CN104640633A - 制备碳纳米管制备用的金属催化剂的方法和使用该催化剂制备碳纳米管的方法 - Google Patents
制备碳纳米管制备用的金属催化剂的方法和使用该催化剂制备碳纳米管的方法 Download PDFInfo
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- CN104640633A CN104640633A CN201380048647.5A CN201380048647A CN104640633A CN 104640633 A CN104640633 A CN 104640633A CN 201380048647 A CN201380048647 A CN 201380048647A CN 104640633 A CN104640633 A CN 104640633A
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- 238000000034 method Methods 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
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- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
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- 239000002245 particle Substances 0.000 claims abstract description 8
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
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- 239000003708 ampul Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 239000002134 carbon nanofiber Substances 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
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- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
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- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0004—Apparatus specially adapted for the manufacture or treatment of nanostructural devices or systems or methods for manufacturing the same
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
提供了制备碳纳米管制备用的金属催化剂的方法和用于使用该催化剂制备碳纳米管的方法。更具体而言,本发明涉及使用沉积-沉淀法制备碳纳米管制备用的金属催化剂的方法,该方法包括:制备载体分散溶液,其中固体载体被分散在溶剂中;并且将金属前体盐溶液和pH调节溶液注入所述分散溶液中以制备混合溶液,并且将由此形成的金属氧化物或金属氢氧化物吸附在所述固体载体的表面上以制备催化剂颗粒。在根据本发明的碳纳米管制备用的金属催化剂中,金属组分(其为催化剂的活性组分)的利用率可以很高,因此碳纳米管的合成产率可以很高,副反应可以很少,并且可以合成具有更均一的形状的碳纳米管。
Description
技术领域
本发明涉及制备碳纳米管制备用的金属催化剂的方法和使用该催化剂制备碳纳米管的方法。
背景技术
碳纳米管具有以下形状:其中由一个碳原子和三个其它碳原子之间的键形成的六边形蜂窝状的石墨面被呈圆形卷起以具有纳米尺寸的直径,并且碳纳米管是根据其尺寸和形状具有独特物理性质的大分子。碳纳米管由于其中是空心的所以轻,并且具有与铜一样好的导电性、与金刚石一样优异的导热性和相当于钢的拉伸强度。由于碳纳米管具有形成圆柱形的键合结构,即使没有有意加入杂质,碳纳米管的电学性质也由于管间的相互作用而从导体至半导体变化。碳纳米管根据卷的形状可分为单壁纳米管(SWNT)、多壁纳米管(MWNT)和绳纳米管。
作为合成碳纳米管的方法,通常已提出电弧放电法、激光烧蚀法、高压化学气相沉积法(CVD)、常压热化学气相沉积法等。其中,电弧放电法和激光烧蚀法由于其简单的原理可以被容易地应用,但是在使用这些方法合成碳纳米管的时候可能包括大量杂质,并且这些方法不适合大规模生产。另一方面,作为用于在低成本下大规模地生产高纯度的碳纳米管的方法,已知热化学气相沉积法是最合适的方法。
用于使用热化学气相沉积法合成碳纳米管的催化剂也对合成有重大影响。通常已使用作为过渡金属的钴、铁、镍等,并且可以通过载体上的金属催化剂合成碳纳米管。
用于制备金属催化剂的方法的实例可以包括:共沉淀法,所述共沉淀法改变pH、温度和/或在溶液状态中的催化剂载体和催化剂金属或金属组合物的组成以共沉淀,然后分离沉淀物以在空气或其它气体气氛下热处理该沉淀物;(初始)浸渍法,所述(初始)浸渍法加热、干燥和蒸发含细颗粒载体材料和催化剂金属的悬浮体;一种方法,其将阳离子细颗粒载体材料例如沸石与催化剂金属盐混合以从而被电离,然后在高温下使用氢气或其它还原方法将被电离的金属还原成金属颗粒;一种方法,其灼烧混合状态的催化剂金属和固体氧化物载体材料例如氧化镁、氧化铝、氧化硅等;或类似方法。此外,在韩国专利特许公开第2003-0091016号(专利文件1)中已公开了喷雾热解法,其为喷雾/细化催化剂金属前体溶液以灼烧催化剂金属前体溶液,但是大部分制备的催化剂具有0.1微米至数微米的平均粒径,使得在细度上存在限制,或存在难以大规模生产该催化剂或经济效率劣化的问题。
[相关技术文件]
[专利文件]
(专利文件1)韩国专利特许公开第2003-0091016号
发明内容
技术问题
本发明的目的是提供制备碳纳米管制备用的金属催化剂的方法,由于通过使用沉积-沉淀混合法的优异的负载均一性,该方法能够以与所注入的催化剂的量相比的高产率合成具有均一定向结构的碳纳米管。
问题的解决方案
在一个一般性的方面,制备碳纳米管制备用的金属催化剂的方法,该方法包括:制备其中固体载体分散在溶剂中的载体分散溶液;并且将金属前体盐溶液和pH调节溶液注入该分散溶液以制备混合溶液,并且将由此形成的金属氧化物或金属氢氧化物吸附在固体载体的表面上以制备催化剂颗粒。
下文中将更详细地描述本发明。
本发明涉及使用沉积-沉淀混合法制备碳纳米管制备用的金属催化剂的方法。在根据本发明的沉积-沉淀混合法中,金属前体盐溶液和pH调节剂在载体分散溶液中互相反应以形成沉淀,并且在载体的表面上吸附并且固化这些沉淀。通过发现在此情况下,催化剂的均一性和碳纳米管的合成产率与通过现有的共沉淀或浸渍法制备的金属催化剂相比得到显著改善,因此通过沉积-沉淀混合法制备的催化剂作为碳纳米管制备用的金属催化剂具有优异的催化活性而完成本发明。
在制备碳纳米管制备用的金属催化剂的方法中,可以通过溶解基于100重量份的溶剂为30重量份至100重量份的含量的过渡金属前体制备金属前体盐溶液。在含量小于30重量份的情况下,用在总反应中的溶剂的量增加,使得可能难以控制反应,在含量大于100重量份的情况下,可能难以溶解过渡金属前体。
根据本发明的过渡金属前体没有特别的限制,只要材料包含金属例如金属盐即可,但是优选地,可以使用包含选自由含铁、钴、镍、钇、钼、铜、铂、钯、钒、铌、钨、铬、铱和钛的金属盐组成的组中的一种或至少两种的材料。具体地,更优选的是过渡金属前体含选自铁、钴和钼中的一种或至少两种。
当金属前体溶液与pH调节溶液混合时,金属前体溶液以金属氧化物或金属氢氧化物颗粒的形式固化,以由此吸附在载体上,并且可以在混合溶液中以金属氧化物(或金属氢氧化物)和载体的混合催化剂颗粒形式沉淀。在这种情况下,催化剂颗粒可以具有0.1μm至100μm的平均直径。
在这种情况下,通过将由加入金属前体盐溶液和pH调节溶液至载体分散溶液而形成的溶液的pH调节至4至8来制备催化剂。在pH小于4的情况下,金属氧化物或金属氢氧化物不从金属前体沉淀,而在pH大于8的情况下,形成可溶的金属络合物,因此不可能获得期望的沉淀形式。在根据本发明制备碳纳米管制备用的金属催化剂的时候,优选地,可以将pH调节至6至8之间,该pH适合于从过渡金属前体形成金属氧化物或金属氢氧化物的沉淀因而是有效的,因此可以促使固定量的金属组分的沉淀。
为了调节混合溶液的pH,在本发明中,可以使用pH调节溶液。pH调节溶液可以基于100重量份的溶剂包含为5重量份至50重量份的含量的pH调节剂。在含量小于5重量份的情况下,用在总反应中的溶剂的量增加,因此可能难以控制反应,而在含量大于50重量份的情况下,可能难以溶解pH调节剂。
pH调节剂可以是选自由碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铵、氢氧化钠和氢氧化钾组成的组中的一种或至少两种的混合物,但是不限于此,只要材料可调节pH即可。
此外,可以通过分散基于100重量份的溶剂为10重量份至80重量份的载体来制备载体分散溶液。在载体含量小于10重量份的情况下,溶剂中的自由成核可以显著发生,而不发生载体表面上(其上形成有金属氧化物或金属氢氧化物的沉淀)的成核,这使负载效率劣化,因此使催化剂的均一性劣化,而在含量大于80重量份的情况下,无法平稳地进行催化剂混合溶液的搅拌,因此反应可能是不均匀的。
在制备碳纳米管制备用的催化剂的时候,载体可以在宽表面积的基础上用于吸附在制备催化剂过程期间形成的金属氧化物或金属氢氧化物的细颗粒以增加催化剂的活性表面积。载体可以是选自金属颗粒、无机颗粒、金属氧化物、金属氢氧化物和碳基颗粒中的一种或至少两种,但不特别限制载体的种类。具体地,可以使用选自以下中的一种或至少两种:氧化物组例如二氧化硅、氧化铝、沸石、氧化钙、氧化锶、氧化钡、氧化镧、氧化铟等,氢氧化物组例如氢氧化铍、氢氧化镁、氢氧化钙、氢氧化锶、氢氧化钡、氢氧化铝、氢氧化钛、氢氧化铬、氢氧化钒、氢氧化锰、氢氧化锌、氢氧化铷、氢氧化铟等,和碳基载体组例如炭黑、碳纤维、石墨、石墨烯、碳纳米管、碳纳米纤维等。
载体可以具有0.01μm至100μm的平均粒径。在平均粒径小于0.01μm的情况下,促使载体颗粒的聚集,因此可能难以合成具有期望的定向结构形式的碳纳米管,而在平均粒径大于100μm的情况下,颗粒的比表面积降低,因此可能难以在载体颗粒的表面上均匀地负载金属氧化物或金属氢氧化物。优选地,载体可以具有0.1μm至10μm的平均粒径。
在本发明中,通常在金属前体盐溶液、pH调节溶液和固体载体分散溶液中可以使用溶剂,并且可以使用任何溶剂,只要该溶剂可以溶解pH调节剂和分散载体即可。作为溶剂,优选地可以使用选自由水、甲醇、乙醇、丙醇、异丙醇、乙二醇和聚乙二醇组成的组中的一种或至少两种的混合物,因为这些溶剂可以容易地溶解过渡金属前体和pH调节剂,并且保持合适的反应温度。
可以通过同时滴加并搅拌基于100重量份的固体载体分散溶液为10重量份至200重量份的金属前体盐溶液和pH调节溶液中的每一种来制备混合溶液。在这种情况下,调节金属前体盐溶液和pH调节溶液的滴加速率和该金属前体盐溶液与pH调节溶液之间的比率,使得可以适当保持混合溶液的pH。
在制备催化剂混合溶液时,加热温度可以是25℃至150℃。在加热温度小于25℃的情况下,形成金属氧化物或金属氢氧化物时的成核可能劣化,使得催化剂的均一性可能劣化,而在加热温度大于150℃的情况下,由于可能发生例如溶剂蒸发的问题,在选择溶剂时应当考虑沸点等,因此可能限制溶剂的选择。更优选地,考虑到改善催化剂的均一性以增加催化活性,将加热温度调节至60℃至100℃之间是有效的。
制备催化剂混合溶液之后,可以通过对催化剂混合溶液中的沉淀物的过滤和洗涤过程以及干燥和研磨过程而以粉末形式制备碳纳米管制备用的金属催化剂。
干燥可以在60℃至250℃下进行6小时至36小时。当干燥温度低于60℃时,干燥时间可能增加,而当干燥温度高于250℃时,催化剂可能被过度氧化或聚集。可以在选自空气、氧气、氩气、氮气、氦气和氢气中的一种气体或至少两种气体的混合物下进行干燥,但不特别受限于此。
所制备的碳纳米管制备用的金属催化剂可以具有0.1μm至100μm,优选0.5μm至10μm的平均粒径。在这种情况下,由于催化剂的表面可以被充分暴露,在合成碳纳米管时反应气体可以均匀地接触催化剂,因此可以保证高的合成产率和均一性。
根据本发明的通过上述方法获得的催化剂也被包括在本发明的范围中。
此外,可以通过本领域的常用方法例如热化学气相沉积法等使用根据本发明的催化剂制备碳纳米管。用于使用根据本发明的催化剂制备碳纳米管的该方法和该碳纳米管也包括在本发明的范围中。
发明的有益效果
根据本发明,通过将碳纳米管制备用的金属催化剂组分吸附在呈金属氧化物或金属氢氧化物的固体形式而非液体形式的载体上来制备催化剂。在碳纳米管制备用的具有此形式的金属催化剂中,金属组分(其为催化剂的活性组分)的利用率可以很高,因此碳纳米管的合成产率可以很高,副反应可以很少,并且可以合成具有更均一的形状的碳纳米管。因此,在制备碳纳米管时,可以制备具有高纯度、高产率和优异的均一性的碳纳米管,因此可以广泛使用根据本发明的金属催化剂作为用于在大规模生产时能够提高生产率的碳纳米管制备用的催化剂。
附图说明
图1是实施例1中制备的碳纳米管制备用的金属催化剂的扫描电子显微镜(SEM)照片。
图2是实施例1中制备的碳纳米管制备用的金属催化剂的透射电子显微镜(TEM)照片。
图3是比较例1中制备的碳纳米管制备用的金属催化剂的扫描电子显微镜(SEM)照片。
图4是比较例2中制备的碳纳米管制备用的金属催化剂的扫描电子显微镜(SEM)照片。
图5是在制备实施例中使用金属催化剂制备的碳纳米管的扫描电子显微镜(SEM)照片,所述金属催化剂为实施例1制备的碳纳米管制备用的金属催化剂。
图6是在制备实施例中使用金属催化剂制备的碳纳米管的扫描电子显微镜(SEM)照片,所述金属催化剂为比较例1制备的碳纳米管制备用的金属催化剂。
图7是在制备实施例中使用金属催化剂制备的碳纳米管的扫描电子显微镜(SEM)照片,所述金属催化剂为比较例2制备的碳纳米管制备用的金属催化剂。
图8是示出在制备实施例1中合成的碳纳米管在低密度聚乙烯(LDPE)聚合物复合材料中的电学性质的图。
图9是实施例1的流程图。
[主要要素详述]
1:金属前体盐溶液
2:pH调节溶液
3:载体分散溶液
3′:催化剂混合溶液
4:pH计
5:机械搅拌器
具体实施方式
[实施例1]碳纳米管制备用的金属催化剂的制备
1.将34.16g九水合硝酸铁(III)和13.27g六水合硝酸钴(II)作为过渡金属前体放入100mL蒸馏水中,并且使用磁力搅拌器搅拌10分钟以使其完全溶解,由此制备过渡金属前体溶液。
2.将100g碳酸铵((NH4)2CO3)作为pH调节剂放入400mL蒸馏水中,并且使用浴式超声波仪使其互相混合2小时以使其完全溶解,由此制备pH调节溶液。
3.将100g氢氧化铝(Al(OH)3)作为载体放入2L烧杯中的200mL蒸馏水中并且混合,由此制备载体分散溶液。
4.使用滴液漏斗以15ml/分钟的速率滴加过渡金属前体溶液和pH调节溶液,同时使用机械搅拌器搅拌所制备的载体分散溶液,并且同时使用pH计将溶液的pH状态实时调节在7.5,由此制备催化剂混合溶液。
5.通过在真空下在布氏漏斗中过滤所制备的催化剂混合溶液来过滤滤液,通过倾倒1L蒸馏水3次来洗涤,然后在箱式烘箱中在150℃下干燥16小时。在300立方厘米混合器中研磨经干燥的催化剂10秒,研磨5次,由此制备呈粉末形式的催化剂。
实施例1的流程图示于图9.
[比较例1]通过浸渍法制备碳纳米管制备用的金属催化剂
1.将34.16g九水合硝酸铁(III)和13.27g六水合硝酸钴(II)作为过渡金属前体放入100mL蒸馏水中,并且使用磁力搅拌器互相混合10分钟以使其完全溶解,由此制备过渡金属前体溶液。
2.将100g氢氧化铝(Al(OH)3)作为载体加入至其中,并且使用机械搅拌器互相混合,由此制备催化剂浆料。
3.在箱式烘箱中在150℃下将所制备的催化剂浆料干燥16小时之后,在300立方厘米混合器中研磨经干燥的催化剂10秒,研磨5次,由此制备呈粉末形式的催化剂。
[比较例2]通过共沉淀法制备碳纳米管制备用的金属催化剂
1.将34.16g九水合硝酸铁(III)、13.27g六水合硝酸钴(II)和500g九水合硝酸铝放入100mL蒸馏水中,并且使用磁力搅拌器互相混合10分钟以使其完全溶解,由此制备水性催化剂前体溶液。
2.将100g碳酸铵作为pH调节剂放入400mL蒸馏水中,然后使用浴式超声波仪互相混合2小时以使其完全溶解,由此制备pH调节溶液。
3.使用滴液漏斗以15ml/分钟的速率滴加pH调节溶液,同时使用机械搅拌器搅拌所制备的水性催化剂前体溶液,并且同时使用pH计将溶液的pH状态实时调节在7.5,由此制备催化剂混合溶液。
4.通过在真空下在布氏漏斗中过滤所制备的催化剂混合溶液来过滤滤液,通过倾倒1L蒸馏水3次来洗涤,然后在箱式烘箱中在150℃下干燥16小时。在300立方厘米混合器中研磨经干燥的催化剂10秒,研磨5次,由此制备呈粉末形式的催化剂。
[制备实施例1]碳纳米管的制备
1.使用在实施例和比较例中获得的催化剂通过热化学气相沉积法制备碳纳米管,制备方法如下。将0.5g催化剂均匀施涂在石英舟上,然后将其置于具有190nm的直径的石英管的中心。反应器的温度在氮气气氛下升高至700℃之后,以1:1的比率注入乙烯气体(1SLM)和氢气(1SLM)30分钟,由此制备碳纳米管。
[实验实施例1]催化剂形状分析
为了分析在实施例1中制备的碳纳米管制备用的金属催化剂的形状,使用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察该形状,并且SEM照片和TEM照片分别示于图1和2。
观察到实施例1中制备的碳纳米管制备用的金属催化剂的平均直径是1.4μm
此外,使用扫描电子显微镜(SEM)观察在比较例1和2中制备的碳纳米管制备用的金属催化剂的形状,并且在比较例1和2中制备的金属催化剂的SEM照片分别示于图3和4。作为分析结果,确定了在比较例1和2中制备的金属催化剂的平均直径分别是23μm和140μm。
[实验实施例2]碳产率测量
为了评估在实施例和比较例中制备的碳纳米管制备用的金属催化剂的催化活性,如下定义并且测量了在制备实施例1中使用相应催化剂合成的碳纳米管的碳产率。
碳产率(%)={(收集的碳纳米管的重量)-(注入的催化剂的重量)}/(注入的催化剂的重量)×100
相应结果示于表1.
表1
[表1]
[实验实施例3]碳纯度测量
为了评估在实施例和比较例中制备的碳纳米管制备用的金属催化剂的催化活性,如下定义并且测量了在制备实施例1中使用相应催化剂合成的碳纳米管的碳纯度。使用热重分析仪(TGA)在空气气氛下以10℃/分钟的加热速率升至800℃进行热重分析之后,通过分析残留量根据以下等式计算碳纯度。
碳纯度(%)=(室温下的重量比率(%))-(800℃下的残留重量比率(%))
相应结果示于表1。
[实验实施例4]碳纳米管形状分析
为了评估在实施例1和比较例1和2中制备的碳纳米管制备用的金属催化剂的催化活性,使用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察在制备实施例1中使用相应催化剂的碳纳米管的形状。测量结果示于表1,并且使用SEM获得的形状分别示于图5(实施例1)、图6(比较例1)和图7(比较例2)。
[实验实施例5]碳纳米管性质评估
为了评估在实施例和比较例中制备的碳纳米管制备用的金属催化剂的催化活性,确定了在制备实施例1中使用相应催化剂的碳纳米管在聚合物复合材料中的分散行为和电学特性。为此目的,通过使用双螺杆挤出机在180℃下进行挤出来制造碳纳米管/聚乙烯(CNT/PE)复合材料粒料,其中加入有碳纳米管(2%)。在将所制造的复合材料粒料通过相同的挤出机以制造粒料(2通粒料)之后,通过施加热(180℃)和压力(30吨)至各个粒料来制造具有20cm的宽度、20cm的长度和3mm的厚度的样品。然后测量样品的表面电阻,并且结果示于图8。
Claims (15)
1.一种制备碳纳米管制备用的金属催化剂的方法,所述方法包括:
制备其中固体载体被分散在溶剂中的载体分散溶液;并且
将金属前体盐溶液和pH调节溶液注入所述分散溶液以制备混合溶液,并且将由此形成的金属氧化物或金属氢氧化物吸附在所述固体载体的表面上以制备催化剂颗粒。
2.根据权利要求1所述的方法,其中在所述金属前体盐溶液中,基于100重量份的溶剂,将30重量份至100重量份的过渡金属前体溶解在所述金属前体盐溶液中。
3.根据权利要求2所述的方法,其中所述过渡金属前体是选自由包括铁、钴、镍、钇、钼、铜、铂、钯、钒、铌、钨、铬、铱和钛的金属盐组成的组中的一种或至少两种。
4.根据权利要求1所述的方法,其中所述pH调节溶液基于100重量份的溶剂含为5重量份至50重量份的pH调节剂。
5.根据权利要求4所述的方法,其中所述pH调节剂是选自由碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸铵、氢氧化钠和氢氧化钾组成的组中的一种或至少两种的混合物。
6.根据权利要求1所述的方法,其中所述固体载体分散溶液基于100重量份的溶剂含为10重量份至80重量份的所述载体。
7.根据权利要求1所述的方法,其中所述固体载体是选自金属颗粒、无机颗粒、金属氧化物、金属氢氧化物和碳基颗粒中的一种或至少两种。
8.根据权利要求1所述的方法,其中所述溶剂中的每一种均为选自水、甲醇、乙醇、丙醇、异丙醇、乙二醇和聚乙二醇中的一种或至少两种的混合物。
9.根据权利要求1所述的方法,其中通过同时滴加和搅拌基于100重量份的所述载体分散溶液为10重量份至200重量份的所述金属前体盐溶液和所述pH调节溶液中的每一种来制备所述混合溶液。
10.根据权利要求1所述的方法,其中所述金属氧化物的平均直径为0.1μm至100μm。
11.根据权利要求7所述的方法,其中所述固体载体的平均直径为0.01μm至100μm。
12.根据权利要求1所述的方法,其中所述混合溶液的温度保持在25℃至150℃。
13.根据权利要求1所述的方法,还包括在选自空气、氧气、氩气、氮气、氦气和氢气中的一种气体或至少两种气体的混合物下在60℃至250℃下将吸附在所述固体载体的所述表面上的所述金属氧化物或金属氢氧化物干燥6小时至36小时。
14.一种碳纳米管制备用的金属催化剂,其通过根据权利要求1所述的方法制备。
15.一种用于制备碳纳米管的方法,其使用根据权利要求14所述的碳纳米管制备用的金属催化剂。
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CN113663690A (zh) * | 2021-08-30 | 2021-11-19 | 福建海梵领航科技有限公司 | 一种制备小管径单壁碳纳米管的催化剂及制备方法和应用 |
CN113663690B (zh) * | 2021-08-30 | 2023-08-15 | 福建海梵领航科技有限公司 | 一种制备小管径单壁碳纳米管的催化剂及制备方法和应用 |
CN116789108A (zh) * | 2023-07-19 | 2023-09-22 | 烯格沃(上海)纳米技术有限公司 | 一种提高单壁碳纳米管产率的组合物及方法 |
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Also Published As
Publication number | Publication date |
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WO2014046471A1 (en) | 2014-03-27 |
EP2897727A1 (en) | 2015-07-29 |
JP2015533638A (ja) | 2015-11-26 |
EP2897727A4 (en) | 2016-06-15 |
KR20140037441A (ko) | 2014-03-27 |
KR101446116B1 (ko) | 2014-10-06 |
US20150224479A1 (en) | 2015-08-13 |
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