CN111777099A - 一种立方尖晶石型纳米片状亚铬酸铜的制备方法 - Google Patents
一种立方尖晶石型纳米片状亚铬酸铜的制备方法 Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 33
- 239000011029 spinel Substances 0.000 title claims abstract description 33
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 6
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 6
- 239000012498 ultrapure water Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 4
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 abstract description 34
- 238000000354 decomposition reaction Methods 0.000 abstract description 12
- 238000000197 pyrolysis Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000265 homogenisation Methods 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 239000002060 nanoflake Substances 0.000 description 9
- 229910002477 CuCr2O4 Inorganic materials 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明公开了一种立方尖晶石型纳米片状亚铬酸铜的制备方法，将硝酸铜和硝酸铬溶解于超纯水中，加入六亚甲基四胺作为均匀沉淀剂，加入四乙基氟化铵、氟化铵、氟化钾等含氟化合物作为形貌调节剂，将溶液超声均匀后微波加热至80～95℃，反应后得到前驱体，将该前驱体用无水乙醇和超纯水多次洗涤后干燥、研磨均匀，然后在400～450℃下焙烧，即可得到立方尖晶石型纳米片状亚铬酸铜。本发明制备方法简单，所得立方尖晶石型纳米片状亚铬酸铜纯度高、比表面积大、表面活性位点多、催化效果好，能够显著降低高氯酸铵热分解的高温分解峰温，并且提升高氯酸铵的表观分解热。
Description
技术领域
本发明属于固体推进剂技术领域，具体涉及一种立方尖晶石型纳米片状亚铬酸铜的制备方法。
背景技术
尖晶石型亚铬酸铜(CuCr2O4)被认为是一种多功能型材料，广泛应用于光催化、半导体、催化加氢等领域。近些年来，研究者发现CuCr2O4对于高氯酸铵(AP)的热分解有着优异的催化性能。李卫等(Solid State Science.2007,9(8):750-755)将立方相Cu-Cr-O纳米粒子加入到AP基的固体推进剂中，发现Cu-Cr-O纳米粒子不仅提高了推进剂燃速，而且降低了推进剂的压力指数。郝嘎子等(火炸药学报.2015,38(01):26-29)通过纳米化粉碎机，以商业的CuCr2O4为原料，制备了60nm的纳米CuCr2O4，使用溶剂挥发法将CuCr2O4和AP混合均匀，经测试，该纳米CuCr2O4可以使AP的高温分解温度降低67℃，表观分解热增加424.57J/g。邢玉静等(火炸药学报.2012,35(4):41-44)采用柠檬酸配位法合成了超细纯立方尖晶石型CuCr2O4，它可以使AP高温分解峰提前至339.6℃，复合改性双基推进剂在6MPa下燃速从35.84mm/s提高到61.00mm/s，压力指数从0.62降低至0.14。
发明内容
本发明的目的是提供一种比表面积大、活性位点多、催化性能好的立方尖晶石型纳米片状CuCr2O4的制备方法。
针对上述目的，本发明采用的技术方案由下述步骤组成：
1、将硝酸铜和硝酸铬完全溶解于超纯水中，然后加入六亚甲基四胺和含氟化合物，超声得到均匀溶液；其中，所述的含氟化合物为四乙基氟化铵、氟化铵、氟化钾中任意一种。
2、将步骤1的溶液微波加热至80～95℃，恒温反应35～45min，反应完后得到绿色的浑浊液。
3、将步骤2的浑浊液进行离心分离、洗涤，所得绿色沉淀经干燥、研磨，得到前驱体。
4、将步骤3的前驱体加热至400～450℃，恒温焙烧2.5～3.5h，得到立方尖晶石型纳米片状亚铬酸铜。
上述步骤1中，优选所述硝酸铜和硝酸铬、六亚甲基四胺、含氟化合物的摩尔比为1:2:4.5～6:4.5～5.5。
上述步骤1中，所述超声的时间为20～30min。
上述步骤2中，所述微波加热的功率为500～600W。
上述步骤3中，所述干燥的温度为80～100℃，干燥时间为10～15h。
上述步骤4中，优选加热的升温速率为0.5～2℃/min。
本发明的有益效果如下：
本发明制备方法简单，产率高，能够在低的煅烧温度下得到CuCr2O4，且所得CuCr2O4为高纯度的立方尖晶石型纳米片状，其厚度约为10～40nm，比表面积为90～100m2·g-1，具有比表面积大、表面活性位点多、催化效果好的优点，可以显著降低高氯酸铵热分解的高温分解峰温，并且提升高氯酸铵的表观分解热。
附图说明
图1是实施例1～3制备的立方尖晶石型纳米片状CuCr2O4的X-射线衍射图。
图2是实施例1制备的立方尖晶石型纳米片状CuCr2O4的扫描电子显微镜图。
图3是实施例2制备的立方尖晶石型纳米片状CuCr2O4的扫描电子显微镜图。
图4是实施例3制备的立方尖晶石型纳米片状CuCr2O4的扫描电子显微镜图。
图5是AP中添加5％实施例1～3制备的立方尖晶石型纳米片状CuCr2O4和纯AP的差示扫描量热分析曲线。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
1、将0.145g(0.6mmol)硝酸铜和0.480g(1.2mmol)硝酸铬溶解于140mL超纯水中，然后加入0.421g(3mmol)六亚甲基四胺和0.555g(3mmol)四乙基氟化铵，超声30min，得到均匀溶液。
2、将步骤1的溶液放置于微波反应器中，在搅拌状态下微波加热至90℃，加热功率为500W，然后恒温反应40min，反应完后冷却至室温，得到绿色的浑浊液。
3、将步骤2的浑浊液进行离心分离，并用无水乙醇和超纯水离心洗涤各5次，离心转速为9000r/min，每次时间为5min，所得绿色沉淀在鼓风干燥箱中80℃干燥12h后，研磨均匀，得到前驱体。
4、将步骤3的前驱体放置于管式炉中，以1℃/min的升温速率加热至400℃，恒温焙烧3h，得到黑色粉末，即立方尖晶石型纳米片状CuCr2O4，产率为87％。
实施例2
本实施例的步骤1中，用等摩尔氟化铵替换四乙基氟化铵，其他步骤与实施例1相同，得到立方尖晶石型纳米片状CuCr2O4，产率为83％，比表面积为95.4m2·g-1。
实施例3
本实施例的步骤1中，用等摩尔氟化钾替换四乙基氟化铵，其他步骤与实施例1相同，得到立方尖晶石型纳米片状CuCr2O4，产率为85％。
采用X-射线衍射仪和扫描电子显微镜对实施例1～3制备的样品进行结构和形貌表征，结果见图1～4。由图1可见，实施例1～3制备的样品的2θ特征峰为18.39°、30.37°、35.59°、37.28°、43.47°、57.55°和63.20°，分别对应晶面(111)、(220)、(311)、(222)、(400)、(511)和(440)，与立方相CuCr2O4的标准PDF卡片(JCPDS:26-0509)对应一致，无其它杂质峰，说明制备的CuCr2O4样品较纯。由图2～4的SEM图可以看出，实施例1～3制备的CuCr2O4的形貌均为纳米片状，厚度为15～40nm。
为了证明本发明的有益效果，发明人以AP为例，对实施例1～3制备的立方尖晶石型纳米片状CuCr2O4的催化性能进行测试，具体实验情况如下：
1、取5mgCuCr2O4、95mg粉末状的高氯酸铵，研磨混合均匀，采用差示扫描量热仪对其催化性能进行测试，实验结果见图5。
从图5中可以看出纯AP的热分解过程分为三个阶段，第一阶段是AP的晶型转变，晶体从低温的斜方晶型转变为高温的立方晶型，图中纯AP的晶型转变在244℃；第二阶段是AP的低温分解阶段，图中AP低温分解的起始温度为265℃，低温分解峰峰温为291℃，低温分解阶段是放热过程，包括解离和升华两个过程，AP的低温分解主要是气-固多相反应；第三阶段是AP的高温分解阶段，从345℃到421℃为AP的高温分解阶段，高温分解峰峰温为406℃，这是是主要的分解阶段，此阶段AP完全分解为HCl、H2O、Cl2、O2、NO、N2O和NO2等挥发性产物。从图5中可以看出，在整个过程中AP的放热并不明显。相同条件下，当在固体推进剂主组分AP中添加5％实施例1～3制备的立方尖晶石型纳米片状CuCr2O4作为催化剂后，AP高温分解阶段的峰温从406℃分别降低至327℃、334℃、342℃，分别降低了79℃、72℃和64℃，明显高于郝嘎子等人(火炸药学报.2015,38(01):26-29)的测试结果，说明实施例1～3制备的立方尖晶石型纳米片状CuCr2O4对AP热分解的促进作用更加明显；另外AP的表观分解热分别增加443J/g、344J/g和323J/g，由此可见，与纯AP在高温分解阶段相比，加入实施例1～3制备的立方尖晶石型纳米片状CuCr2O4后，AP的高温分解阶段呈现集中放热现象，AP热分解的高温分解峰温明显的降低，并且体系放出的热量较纯AP增大很多，说明本发明制备的立方尖晶石型纳米片状CuCr2O4对AP的热分解具有良好的燃烧催化作用，其中实施例1制备的立方尖晶石型纳米片状CuCr2O4对AP热分解催化效果最好。
Claims (6)
1.一种立方尖晶石型纳米片状亚铬酸铜的制备方法，其特征在于所述方法由以下步骤组成：
(1)将硝酸铜和硝酸铬完全溶解于超纯水中，然后加入六亚甲基四胺和含氟化合物，超声得到均匀溶液；其中，所述的含氟化合物为四乙基氟化铵、氟化铵、氟化钾中任意一种；
(2)将步骤(1)的溶液微波加热至80～95℃，恒温反应35～45min，反应完后得到绿色的浑浊液；
(3)将步骤(2)的浑浊液进行离心分离、洗涤，所得绿色沉淀经干燥、研磨，得到前驱体；
(4)将步骤(3)的前驱体加热至400～450℃，恒温焙烧2.5～3.5h，得到立方尖晶石型纳米片状亚铬酸铜。
2.根据权利要求1所述的立方尖晶石型纳米片状亚铬酸铜的制备方法，其特征在于：步骤(1)中，所述硝酸铜和硝酸铬、六亚甲基四胺、含氟化合物的摩尔比为1:2:4.5～6:4.5～5.5。
3.根据权利要求1所述的立方尖晶石型纳米片状亚铬酸铜的制备方法，其特征在于：步骤(1)中，所述超声的时间为20～30min。
4.根据权利要求1所述的立方尖晶石型纳米片状亚铬酸铜的制备方法，其特征在于：步骤(2)中，所述微波加热的功率为500～600W。
5.根据权利要求1所述的立方尖晶石型纳米片状亚铬酸铜的制备方法，其特征在于：步骤(3)中，所述干燥的温度为80～100℃，干燥时间为10～15h。
6.根据权利要求1所述的立方尖晶石型纳米片状亚铬酸铜的制备方法，其特征在于：步骤(4)中，加热的升温速率为0.5～2℃/min。
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