CN110690425A - 硼掺杂还原碳纳米管负载氧化铁复合材料及其制备方法 - Google Patents
硼掺杂还原碳纳米管负载氧化铁复合材料及其制备方法 Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 47
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- -1 amino carbon nanotube Chemical compound 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000007865 diluting Methods 0.000 claims abstract description 7
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 7
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
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- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
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- 229910021397 glassy carbon Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
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- 235000003891 ferrous sulphate Nutrition 0.000 description 1
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- 235000014413 iron hydroxide Nutrition 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法及其制备方法，该制备方法包括以下步骤：(1)将可溶性铁盐的水溶液和多壁氨基碳纳米管分散液混合后稀释；(2)加入硼氢化钠，反应生成氧化铁纳米晶核；(3)水热反应，得到纳米粒子，固液分离、冻干，得到所述的硼掺杂还原碳纳米管负载氧化铁复合材料。与现有技术相比，本发明的制备方法简单，制备的材料导电性能良好，N、B共掺杂形成协同作用使得材料在电化学性能方面具有良好的效果，适合应用于电催化析氢、析氧、超级电容器以及锂离子电池等。
Description
技术领域
本发明属于能源材料技术领域，尤其是涉及一种R-CNTs-Fe2O3-B复合材料及其制备方法。
背景技术
碳纳米管自被发现以来，人们对其合成方法、性能和应用等方面展开了大量研究。例如高性能复合材料的增强基、纳米管场发射体、能量存储材料和催化剂载体等。目前，采用碳纳米管取代活性炭制备活性更高的复合催化剂已成为一个新的研究热点。
碳纳米管除了具有纳米级管腔结构、较高的比表面积、类石墨的多层管壁和优良的导电性等特点外，还具有可以裁剪以及表面修饰的特性，可满足作为催化剂载体的特殊需要，同时可作为模板制备纳米催化剂，使它在作为催化剂载体方面有着良好的应用前景。目前，在碳纳米管负载金属的催化应用方面已有一些尝试性工作。这些工作主要集中在利用碳纳米管作为贵金属催化剂的载体，使活性贵金属和促进剂的前驱体得到充分的分散，从而提高贵金属的利用率，防止金属粒子烧结；而且由于碳纳米管与活性贵金属之间的强相互作用，提高了金属催化剂的活性、选择性和稳定性。此外，在碳纳米管上负载金属氧化物如氧化钡、氧化铝、氧化铁催化剂的研究也有报道。Fe2O3在合成氨与F-T合成催化方面是一类重要的催化剂，已有报道采用双氧水与硫酸亚铁对碳纳米管进行表面修饰的同时，在管壁上均匀吸附铁的氢氧化物，再通过不同气氛的热处理得到不同结构的碳纳米管负载Fe2O3催化剂，但对Fe2O3负载的机理并未作深入研究。
过渡金氧化物用作电极材料的缺点，在充放电过程中会出现体积效应，循环稳定较差。此种材料的反动力学比较左，而且充放电电滞后现象比较严。过渡金属氧化物电化学稳定性差主要有三点：第一是导电性较差，离子或电子扩散系数不大，降低了电极反应的可逆性；第二是过渡金属氧化物活性颗粒之间、集体流和活性颗粒之间失去电接触，丧失触点的粒子不再参与电极反应，电化学性能开始衰减；第三是过渡金属氧化物作为电极材料多次发生反应后可能生成金属纳米颗粒，这些颗粒在多次循环后产生团聚，从活性物质变少，电化学性能减弱。
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充分协调了金属与非金属之间以及非金属与非金属之间的协同作用，电化学性能良好的硼掺杂还原碳纳米管负载氧化铁复合材料及其制备方法。
本发明的目的可以通过以下技术方案来实现：
本发明提供一种硼掺杂还原碳纳米管负载氧化铁(R-CNTs-Fe2O3-B)复合材料的制备方法，包括以下步骤：
(1)将可溶性铁盐的水溶液和多壁氨基碳纳米管分散液混合后稀释；
(2)加入硼氢化钠，反应生成氧化铁纳米晶核；
(3)水热反应，得到纳米粒子，固液分离、冻干，得到所述的R-CNTs-Fe2O3-B复合材料。
优选地，步骤(1)中，所述的可溶性铁盐为九水合硝酸铁。
优选地，步骤(1)中，所述的可溶性铁盐的水溶液为采用九水合硝酸铁配制的0.2～2M的水溶液。
优选地，步骤(1)中，多壁氨基碳纳米管分散液的浓度为10wt.％，多壁氨基碳纳米管与可溶性铁盐的质量之比为1：(4-40)。
进一步优选地，步骤(1)中，多壁氨基碳纳米管采用市售的先丰纳米生产的编号为XFWDM、货号为100320的多壁氨基碳纳米管。
优选地，步骤(1)中，稀释到原体积的4-10倍。
优选地，步骤(2)中硼氢化钠的用量为0.1-0.5mmol。
优选地，步骤(2)中，反应在高温下进行，加热的温度为60～90℃，加热时间为12～18h。
优选地，步骤(3)中，水热反应的温度为120～180℃，水热反应时间为6～24h。
本发明还提供一种上述制备方法制得的硼掺杂还原碳纳米管负载氧化铁(R-CNTs-Fe2O3-B)复合材料。
与现有技术相比，本发明具有以下有益效果：
(1)本发明以多壁氨基碳纳米管负载氧化铁纳米颗粒，多壁氨基碳纳米管具有较大的比表面积，而且二维碳纳米材料具有良好的导电性，这增强了材料的电化学性能。
(2)氮掺杂碳材料——多壁氨基碳纳米管由于层两种材料类似的电子层结构，可以在保证导电率的同时，增加法拉第电容反应，即是在电极表面或体相中的二维或准二维空间上，电活性物质进行欠电位沉积，发生高度可逆的化学吸附，脱附或氧化，还原反应。
本发明以NaBH4为还原剂，一方面掺入了B元素，与多壁氨基碳纳米管中的C与N元素形成了协同作用，进一步增强了材料的电化学性能；此外，NaBH4是强还原剂，使得CNTs还原成了R-CNTs，增加了材料的石墨化缺陷程度，在电化学领域有着较好的性能。
(3)本发明的方法制备出的电极材料具有蓬松多孔结构，这种结构孔径分布均一，具有高的比表面积，在吸附、超级电容器、锂离子电池甚至催化等领域具有广泛的应用前景。
附图说明
图1(a)为实施例1得到的硼掺杂还原碳纳米管负载氧化铁(R-CNTs-Fe2O3-B)复合材料的拉曼曲线图，图1(b)和图1(c)为实施例1得到R-CNTs-Fe2O3-B复合材料在应用实施例1中的电催化析氢性能曲线图；
图2(a)和图2(b)为实施例2得到R-CNTs-Fe2O3-B复合材料在应用实施例2的电催化析氢性能曲线图；
图3(a)和图3(b)为实施例3得到R-CNTs-Fe2O3-B复合材料在应用实施例3的电催化析氢性能曲线图。
具体实施方式
一种硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，包括以下步骤：
(1)将可溶性铁盐的水溶液和多壁氨基碳纳米管分散液混合后稀释；
(2)加入硼氢化钠，反应生成氧化铁纳米晶核；
(3)水热反应，得到纳米粒子，固液分离、冻干，得到所述的R-CNTs-Fe2O3-B复合材料。
优选地，步骤(1)中，所述的可溶性铁盐为九水合硝酸铁。
优选地，步骤(1)中，所述的可溶性铁盐的水溶液为采用九水合硝酸铁配制的0.2～2M的水溶液。
优选地，步骤(1)中，多壁氨基碳纳米管分散液的浓度为10wt.％，多壁氨基碳纳米管与可溶性铁盐的质量之比为1：(4-40)。
优选地，步骤(1)中，稀释到原体积的4-10倍。
优选地，步骤(2)中硼氢化钠的用量为0.1-0.5mmol。
优选地，步骤(2)中，反应在高温下进行，加热的温度为60～90℃，加热时间为12～18h。
优选地，步骤(3)中，水热反应的温度为120～180℃，水热反应时间为6～24h。
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
本实施例硼掺杂还原碳纳米管负载氧化铁(R-CNTs-Fe2O3-B)复合材料的原料配方如下：
R-CNTs-Fe2O3-B复合材料的制备方法，该方法包括以下步骤：首先，将Fe(NO3)3·9H2O配成1mL溶液，接着取0.2mL 10wt.％多壁氨基CNTs混匀，用去离子水将混合液稀释至10mL，称量4mg NaBH4加入溶液中，在80℃下搅拌12h，将溶液转移到水热釜中，150℃下水热6h，然后冷却，离心分离，用水和乙醇的混合液洗两次，最后冻干，得到R-CNTs-Fe2O3-B复合材料，材料具有良好的石墨化缺陷和堆垛结构，材料的拉曼表征如图1a所示。
应用实施例1
将实施例1的样品进行研磨，将玻碳电极表面使用0.05μm的氧化铝研磨干净，除去残留样品，使用乙醇和水冲洗干净，晾干。
(1)用无水甲醇配Nafion溶液0.5wt.％。称取1mg上述杂化催化剂(R-CNTs-Fe2O3-B复合材料)溶解在100μL配制好的Nafion溶液与甲醇混合液中，在超声下均匀分散两个小时。然后再将该溶液吸取12μL于玻碳电极上，自然晾干。
(2)配制1M的KOH水溶液作为电催化的电解液，通入氮气赶跑空气，用1M的KOH水溶液清洗玻碳电极的电极表面，接着将玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在碱性溶液中测得该电极材料电催化析氢的性能，该材料在电流密度为10mA cm-2的过电位为240mV(图1b)，Tafel斜率为143mV dec-1(图1c)。
实施例2
本实施例的R-CNTs-Fe2O3-B复合材料的原料配方如下：
R-CNTs-Fe2O3-B复合材料的制备方法，该方法包括以下步骤：首先，将Fe(NO3)3·9H2O配成2mL溶液，接着取0.2mL 10wt.％多壁氨基CNTs混匀，用去离子水将混合液稀释至10mL，称量8mg NaBH4加入溶液中，在80℃下搅拌18h，将溶液转移到水热釜中，180℃下水热12h，然后冷却，离心分离，用水和乙醇的混合液洗两次，最后冻干，得到R-CNTs-Fe2O3-B复合材料。
应用实施例2
将实施例2的样品进行研磨，将玻碳电极表面使用0.05μm的氧化铝研磨干净，除去残留样品，使用乙醇和水冲洗干净，晾干。
(1)用无水甲醇配Nafion溶液0.5wt.％。称取1mg上述杂化催化剂溶解在100μL配制好的Nafion溶液与甲醇混合液中，在超声下均匀分散两个小时。然后再将该溶液吸取12μL于玻碳电极上，自然晾干。
(2)配制1M的KOH水溶液作为电催化的电解液，通入氮气赶跑空气，用1M的KOH水溶液清洗玻碳电极的电极表面，接着将玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在碱性溶液中测得该电极材料电催化析氢的性能，该材料在电流密度为10mA cm-2的过电位为329mV(图2a)，Tafel斜率为131mV dec-1(图2b)。
实施例3
本实施例R-CNTs-Fe2O3-B复合材料的原料配方如下：
本实施例R-CNTs-Fe2O3-B复合材料的制备方法，该方法包括以下步骤：首先，将Fe(NO3)3·9H2O配成1mL溶液，接着取0.5mL 10wt.％多壁氨基CNTs混匀，用去离子水将混合液稀释至10mL，称量18mg NaBH4加入溶液中，在90℃下搅拌12h，将溶液转移到水热釜中，180℃下水热6h，然后冷却，离心分离，用水和乙醇的混合液洗两次，最后冻干，得到R-CNTs-Fe2O3-B复合材料。
应用实施例3
将实施例3的样品进行研磨，将玻碳电极表面使用0.05μm的氧化铝研磨干净，除去残留样品，使用乙醇和水冲洗干净，晾干。
(1)用无水甲醇配Nafion溶液0.5wt.％。称取1mg上述杂化催化剂溶解在100μL配制好的Nafion溶液与甲醇混合液中，在超声下均匀分散两个小时。然后再将该溶液吸取12μL于玻碳电极上，自然晾干。
(2)配制1M的KOH水溶液作为电催化的电解液，通入氮气赶跑空气，用1M的KOH水溶液清洗玻碳电极的电极表面，接着将玻碳电极、Ag/AgCl电极、铂电极接上电化学工作站，在碱性溶液中测得该电极材料电催化析氢的性能，该材料在电流密度为10mA cm-2的过电位为417mV(图3a)，Tafel斜率为133mV dec-1(图3b)。
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (9)
1.一种硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，其特征在于，包括以下步骤：
(1)将可溶性铁盐的水溶液和多壁氨基碳纳米管分散液混合后稀释；
(2)加入硼氢化钠，反应生成氧化铁纳米晶核；
(3)水热反应，得到纳米粒子，固液分离、冻干，得到所述的R-CNTs-Fe2O3-B复合材料。
2.根据权利要求1所述的硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，其特征在于，步骤(1)中，所述的可溶性铁盐为九水合硝酸铁。
3.根据权利要求2所述的硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，其特征在于，步骤(1)中，所述的可溶性铁盐的水溶液为采用九水合硝酸铁配制的0.2～2M的水溶液。
4.根据权利要求1所述的硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，其特征在于，步骤(1)中，多壁氨基碳纳米管分散液的浓度为10wt.％，多壁氨基碳纳米管与可溶性铁盐的质量之比为1：(4-40)。
5.根据权利要求1所述的硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，其特征在于，步骤(1)中，稀释到原体积的4-10倍。
6.根据权利要求1所述的硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，其特征在于，步骤(2)中硼氢化钠的用量为0.1-0.5mmol。
7.根据权利要求1所述的硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，其特征在于，步骤(2)中，反应在高温下进行，加热的温度为60～90℃，加热时间为12～18h。
8.根据权利要求1所述的硼掺杂还原碳纳米管负载氧化铁复合材料的制备方法，其特征在于，步骤(3)中，水热反应的温度为120～180℃，水热反应时间为6～24h。
9.一种如权利要求1～9任一所述的制备方法制得的硼掺杂还原碳纳米管负载氧化铁复合材料。
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