳米片组装的氧化镍中空微球(Jian Liu,Shangfeng Du,Lianqi Wei,Haidi Liu,Yajun Tian,YunfaChen,Template-free synthesis of NiO hollow microspheres covered withnanoflakes,Mater.Lett.,60(2006)3601-3604;Suqin Ci,Taizhong Huang,Zhenhai Wen,Shumao Cui,Shun Mao,Douglas A.Steeber,Junhong Chen,Nickel oxide hollowmicrosphere for non-enzyme glucose detection,Biosensors and Bioelectronics,54(2014),251-257);Cho等采用高分子聚甲基丙烯酸甲酯(PMMA)为模板制得了氧化镍半球(Nam Gyu Cho,In-Sung Hwang,Ho-Gi Kim,Jong-Heun Lee,Il-Doo Kim,Gas sensingproperties of p-type hollow NiO hemispheres prepared by polymeric colloidaltemplating method,Sens.Actuators B,155(2011),366-371);Ding等采用磺化的聚苯乙烯(PS)小球为模板、Zhang等采用功能化的PS小球为模板、Yu等以羧基化的PS小球为模板分别制得了分级结构的中空氧化镍微纳米球(Shujiang Ding,Ting Zhu,Jun Song Chen,Zhiyu Wang,Chongli Yuan,Xiong Wen(David)Lou,Controlled synthesis ofhierarchical NiO nanosheet hollow spheres with enhanced supercapacitiveperformance,J.Mater.Chem.,2011,21,6602-6606;Peipei Zhang,Xiaoming Ma,YumingGuo,Qianqian Cheng,Lin Yang,Size-controlled synthesis of hierarchical NiOhollow microspheres and the adsorption for Congo red in water,Chem.Eng.J.,189-190(2012),188-195;Wei Yu,Xinbing Jiang,Shujiang Ding,Ben Q.Li,Preparationand electrochemical characteristics of porous hollow spheres of NiOnanosheets as electrodes of supercapacitors,Journal of Power Sources,256(2014),440-448);Chengchao Li等、Cui等和Hao Li等分别采用碳球(carbon sphere)为模板,再通过水热合成技术制得了不同微纳结构的氧化镍中空纳米球(Chengchao Li,YanliLiu,Limiao Li,Zhifeng Du,Shoujiang Xu,Ming Zhang,Xiaoming Yin,TaihongWang,Anovel amperometric biosensor based on NiO hollow nanospheres for biosensingglucose,Talanta 77(2008)455-459;Zhenzhen Cui,Haoyong Yin,Qiulin Nie,DongyuQin,Weiwei Wu,Xiaolong He,Hierarchical flower-like NiO hollowmicrospheres fornon-enzymatic glucose sensors,J.Electroanal.Chem.,757(2015),51-57;Hao Li,Haoran Ma,Mei Yang,Bao Wang,Hui Shao,Lei Wangb,Ranbo Yu,Dan Wang,Highlycontrolled synthesis of multi-shelled NiO hollow microspheres for enhancedlithium storage properties,Materials Research Bulletin,87(2017),224-229);Huang等在间苯二酚-甲醛混合溶剂中制得碳球/Ni干凝胶,然后在氩气气氛下700℃焙烧得到了氧化镍空心微球(X.H.Huang,J.P.Tu,C.Q.Zhang,F.Zhou,Hollow microspheres ofNiO as anode materials for lithium-ion batteries,Electrochimica Acta,55(2010),8981-8985);还有一种特殊的模板工艺,如Hao等采用柠檬酸锌微球为模板通过化学侵蚀方法制得了由纳米粒子组装而成的氧化镍空心微球(Shiji Hao,Bowei Zhang,Sarah Ball,Bo Hu,Junsheng Wu,Yizhong Huang,Porous and hollow NiO microspheresfor high capacity and long-life anode materials of Li-ion batteries,Materialsand Design,92(2016),160-165)。
但上述相关的制备方法均存在一定的缺陷。
发明内容
本发明的目的是提供一种具有三级孔结构的氧化镍中空微球,具有独特的三级孔结构,具有高的比表面积和孔隙率。
一种氧化镍微球,其特征在于:为内部中空的球形结构,球壳由各氧化镍纳米片组装而成,氧化镍纳米片所处的平面与氧化镍中空微球的球壳厚度方向保持一致,球壳上有孔隙,孔隙由相邻纳米片之间围合的区域构成,孔隙的孔截面为多边形,孔隙的孔截面尺寸随着方向a逐渐增大,方向a为球壳内侧指向球壳外侧的方向,氧化镍纳米片的表面为介孔结构。
氧化镍微球的外径为600~1000nm,球壳的厚度为200~300nm,纳米片的厚度为7~9nm,氧化镍纳米片的表面的介孔的孔径为5~20nm。
本发明还提供了一种氧化镍微球的制备方法,其特征在于:包括制备海胆状β-Ni(OH)2微球和将β-Ni(OH)2微球在空气氛围中进行热处理。
具体的:β-Ni(OH)2微球采用无模板化学浴沉积方法制得。
将溶液B加入溶液A中混合,然后再加入溶液C进行混合得到反应液,随后将反应液进行恒温反应,恒温反应结束后回收沉淀生成物,将沉淀生成物进行退火处理即可制得氧化镍微球;
所述溶液A为NiCl2水溶液;
所述溶液B为CO(NH2)2水溶液;
所述溶液C为氨水。
反应液中NiCl2与CO(NH2)2的摩尔比为1:2。
溶液C为质量百分比28%的氨水,按照每1mol NiCl2加入3~5mL溶液C的比例混合配制反应液。
恒温反应在恒温水浴锅中进行,控制水浴的温度为90℃,恒温反应3~5h。
退火处理在马弗炉中进行,设置升温速率2℃/min,退火温度为350~400℃,时间2~4小时。
恒温反应结束后,将反应液自然冷却至室温,过滤回收沉淀生成物,分别用水和无水乙醇洗涤沉淀生成物,洗涤后将沉淀生成物置于温度为60~80℃烘箱中加热6~10小时,收集得到β-Ni(OH)2微球。
与现有技术相比,本发明具备的技术效果为:
1)、本发明制备的具有三级孔结构的氧化镍中空微球,外直径约600~1000nm,内部有较大空腔,球壳由纳米片互相交错连接而成,在交接处形成孔隙,纳米片平均厚度约8nm,片表面上含有大量的微孔。这种氧化镍中空微球具有独特的三级孔结构,具有高的比表面积和孔隙率,有望用于气敏元件、吸附剂、超级电容器和太阳能电池等领域。
2)、本发明的具有三级孔结构的氧化镍中空微球的制备方法,不使用模板剂,反应条件温和,工艺设备简单,操作简便,重复性好,原料价廉易得,适合产业化生产。
附图说明
图1是实施例1制备的具有三级孔结构的氧化镍中空微球的X射线衍射分析(XRD)谱图;
图2是实施例1制备的具有三级孔结构的氧化镍中空微球的场发射扫描电子显微镜(FE-SEM)低倍照片;
图3是实施例1制备的具有三级孔结构的氧化镍中空微球的场发射扫描电子显微镜(FE-SEM)中倍照片;
图4是实施例1制备的具有三级孔结构的氧化镍中空微球的场发射扫描电子显微镜(FE-SEM)高倍照片;
图5是实施例1制备的具有三级孔结构的氧化镍中空微球的透射电子显微镜(TEM)照片;
图6是实施例1制备的具有三级孔结构的氧化镍中空微球的三阶孔结构。
具体实施方式
为了使本发明的目的及优点更加清楚明白,以下结合实施例对本发明进行具体说明。应当理解,以下文字仅仅用以描述本发明的一种或几种具体的实施方式,并不对本发明具体请求的保护范围进行严格限定。
实施例1
称取1.0mmol结晶二水合氯化镍NiCl2·6H2O用去离子水搅拌水解成蓝绿色溶液A;称取2.0mmol尿素(CO(NH2)2)用去离子水配制成无色溶液B;在搅拌情况下,将溶液B加入溶液A到中,再量取4mL质量百分比28%的NH3·H2O加入到混合反应液中,继续搅拌10分钟,反应溶液总体积为60mL;将反应液转移到100mL的高脚烧杯中,用聚乙烯膜(PE)覆盖。然后将盛有反应混合液的高脚烧杯置于恒温水浴锅中,设置水浴温度为90℃,保温时间为4小时,反应结束后,取出自然冷却至室温,过滤沉淀物,分别用水和无水乙醇洗涤2~3次,将沉淀物置于温度为60~80℃烘箱中加热6~10小时,收集粉浅绿色粉体;再将盛有适量粉浅绿色粉体的陶瓷干锅置于马弗炉中,在空气中退火处理,设置升温速率2℃/min,退火温度为400℃,保温时间2小时,自然冷却至室温,收集粉体即得到本发明的具有三级孔结构的氧化镍中空微球纳米材料。
参见附图1,按实施例1制得的具有三级孔结构的氧化镍中空微球的X-射线粉末衍射分析(XRD)谱图。图中可见所有谱线峰对应于JCPDF标准卡片(47-1049)的所有衍射晶面,指标为立方相的NiO晶体,衍射峰强度大,表明晶体结晶性好;没有发现其他杂质峰,表明样品纯度高。
参见附图2-4,按实施例1制备的具有三级孔结构的氧化镍中空微球的场发射扫描电子显微镜(FE-SEM)低倍、中倍和高倍照片。从图2中可以看出,由纳米片组装而成的微球分散性较好,粒径现对均匀,外直径介于600-1000nm;图3显示了一个完整的由多孔纳米片组装而成的氧化镍中空微球,清晰地显示球壳由多孔纳米片互相交错连接而成,在交接处形成“漏斗状”孔隙;从图4高倍SEM照片中,可以计算出纳米片的平均厚度约8nm,纳米片表面上含有大量的介孔结构,孔径约5-20nm。
参见附图5,按实施例1制备的具有三级孔结构的氧化镍中空微球的透射电子显微镜(TEM)照片,从图中明显地看出微球内部有较大孔腔。
参见附图6,按实施例1制备的具有三级孔结构的独特的三级孔结构,具有高的比表面积和孔隙率。
实施例2
称取1.0mmol结晶二水合氯化镍NiCl2·6H2O用去离子水搅拌水解成蓝绿色溶液A;称取2.0mmol尿素(CO(NH2)2)用去离子水配制成无色溶液B;在搅拌情况下,将溶液B加入溶液A到中,再量取3mL质量百分比28%的NH3·H2O加入到混合反应液中,继续搅拌10分钟,反应溶液总体积为60mL;将反应液转移到100mL的高脚烧杯中,用聚乙烯膜(PE)覆盖。然后将盛有反应混合液的高脚烧杯置于恒温水浴锅中,设置水浴温度为90℃,保温时间为5小时,反应结束后,取出自然冷却至室温,过滤沉淀物,分别用水和无水乙醇洗涤2~3次,将沉淀物置于温度为60~80℃烘箱中加热6~10小时,收集粉浅绿色粉体;再将盛有适量粉浅绿色粉体的陶瓷干锅置于马弗炉中,在空气中退火处理,设置升温速率2℃/min,退火温度为400℃,保温时间2小时,自然冷却至室温,收集粉体即得到本发明的具有三级孔结构的氧化镍中空微球纳米材料。
实施例3
称取1.0mmol结晶二水合氯化镍NiCl2·6H2O用去离子水搅拌水解成蓝绿色溶液A;称取2.0mmol尿素(CO(NH2)2)用去离子水配制成无色溶液B;在搅拌情况下,将溶液B加入溶液A到中,再量取4mL质量百分比28%的NH3·H2O加入到混合反应液中,继续搅拌10分钟,反应溶液总体积为60mL;将反应液转移到100mL的高脚烧杯中,用聚乙烯膜(PE)覆盖。然后将盛有反应混合液的高脚烧杯置于恒温水浴锅中,设置水浴温度为90℃,保温时间为5小时,反应结束后,取出自然冷却至室温,过滤沉淀物,分别用水和无水乙醇洗涤2~3次,将沉淀物置于温度为60~80℃烘箱中加热6~10小时,收集粉浅绿色粉体;再将盛有适量粉浅绿色粉体的陶瓷干锅置于马弗炉中,在空气中退火处理,设置升温速率2℃/min,退火温度为400℃,保温时间3小时,自然冷却至室温,收集粉体即得到本发明的具有三级孔结构的氧化镍中空微球纳米材料。
实施例4
称取1.0mmol结晶二水合氯化镍NiCl2·6H2O用去离子水搅拌水解成蓝绿色溶液A;称取2.0mmol尿素(CO(NH2)2)用去离子水配制成无色溶液B;在搅拌情况下,将溶液B加入溶液A到中,再量取5mL质量百分比28%的NH3·H2O加入到混合反应液中,继续搅拌10分钟,反应溶液总体积为60mL;将反应液转移到100mL的高脚烧杯中,用聚乙烯膜(PE)覆盖。然后将盛有反应混合液的高脚烧杯置于恒温水浴锅中,设置水浴温度为90℃,保温时间为3小时,反应结束后,取出自然冷却至室温,过滤沉淀物,分别用水和无水乙醇洗涤2~3次,将沉淀物置于温度为60~80℃烘箱中加热6~10小时,收集粉浅绿色粉体;再将盛有适量粉浅绿色粉体的陶瓷干锅置于马弗炉中,在空气中退火处理,设置升温速率2℃/min,退火温度为400℃,保温时间5小时,自然冷却至室温,收集粉体即得到本发明的具有三级孔结构的氧化镍中空微球纳米材料。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (2)
1.一种氧化镍微球的制备方法,其特征在于:包括制备海胆状β-Ni(OH)2微球和将β-Ni(OH)2微球在空气氛围中进行热处理;β-Ni(OH)2微球采用无模板化学浴沉积方法制得;将溶液B加入溶液A中混合,然后再加入溶液C进行混合得到反应液,随后将反应液进行恒温反应,恒温反应结束后回收沉淀生成物,将沉淀生成物进行退火处理即可制得氧化镍微球;
所述溶液A为NiCl2水溶液;
所述溶液B为CO(NH2)2水溶液;
所述溶液C为氨水;
反应液中NiCl2与CO(NH2)2的摩尔比为1:2;
溶液C为质量百分比28%的氨水,按照每1mol NiCl2加入3~5mL溶液C的比例混合配制反应液;恒温反应在恒温水浴锅中进行,控制水浴的温度为90℃,恒温反应3~5h;
退火处理在马弗炉中进行,设置升温速率2℃/min,退火温度为350~400℃,时间2~4小时;
所述氧化镍微球为内部中空的球形结构,球壳由各氧化镍纳米片组装而成,氧化镍纳米片所处的平面与氧化镍中空微球的球壳厚度方向保持一致,球壳上有孔隙,孔隙由相邻纳米片之间围合的区域构成,孔隙的孔截面为多边形,孔隙的孔截面尺寸随着方向a逐渐增大,方向a为球壳内侧指向球壳外侧的方向,氧化镍纳米片的表面为介孔结构;氧化镍微球的外径为600~1000nm,球壳的厚度为200~300nm,纳米片的厚度为7~9nm,氧化镍纳米片的表面的介孔的孔径为5~20nm。
2.根据权利要求1所述的氧化镍微球的制备方法,其特征在于,恒温反应结束后,将反应液自然冷却至室温,过滤回收沉淀生成物,分别用水和无水乙醇洗涤沉淀生成物,洗涤后将沉淀生成物置于温度为60~80℃烘箱中加热6~10小时,收集得到β-Ni(OH)2微球。
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