CN105601266A - 气液界面法制备磷酸银二维有序纳米网薄膜及其方法 - Google Patents
气液界面法制备磷酸银二维有序纳米网薄膜及其方法 Download PDFInfo
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- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910000161 silver phosphate Inorganic materials 0.000 title abstract description 8
- 229940019931 silver phosphate Drugs 0.000 title abstract 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
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- 239000000758 substrate Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000005357 flat glass Substances 0.000 claims description 13
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 12
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- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 11
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 11
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 11
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 13
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- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 4
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- AMHXQVUODFNFGR-UHFFFAOYSA-K [Ag+3].[O-]P([O-])([O-])=O Chemical class [Ag+3].[O-]P([O-])([O-])=O AMHXQVUODFNFGR-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
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- 229920006389 polyphenyl polymer Polymers 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
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- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
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Abstract
本发明涉及气液界面制备磷酸银二维有序纳米网薄膜及其方法，通过聚苯乙烯球在气-液界面形成有序单层自组装膜，转移硝酸银水溶液的液面上，通过还原性气体的缓慢释放，在聚苯乙烯球模板表面包覆银纳米微晶，其在大面积呈二维有序纳米网结构，再转移至过氧化氢反应液中，通过原位置换反应得到磷酸银-聚苯乙烯二维有序结构，最后在甲苯溶液浸泡去除聚苯乙烯模板。本发明制备的磷酸银二维有序纳米网薄膜中膜的厚度均匀，晶化度良好，长程有序性好，可以大面积制备，其光催化降解有机染料的催化性能优于同比条件下的磷酸银单晶材料，将其作为超级电容器电极发现其具有良好的循环性能，在光催化以及超级电容器领域都有很好的应用。
Description
技术领域
本发明涉及结构可控的无机半导体材料薄膜的制备方法，尤其是涉及一种气液界面制备磷酸银二维有序纳米网薄膜及其方法。
背景技术
磷酸银纳米半导体材料具有优良光电性能，在光解水制氧、纳米抗菌、光降解有机染料以及超级电容器等领域得到了良好的应用“FacetEffectofSingle-CrystallineAg3PO4Sub-microcrystalsonPhotocatalyticProperties”[Bi,Y.P.；Ouyang,S.X.；Umezawa,N.J.Am.Chem.Soc,2011,133,6490–6492]。目前，在已报道的磷酸银基纳米材料中，可以发现由于磷酸银具有溶液相中迅速成核的特性，其形貌调控主要集中在零维与一维的复合结构“PhotocatalyticandPhotoelectricPropertiesofCubicAg3PO4Sub-microcrystalswithSharpCornersandEdges”[Bi,Y.P.；Hu,H.Y.；Ouyang,S.X.Chem.Commun.,2012,48,3748–3750]，而二维长程有序的磷酸银纳米网薄膜类结构极为少见。磷酸银二维有序薄膜具有比表面大、表面能高、连贯性好、质子的传输效率高等优势，但是其在化学合成方面具有一定的挑战性。对于二维薄膜的制备，目前已有溅射法、气相沉积法、溶胶-凝胶法等成熟的方案，但是这些方法制备的薄膜在应用时受到厚度相对较大、薄膜涂覆不均匀、产品缺陷较多等诸多限制“Photo-catalyticEffectEnhancedbytheChemisorptionofPhenylethyl-mercaptan-assembledMonolayersonAu-clusters/TiO2-anataseThinFilm”[Kao,C.Y.；Liao,J.D.；Huang,W.I.Surface&CoatingsTechnology,2012,206,4887-4891]。因而制备厚度均匀可控、周期性好、廉价易得、条件简单的高产量的二维有序薄膜具有较高的挑战性。
中国专利CN104190451A公开了一种磷酸银薄膜的制备方法，属于半导体光催化与光电化学材料的制备方法。步骤：1)用酒精、丙酮试剂依次超声清洗玻璃或硅片基底；2)用溅射、热蒸发方法在基底上沉积一层Ag膜；3)在Ag膜层上滴满硝酸银AgNO3，旋涂、干燥；再滴上磷酸氢二钠Na2HPO4水溶液，旋涂、干燥；4)再将其置于马弗炉中，升温至300～550℃，保温烧结0.5～3h，得到磷酸银Ag3PO4薄膜。所述的硝酸银AgNO3水溶液的质量百分比浓度为0.017％-0.34％；的磷酸氢二钠Na2HPO4水溶液的质量百分比浓度为0.014％-0.28％；磷酸银Ag3PO4薄膜为结构，厚度为0.3～10μm。该专利通过溅射、热蒸发方法制备银膜，存在薄膜的厚度相对较大、薄膜涂覆不均匀、产品缺陷较多等缺陷；由此制备的Ag3PO4薄膜中磷酸银颗粒的分布较为杂乱无序。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种晶化度良好，长程有序性好，薄膜结构可控的气液界面制备磷酸银二维有序纳米网薄膜及其方法。
本发明的目的可以通过以下技术方案来实现：
气液界面制备磷酸银二维有序纳米网薄膜的方法，采用以下步骤：
(1)将含有聚苯乙烯球的乙醇-水混合溶液缓慢滴加至水面，聚苯乙烯球在表面张力的驱动下扩散组装成有序的单层膜；
(2)取保干器作为反应容器，其上层放置盛有硝酸银溶液的培养皿，以光滑洁净的玻璃片为基底将步骤(1)中获得的聚苯乙烯球单层组装膜转移至该培养皿中；在下层放置研细的二甲胺基甲硼烷粉末及硝酸水溶液，反应10-20h得到银-聚苯乙烯二维有序纳米网薄膜；
(3)将双氧水与磷酸二氢钠组成的混合反应液于干净的培养皿中，取光滑洁净的玻璃片将步骤(2)中制备的银-聚苯乙烯二维有序纳米网薄膜转移至上述培养皿的反应液中，反应2-30min得到磷酸银-聚苯乙烯二维纳米网薄膜；
(4)将负载有磷酸银-聚苯乙烯薄膜的基片浸泡在甲苯溶液中，反应1-3h，去除聚苯乙烯球二维模板，即为磷酸银二维有序纳米网薄膜。
步骤(1)中聚苯乙烯球的乙醇-水混合中乙醇和水的体积比为1:1；聚苯乙烯球浓度是50-80g/L；聚苯乙烯球的直径为300-400nm。
步骤(2)中硝酸银溶液的浓度为20-50mmol/L，硝酸水溶液的浓度为3-5mol/L，二甲胺基甲硼烷与硝酸的摩尔比为0.01-0.03。
步骤(3)中双氧水的体积分数为2-8％，磷酸二氢钠在混合反应液中的浓度为0.1-0.2mol/L。
气液界面法制备磷酸银二维有序纳米网薄膜的厚度为150-250nm；晶化度良好，长程有序性好。
与现有技术相比，本发明利用气液界面反应法制备磷酸银二维有序纳米网薄膜，其薄膜厚度仅有200-350纳米，而且膜的厚度相对均匀，晶化度良好，长程有序性好，可以大面积制备。开发的气液界面反应法，以中间产物二维有序银-聚苯乙烯薄膜为模板，成功制备了磷酸银二维有序纳米网薄膜。该发明中借助于胶体界面自主装制备的聚苯乙烯球为前体模板，使得制备的可反应银-聚苯乙烯模板具有高度有序性，最终在银-聚苯乙烯膜转化为磷酸银膜中发挥了重要作用。因而，本发明制备的磷酸银二维有序纳米网薄膜中膜的厚度均与，晶化度良好，长程有序性好。光电性能测试表明，该产品在光催化以及超级电容器领域都有很好的应用。
我们的发明。
附图说明
图1为聚苯乙烯球(A)、聚苯乙烯球自组装膜(B)、聚苯乙烯-磷酸银薄膜(C)、磷酸银二维有序纳米网薄膜(D-F)纳米中空球薄膜的SEM图。
图2为时间效应对磷酸银薄膜形成的影响图：2分钟(AB)、5分钟(CD)、20分钟(EF)、30分钟(GH)。
图3为过氧化氢的浓度对磷酸银薄膜形貌的影响：2％(AB)、4％(CD)、8％(EF)。
图4为磷酸银薄膜光催化降解罗丹明B性能图
图5为磷酸银薄膜作为超级电容器电极的充放电以及循环性能图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
气液界面制备磷酸银二维有序纳米网薄膜的方法，包括以下步骤：
(1)将含有聚苯乙烯球(图1A)的乙醇-水(V乙醇：V水＝1:1)混合溶液，缓慢滴加至水面，聚苯乙烯球在表面张力的驱动下扩散组装成有序的单层膜(图1B)；
(2)取保干器作为反应容器，其上层放置盛有30毫摩尔/升硝酸银溶液的培养皿，以光滑洁净的玻璃片为基底将(1)中获得的聚苯乙烯球单层组装膜转移至该培养皿中；在下层放置5克研细的二甲胺基甲硼烷粉末以及3毫升浓度为5摩尔/升的硝酸水溶液。反应约12小时后，即可得到银-聚苯乙烯二维有序纳米网薄膜。根据图2所示，聚苯乙烯球的粒径约为350纳米，在聚苯乙烯单层自组装薄膜中，聚苯乙烯球呈高度有序排列，银-聚苯乙烯二维纳米网薄膜呈蜂窝状有序排列。
实施例2
气液界面制备磷酸银二维有序纳米网薄膜的方法，包括以下步骤：
(1)将含有聚苯乙烯球(图1A)的乙醇-水(V乙醇：V水＝1:1)混合溶液，缓慢滴加至水面，聚苯乙烯球在表面张力的驱动下扩散组装成有序的单层膜(图1B)；
(2)取保干器作为反应容器，其上层放置盛有30毫摩尔/升硝酸银溶液的培养皿，以光滑洁净的玻璃片为基底将(1)中获得的聚苯乙烯球单层组装膜转移至该培养皿中；在下层放置5克研细的二甲胺基甲硼烷粉末以及3毫升浓度为5摩尔/升的硝酸水溶液。反应约12小时后，即可得到银-聚苯乙烯二维有序纳米网薄膜(图1C)。
(3)移取双氧水(4％)与磷酸二氢钠(0.2摩尔/升)组成的混合反应液于干净的培养皿中。取光滑洁净的玻璃片(1cm×1cm)将(2)中制备的银-聚苯乙烯二维有序纳米网薄膜转移至上述培养皿的反应液中，反应2-20分钟后，即可得到磷酸银-聚苯乙烯二维纳米网薄膜。
(4)将负载有磷酸银-聚苯乙烯薄膜的基片(3)浸泡在甲苯溶液中，反应2小时，去除聚苯乙烯球模板，即得到磷酸银二维有序纳米网薄膜(图1D-F)，该薄膜由数个磷酸银小纳米粒子有序密堆积而成。根据图2所示，反应时间为2-10分钟较为适宜(A-F)，磷酸银薄膜的连续程度高，薄膜较为完整，同时，随着反应时间的增加，薄膜的颗粒感增强而且磷酸银颗粒有变大的趋势。
实施例3
气液界面制备磷酸银二维有序纳米网薄膜的方法，包括以下步骤：
(1)将含有聚苯乙烯球(图1A)的乙醇-水(V乙醇：V水＝1:1)混合溶液，缓慢滴加至水面，聚苯乙烯球在表面张力的驱动下扩散组装成有序的单层膜(图1B)；
(2)取保干器作为反应容器，其上层放置盛有30毫摩尔/升硝酸银溶液的培养皿，以光滑洁净的玻璃片为基底将(1)中获得的聚苯乙烯球单层组装膜转移至该培养皿中；在下层放置5克研细的二甲胺基甲硼烷粉末以及3毫升浓度为5摩尔/升的硝酸水溶液。反应约12小时后，即可得到银-聚苯乙烯二维有序纳米网薄膜(图1C)。
(3)移取双氧水(4％)与磷酸二氢钠(0.2摩尔/升)组成的混合反应液于干净的培养皿中。取光滑洁净的玻璃片(1cm×1cm)将(2)中制备的银-聚苯乙烯二维有序纳米网薄膜转移至上述培养皿的反应液中，反应2-20分钟后，即可得到磷酸银-聚苯乙烯二维纳米网薄膜。
(4)将负载有磷酸银-聚苯乙烯薄膜的基片(3)浸泡在甲苯溶液中，反应2小时，去除聚苯乙烯球模板，即得到磷酸银二维有序纳米网薄膜。根据图2所示，反应时间超过20分钟后(GH)，部分薄膜的开始破裂，有序结构遭到破坏。
实施例4
气液界面制备磷酸银二维有序纳米网薄膜的方法，包括以下步骤：
(1)将含有聚苯乙烯球(图1A)的乙醇-水(V乙醇：V水＝1:1)混合溶液，缓慢滴加至水面，聚苯乙烯球在表面张力的驱动下扩散组装成有序的单层膜(图1B)；
(2)取保干器作为反应容器，其上层放置盛有30毫摩尔/升硝酸银溶液的培养皿，以光滑洁净的玻璃片为基底将(1)中获得的聚苯乙烯球单层组装膜转移至该培养皿中；在下层放置5克研细的二甲胺基甲硼烷粉末以及3毫升浓度为5摩尔/升的硝酸水溶液。反应约12小时后，即可得到银-聚苯乙烯二维有序纳米网薄膜(图1C)。
(3)移取双氧水(2-8％)与磷酸二氢钠(0.2摩尔/升)组成的混合反应液于干净的培养皿中。取光滑洁净的玻璃片(1cm×1cm)将(2)中制备的银-聚苯乙烯二维有序纳米网薄膜转移至上述培养皿的反应液中，反应10分钟后，即可得到磷酸银-聚苯乙烯二维纳米网薄膜。
(4)将负载有磷酸银-聚苯乙烯薄膜的基片(3)浸泡在甲苯溶液中，反应2小时，去除聚苯乙烯球模板，即得到磷酸银二维有序纳米网薄膜。根据图3所示，过氧化氢反应液浓度在4％较为适宜(CD)，浓度过高(AB)与过低(EF)均将导致薄膜的有序性破坏。
与现有技术相比，本发明采用的方法合成的磷酸银二维有序纳米网薄膜，具有晶化度良好，长程有序性好以及薄膜结构可控的优势，而且根据图4的光催化降解罗丹明B测试表明，其光催化降解有机染料的催化曲线斜率比同比条件下的磷酸银单晶材料更大，催化速率更快，说明其具有更好的光催化性能；根据图5超级电容器性能测试，其循环伏安特性曲线呈超级电容器特有的“矩形”(图5A)；充放电曲线发现其充电时间高于放电时间，能够迅速放电(图5B)；循环曲线发现该材料进行充放电十万次以后，电容衰减仅为2％左右(图5C)，具有良好的循环性能，是作为超级电容器电极的良好材料。
实施例5
气液界面制备磷酸银二维有序纳米网薄膜的方法，采用以下步骤：
(1)将含有聚苯乙烯球的乙醇-水混合溶液缓慢滴加至水面，聚苯乙烯球的乙醇-水混合中乙醇和水的体积比为1:1；聚苯乙烯球浓度为50g/L；聚苯乙烯球的直径为300nm，聚苯乙烯球在表面张力的驱动下扩散组装成有序的单层膜；
(2)取保干器作为反应容器，其上层放置盛有浓度为20mmol/L的硝酸银溶液的培养皿，以光滑洁净的玻璃片为基底将步骤(1)中获得的聚苯乙烯球单层组装膜转移至该培养皿中；在下层放置研细的二甲胺基甲硼烷粉末及浓度为3mol/L硝酸水溶液，二甲胺基甲硼烷与硝酸的摩尔比为0.01，反应10h得到银-聚苯乙烯二维有序纳米网薄膜；
(3)将体积分数为2％双氧水与磷酸二氢钠组成的混合反应液于干净的培养皿中，磷酸二氢钠在混合反应液中的浓度为0.1mol/L，取光滑洁净的玻璃片将步骤(2)中制备的银-聚苯乙烯二维有序纳米网薄膜转移至上述培养皿的反应液中，反应2min得到磷酸银-聚苯乙烯二维纳米网薄膜；
(4)将负载有磷酸银-聚苯乙烯薄膜的基片浸泡在甲苯溶液中，反应1h，去除聚苯乙烯球二维模板，即为磷酸银二维有序纳米网薄膜，厚度为150nm；晶化度良好，长程有序性好。
实施例6
气液界面制备磷酸银二维有序纳米网薄膜的方法，采用以下步骤：
(1)将含有聚苯乙烯球的乙醇-水混合溶液缓慢滴加至水面，聚苯乙烯球的乙醇-水混合中乙醇和水的体积比为1:1；聚苯乙烯球浓度是80g/L；聚苯乙烯球的直径为400nm，聚苯乙烯球在表面张力的驱动下扩散组装成有序的单层膜；
(2)取保干器作为反应容器，其上层放置盛有浓度为50mmol/L的硝酸银溶液的培养皿，以光滑洁净的玻璃片为基底将步骤(1)中获得的聚苯乙烯球单层组装膜转移至该培养皿中；在下层放置研细的二甲胺基甲硼烷粉末及浓度为5mol/L的硝酸水溶液，二甲胺基甲硼烷与硝酸的摩尔比为0.03，反应20h得到银-聚苯乙烯二维有序纳米网薄膜；
(3)将体积分数为8％的双氧水与磷酸二氢钠组成的混合反应液于干净的培养皿中，磷酸二氢钠在混合反应液中的浓度为0.2mol/L，取光滑洁净的玻璃片将步骤(2)中制备的银-聚苯乙烯二维有序纳米网薄膜转移至上述培养皿的反应液中，反应30min得到磷酸银-聚苯乙烯二维纳米网薄膜；
(4)将负载有磷酸银-聚苯乙烯薄膜的基片浸泡在甲苯溶液中，反应1-3h，去除聚苯乙烯球二维模板，即为磷酸银二维有序纳米网薄膜，厚度为250nm；晶化度良好，长程有序性好。
Claims (9)
1.气液界面制备磷酸银二维有序纳米网薄膜的方法，其特征在于，该方法采用以下步骤：
(1)将含有聚苯乙烯球的乙醇-水混合溶液缓慢滴加至水面，聚苯乙烯球在表面张力的驱动下扩散组装成有序的单层膜；
(2)取保干器作为反应容器，其上层放置盛有硝酸银溶液的培养皿，以光滑洁净的玻璃片为基底将步骤(1)中获得的聚苯乙烯球单层组装膜转移至该培养皿中；在下层放置研细的二甲胺基甲硼烷粉末及硝酸水溶液，反应10-20h得到银-聚苯乙烯二维有序纳米网薄膜；
(3)将双氧水与磷酸二氢钠组成的混合反应液于干净的培养皿中，取光滑洁净的玻璃片将步骤(2)中制备的银-聚苯乙烯二维有序纳米网薄膜转移至上述培养皿的反应液中，反应2-30min得到磷酸银-聚苯乙烯二维纳米网薄膜；
(4)将负载有磷酸银-聚苯乙烯薄膜的基片浸泡在甲苯溶液中，反应1-3h，去除聚苯乙烯球二维模板，即为磷酸银二维有序纳米网薄膜。
2.根据权利要求1所述的气液界面制备磷酸银二维有序纳米网薄膜的方法，其特征在于，步骤(1)中所述的聚苯乙烯球的乙醇-水混合中乙醇和水的体积比为1:1；聚苯乙烯球浓度是50-80g/L。
3.根据权利要求1所述的气液界面制备磷酸银二维有序纳米网薄膜的方法，其特征在于，步骤(1)中所述的聚苯乙烯球的直径为300-400nm。
4.根据权利要求1所述的气液界面制备磷酸银二维有序纳米网薄膜的方法，其特征在于，步骤(2)中硝酸银溶液的浓度为20-50mmol/L。
5.根据权利要求1所述的气液界面制备磷酸银二维有序纳米网薄膜的方法，其特征在于，步骤(2)中硝酸水溶液的浓度为3-5mol/L。
6.根据权利要求1所述的气液界面制备磷酸银二维有序纳米网薄膜的方法，其特征在于，步骤(2)中二甲胺基甲硼烷与硝酸的摩尔比为0.01-0.03。
7.根据权利要求1所述的气液界面制备磷酸银二维有序纳米网薄膜的方法，其特征在于，步骤(3)中双氧水的体积分数为2-8％。
8.根据权利要求1所述的气液界面制备磷酸银二维有序纳米网薄膜的方法，其特征在于，步骤(3)中磷酸二氢钠在混合反应液中的浓度为0.1-0.2mol/L。
9.如权利要求1所述的气液界面法制备磷酸银二维有序纳米网薄膜，其特征在于，磷酸银二维有序纳米网薄膜的厚度为150-250nm；晶化度良好，长程有序性好。
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| CN111421133A (zh) * | 2020-03-30 | 2020-07-17 | 扬州大学 | 银纳米片团簇阵列及其制备方法 |
| CN113200534A (zh) * | 2021-05-19 | 2021-08-03 | 重庆交通大学 | 基于平面基膜的氧化石墨烯还原自组装薄膜制备方法 |
| CN113333013A (zh) * | 2021-06-22 | 2021-09-03 | 广西大学 | 一种Ag3PO4-CoFe2O4/g-C3N4复合高效光催化剂及其制备方法 |
| CN113680358A (zh) * | 2021-07-13 | 2021-11-23 | 湖南农业大学 | 磷酸银/碳化硼复合光催化剂及其制备方法和应用 |
| CN116130608A (zh) * | 2023-04-04 | 2023-05-16 | 山东科技大学 | 一种通过自组装技术制备氧化钛薄膜柔性电极的方法 |
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| CN111421133A (zh) * | 2020-03-30 | 2020-07-17 | 扬州大学 | 银纳米片团簇阵列及其制备方法 |
| CN111421133B (zh) * | 2020-03-30 | 2022-01-21 | 扬州大学 | 银纳米片团簇阵列及其制备方法 |
| CN113200534A (zh) * | 2021-05-19 | 2021-08-03 | 重庆交通大学 | 基于平面基膜的氧化石墨烯还原自组装薄膜制备方法 |
| CN113333013A (zh) * | 2021-06-22 | 2021-09-03 | 广西大学 | 一种Ag3PO4-CoFe2O4/g-C3N4复合高效光催化剂及其制备方法 |
| CN113680358A (zh) * | 2021-07-13 | 2021-11-23 | 湖南农业大学 | 磷酸银/碳化硼复合光催化剂及其制备方法和应用 |
| CN113680358B (zh) * | 2021-07-13 | 2023-09-12 | 湖南农业大学 | 磷酸银/碳化硼复合光催化剂及其制备方法和应用 |
| CN116130608A (zh) * | 2023-04-04 | 2023-05-16 | 山东科技大学 | 一种通过自组装技术制备氧化钛薄膜柔性电极的方法 |
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