CN115180650B - 二硫化钼纳米片组装的二硫化钼纳米棒及制备方法和用途 - Google Patents
二硫化钼纳米片组装的二硫化钼纳米棒及制备方法和用途 Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 108
- 239000002073 nanorod Substances 0.000 title claims abstract description 52
- 239000002135 nanosheet Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- -1 ammonium heptamolybdate tetrahydrate Chemical class 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 239000002057 nanoflower Substances 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
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- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- FASDKYOPVNHBLU-ZETCQYMHSA-N pramipexole Chemical compound C1[C@@H](NCCC)CCC2=C1SC(N)=N2 FASDKYOPVNHBLU-ZETCQYMHSA-N 0.000 description 1
- 229960003089 pramipexole Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Abstract
本发明公开了一种二硫化钼纳米片组装的二硫化钼纳米棒及制备方法和用途,所述二硫化钼纳米棒长度为1~3μm,直径为350~450nm。所述二硫化钼纳米棒的二硫化钼纳米片单体的厚度为30nm以下。本发明制备方法在水溶液中不使用有机表面活性剂一步合成得到的产物为由片层很薄的二维二硫化钼纳米片组装成的单一物相的一维二硫化钼纳米棒;用于对氯硝基苯加氢得到对氯苯胺,转化率和选择性可以为100%。性能超过典型的纳米花状二硫化钼催化剂。
Description
技术领域
本发明属于二硫化钼基催化剂的合成技术领域,具体涉及一种二硫化钼纳米片组装的二硫化钼纳米棒、其制备方法及用途。
背景技术
二硫化钼是一类典型的二维层状纳米材料,由于其独特的结构和理化性质被广泛应用于催化、能源存储、摩擦学、光子晶体等领域。二硫化钼的活性位点通常被确定为边缘配位不饱和位点,而基面通常是惰性的。因此,降低其维度或层数是增加活性位点的有效方法。但是通过剥离手段获得的二维二硫化钼纳米片或典型水热合成得到的准零维纳米颗粒很容易团聚,导致活性位点的损失。
构建层次结构是利用二硫化钼固有属性和独特结构优势的有效方法之一。近来的报道已经表明,纳米花及微球结构的二硫化钼纳米片组装体可以很容易的通过水热法合成出来。但是纳米片组装的纳米棒的一步水热合成仍很少报道,特别是在水性溶剂中,不使用有机物的情况下,进行一步合成。中国专利CN 111233039 B公开了一种以有机胺和钼酸铵首先合成棒状中间体,再二次水热制备棒状二硫化钼的合成方法;中国专利CN 105366727B公开了以苄基三乙基氯化铵、普兰尼克F-127、十二烷基苯磺酸钠或聚乙二醇中两种的混合物为表面活性剂制备棒状二硫化钼的合成方法。二者均没有同时满足一步合成和无有机表面活性剂参与。
对氯苯胺是染料、医药、农药等精细化工产品的关键原料和中间体,通过催化对氯硝基苯选择性加氢是合成对氯苯胺的有效途径。目前二硫化钼作为硝基加氢还原的催化剂还罕有报道。本发明制备的二硫化钼纳米片组装的二硫化钼纳米棒在硝基加氢领域具有广阔的应用前景。
发明内容
为了解决现有技术存在的问题,本发明提供一种二硫化钼纳米片组装的二硫化钼纳米棒及制备方法和用途,在水溶液中不使用有机表面活性剂一步合成得到的产物为由片层很薄的二维二硫化钼纳米片组装成的单一物相的一维二硫化钼纳米棒;用于对氯硝基苯加氢得到对氯苯胺,转化率和选择性可以为100%。性能超过典型的纳米花状二硫化钼催化剂。
本发明的技术方案如下:
本发明第一方面公开了一种二硫化钼纳米片组装的二硫化钼纳米棒,所述二硫化钼纳米棒的长度为1~3μm,直径为350~450nm,所述二硫化钼纳米棒的二硫化钼纳米片单体的厚度为30nm以下。
优选地,所述二硫化钼纳米棒是由二维二硫化钼纳米片单体组装而成的一维形态,不存在其它形貌或物相。
本发明第二方面公开了所述具有褶皱的二硫化钼纳米片的制备方法,包括如下步骤:
①将氯化钠溶解到去离子水中,得到相应的饱和氯化钠水溶液;
②将四水合七钼酸铵和硫脲分散到步骤①得到的饱和氯化钠水溶液中;
③将步骤②得到的分散液转移到聚四氟乙烯内衬的反应釜中,密封置于烘箱中,采用加热程序加热;
④将步骤③所得产物取出后用无水乙醇和去离子水进行洗涤、离心、干燥,得到最终产物,即为所述的二硫化钼纳米片组装的二硫化钼纳米棒。
优选地,步骤①的氯化钠的溶解温度为25~35℃。
优选地,步骤②的四水合七钼酸铵和硫脲的摩尔比为1:30,四水合七钼酸铵的用量为1~2mmol,氯化钠水溶液的用量为30~40mL。
优选地,步骤③的加热程序为首先在80℃恒温20~40min,再以5℃/min升至180℃,恒温保持20~48h,随后自然冷却至室温。
本发明第三方面公开所述的二硫化钼纳米片组装的二硫化钼纳米棒用于催化对氯硝基苯加氢为对氯苯胺的用途。
本发明的有益效果:
1、本发明的二硫化钼纳米片组装的二硫化钼纳米棒,其组成单体二硫化钼纳米片厚度较小、在30nm以下,组装形成的一维二硫化钼纳米棒具有开放的孔道结构,使得活性位点充分暴露。
2、本发明的二硫化钼纳米片组装的二硫化钼纳米棒的制备方法工序简单快速,原料廉价。由于饱和氯化钠水溶液的添加,促使一维形态的反应中间体钼酸铵钠形成,进而在水热反应过程中形成二硫化钼纳米片组装的二硫化钼纳米棒,获得充分开放的孔道结构,活性位点得到充分的暴露。所制备得到的二硫化钼纳米片组装的二硫化钼纳米棒是催化对氯硝基苯加氢为对氯苯胺的高效催化剂;用于对氯硝基苯的加氢催化,对氯硝基苯的转化率为100%,对氯苯胺的选择性100%。性能超过典型的纳米花状二硫化钼催化剂。
3、本发明在二硫化钼纳米片组装的二硫化钼纳米棒合成过程中,没有使用任何昂贵、难以去除的有机表面活性剂或模板剂。采用廉价、易于去除的氯化钠作为添加剂,通过简单的一步水热反应,自发形成棒状反应中间体,并进而得到二硫化钼纳米片组装的二硫化钼纳米棒。该方案简单、有效、成本低。
附图说明
图1是实施例1所制得的二硫化钼纳米片组装的二硫化钼纳米棒的XRD图;
图2是实施例1所制得的二硫化钼纳米片组装的二硫化钼纳米棒的SEM图;
图3是实施例1所制得的二硫化钼纳米片组装的二硫化钼纳米棒的TEM图;
图4是对比例所制得的二硫化钼纳米花的SEM图。
具体实施方式
为了使本发明的目的、技术方案和有益效果更加清楚,下面将结合实施例进行详细的说明,以方便技术人员理解。
本发明的一种二硫化钼纳米片组装的二硫化钼纳米棒的制备方法,包括如下步骤:
1、将氯化钠在温度为25~35℃下溶解到去离子水中,得到相应的饱和氯化钠水溶液;
2、将四水合七钼酸铵和硫脲分散到步骤1得到的饱和氯化钠水溶液中;其中,所述的四水合七钼酸铵和硫脲的摩尔比为1:30,四水合七钼酸铵的用量为1~2mmol,氯化钠水溶液的用量为30~40mL;
3、将步骤2得到的分散液转移到50mL聚四氟乙烯内衬的反应釜中,密封置于烘箱中,采用加热程序加热;其中,所述的加热程序为首先在80℃恒温20~40min,再以5℃/min升至180℃,恒温保持20~48h,随后自然冷却至室温。
4、将步骤3所得产物取出后用无水乙醇和去离子水进行洗涤、离心、干燥,得到最终产物、即为所述的二硫化钼纳米片组装的二硫化钼纳米棒。
下面结合实施例和附图对本发明的一种二硫化钼纳米片组装的二硫化钼纳米棒、其制备方法及应用做出详细说明。
实施例1:二硫化钼纳米片组装的二硫化钼纳米棒的制备
步骤1:在35℃的水浴中,通过搅拌,在装有去离子水的烧杯中溶解氯化钠,直至得到35℃下的饱和氯化钠水溶液;
步骤2:取1mmol四水和七钼酸铵和30mmol硫脲,通过搅拌分散到35mL步骤1得到的饱和氯化钠水溶液中,得到分散液;
步骤3:取步骤2得到的分散液,转移到50mL聚四氟乙烯内衬的反应釜中,密封置于烘箱中,首先在80℃恒温30min,再以5℃/min升至180℃,恒温保持24h,随后自然冷却至室温;
步骤4:将步骤3所得产物取出后通过离心法用150mL无水乙醇洗涤3次,再用150mL去离子水洗涤3次;再将产物重新分散在20mL去离子水中,在–4℃冷冻12小时后,再在–40℃冷冻干燥机中干燥72小时,得到最终产物、即为所述的二硫化钼纳米片组装的二硫化钼纳米棒。
图1是所制得的二硫化钼纳米片组装的二硫化钼纳米棒的XRD图,图2是SEM图,图3是TEM图。由图1可以看出所得产物是单纯的MoS2物质,由图2可以看出产物由二维纳米片组装的一维纳米棒,直径约为350~400nm,长度为1~3μm,纳米片单体厚度较小、在30nm以下;从图3可以看出,所得到的产物为由几乎透明的超薄纳米片组装而成,纳米片在纳米棒上垂直排列,形成高度开放的传质通道。
实施例2:二硫化钼纳米片组装的二硫化钼纳米棒的制备
步骤1:在30℃的水浴中,通过搅拌,在装有去离子水的烧杯中溶解氯化钠,直至得到30℃下的饱和氯化钠水溶液;
步骤2:取1.5mmol四水和七钼酸铵和45mmol硫脲,通过搅拌分散到40mL步骤1得到的饱和氯化钠水溶液中,得到分散液;
步骤3:取步骤2得到的分散液,转移到50mL聚四氟乙烯内衬的反应釜中,密封置于烘箱中,首先在80℃恒温20min,再以5℃/min升至180℃,恒温保持30h,随后自然冷却至室温;
步骤4:将步骤3所得产物取出后通过离心法用150mL无水乙醇洗涤3次,再用150mL去离子水洗涤3次;再将产物重新分散在20mL去离子水中,在–4℃冷冻12小时后,再在–40℃冷冻干燥机中干燥72小时,得到最终产物、即为所述的二硫化钼纳米片组装的二硫化钼纳米棒。
得到的二硫化钼纳米片组装的二硫化钼纳米棒为二维纳米片组装成的一维纳米棒;得到产物的组成、长度、直径,片层和厚度与实施例1的结果类似。
实施例3:得到的二硫化钼纳米片组装的二硫化钼纳米棒用于对氯硝基苯的加氢催化,步骤如下:
将实施例1制备得到的二硫化钼纳米片组装的二硫化钼纳米棒与对氯硝基苯按质量比1∶4.2,超声15分钟均匀分散于异丙醇中;在1.6MPa氢压和150℃反应温度、以及500rpm搅拌速度下在间歇釜式反应器中进行加氢反应,反应时间为1小时;
反应结束后,通过气相色谱分析液相产物,对氯硝基苯转化率为100%,对氯苯胺选择性为100%。
对比例
将实施例1中的饱和氯化钠水溶液替换为去离子水制备得到典型二硫化钼纳米花。图4是所制得的二硫化钼纳米花的SEM图,可以看出其由纳米片组装而成的纳米花。将所得的二硫化钼纳米花在实施例3的条件下用于对氯硝基苯的加氢催化。通过气相色谱分析液相产物,对氯硝基苯转化率为63%,对氯苯胺选择性为100%。
由实施例3和对比例可以看出,本发明得到的二硫化钼纳米片组装的二硫化钼纳米棒用于对氯硝基苯的加氢催化,催化性能优于经典方法制备的二硫化钼纳米花。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本领域的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (5)
1.一种由二硫化钼纳米片组装的二硫化钼纳米棒的制备方法,其特征在于,包括如下步骤:
①将氯化钠溶解到去离子水中,得到相应的饱和氯化钠水溶液;
②将四水合七钼酸铵和硫脲分散到步骤①得到的饱和氯化钠水溶液中;
③将步骤②得到的分散液转移到聚四氟乙烯内衬的反应釜中,密封置于烘箱中,采用加热程序加热;
④将步骤③所得产物取出后用无水乙醇和去离子水进行洗涤、离心、干燥,得到最终产物,即为所述的二硫化钼纳米片组装的二硫化钼纳米棒;
所述二硫化钼纳米棒的长度为1~3μm,直径为350~450nm,所述二硫化钼纳米棒的二硫化钼纳米片单体的厚度为30nm以下。
2.根据权利要求1所述的制备方法,其特征在于,步骤①的氯化钠的溶解温度为25~35℃。
3.根据权利要求1所述的制备方法,其特征在于,步骤②的四水合七钼酸铵和硫脲的摩尔比为1:30,四水合七钼酸铵的用量为1~2mmol,氯化钠水溶液的用量为30~40mL。
4.根据权利要求1所述的制备方法,其特征在于,步骤③的加热程序为首先在80℃恒温20~40min,再以5℃/min升至180℃,恒温保持20~48h,随后自然冷却至室温。
5.权利要求1所述的二硫化钼纳米片组装的二硫化钼纳米棒的制备方法制备得到的二硫化钼纳米片组装的二硫化钼纳米棒用于催化对氯硝基苯为对氯苯胺的用途。
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