CN106582817A - 一种制备氮掺杂三维石墨烯的简便方法 - Google Patents
一种制备氮掺杂三维石墨烯的简便方法 Download PDFInfo
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- CN106582817A CN106582817A CN201611235509.XA CN201611235509A CN106582817A CN 106582817 A CN106582817 A CN 106582817A CN 201611235509 A CN201611235509 A CN 201611235509A CN 106582817 A CN106582817 A CN 106582817A
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- abpbi
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- doped graphene
- pyrolysis
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 238000000197 pyrolysis Methods 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
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- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract 2
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Abstract
一种用可溶解的聚(2,5‑苯并咪唑)(ABPBI)溶液在模板剂纳米SiO2作用下制备三维氮掺杂石墨烯的简便方法。ABPBI高分子链是由芳香性的刚性苯并咪唑组成,且分子中含有富含氮元素的咪唑环和端氨基,氩气保护下热解,易形成氮掺杂石墨烯结构。具体制备工艺为:ABPBI溶液与一定粒径的纳米SiO2按照一定比例混合均匀,搅拌下蒸干、研细,在氩气保护下高温热解、去除模板等工艺制备三维氮掺杂石墨烯。要求:ABPBI黏均分子量1~3万;SiO2粒径为5~50nm二者的质量比为3:1~1:3;热解温度为600~1200℃,热解2~3h,用稀氢氟酸洗涤3次,去离子水洗涤3次。制备d的三维氮掺杂石墨烯用于氧还原催化剂、氧析出催化剂,用于燃料电池、金属空气电池和超级电容器等电化学能源存储与转换器件。
Description
技术领域
属于纳米材料制备领域,用于化工生产中的氧化还原反应催化剂,清洁能源领域的燃料电池、金属空气电池阴极催化剂,电解水催化剂,锂离子电池材料,超级电容器电极材料和电化学传感器等领域。
背景技术
石墨烯是一类碳原子构成的正六边形扩展的二维网格结构的纳米材料,由于其性能优异且具有多种潜在的应用,所以,其开发研究及应用受到人们的重视,成为当今广受关注的研究热点(Kim K S, et al. Nature(自然), 2009, 457: 706)。然而,在宏观世界,二维石墨烯之间又极易层-层相互叠加形成石墨结构,从而使其优异的性能丧失。所以,如何阻止石墨烯分子层-层之间的叠加,使其在宏观世界还能保持其石墨烯特性成为人们需要解决的关键问题。因此,三维石墨烯的制备及性能研究成为当今纳米材料领域的研究热点(Chen Z, et al. Nat Mater(自然材料), 2011, 10: 424; Biener J, et al. AdvMater(先进材料), 2012, 24: 5083)。三维石墨烯具有多种用途:如,用于氧还原催化剂或催化剂载体,用于燃料电池、金属空气电池等能源转换的重要材料,也是锂离子电池、超级电容器、电化学传感器和电解等领域的重要材料(Dai L. Acc Chem Res(化学研究评述),2013, 46(1): 31)。研究发现,氮掺杂的石墨烯由于石墨烯分子内C-N键间的极性,使石墨烯分子上的电子云密度发生变化,因此氮掺杂石墨烯催化氧还原性能优于石墨烯。三维氮掺杂石墨烯的制备方法很多:如,氧化石墨烯化合物用含氮的材料还原或在氮气、氨气气氛下还原(Xu Y, et al. ACS Nano(美国化学会-纳米杂志), 2013, 7(5): 4042);用聚苯胺热解制备 (Ding W, et al. Angew Chem Int Ed(德国应用化学-国际版), 2013, 52:1175) 等等。
本发明是利用芳香性的苯并咪唑单元的高分子材料,聚(2,5-苯并咪唑)(ABPBI)为碳源和氮源,在惰性气体保护下热解制备含氮的石墨烯类的碳材料,用硬模板的含量、颗粒度来控制制备的碳材料的孔径、孔隙率和石墨烯的层数,该种方法可以用来制备三维多层氮掺杂石墨烯。
聚苯并咪唑(PBI)是一类含有苯并咪唑基团的高分子聚合物,分子中苯并咪唑环属于芳香性的刚性环,在PBI分子中极易堆积聚集,分子中咪唑环上含有咪唑氮,所以,PBI与金属离子(如Cu、Mn、Fe、Ru、Ti、Mo和Os等)配位后形成的配合物可用于有机化合物的氧化还原反应催化剂(Olason G, et al. React Funct Polmer, (反应与功能高分子) 1999,42: 163; Cameron C G, et al. J Phys Chem B,((美国)物理化学学报 B)2001, 105:8838 ;Mbelck R, et al. React Funct Polmer, (反应与功能高分子)2007, 67:1448),DArchivio研究了多孔PBI树脂材料的制备方法和性能,并且研究了其与金属离子配位制备的催化剂(D Archivio,et al. Chem-A Eur J,(欧洲化学杂志)2000, 6(5)794)。
作为能源、传感器、电解等领域所用的催化剂即电催化剂,需要有一定的电子导电性能。因此,高分子材料热解碳材料是常用的方法,如用酚醛树脂、尿醛树脂和三聚氰胺树脂等热解制备碳材料。
在PBI家族中,聚(2,5-苯并咪唑)(ABPBI)是最简单的一种,用3,4-二氨基苯甲酸为原料,在多聚磷酸(PPA)中,油浴锅内加热220℃,惰性气体保护下缩合聚合得到。其制备反应方程式为:
ABPBI与以上酚醛树脂、尿醛树脂等高分子材料不同的是:ABPBI分子中苯并咪唑环属于芳香性的刚性环,分子中咪唑环上含有咪唑氮,属于富含氮的芳香型高分子聚合物。因此,其热解可以得到氮掺杂的碳材料,如果在合适的模板作用下,控制分子的芳香环的平面按照一个方向排列,其热解可以得到三维多层氮掺杂的石墨烯材料。
有文献报道聚吡咯,聚苯胺等含氮高分子材料与过渡金属盐一起热解制备二维石墨烯用于燃料电池催化剂的报道(Wei Z, et al. J Am Chem Soc(美国化学会志), 2015,137: 5414)。也有三聚氰胺树脂热解制备氧还原催化剂的报道(Li M, Xue J. J PhysChem C(美国物理化学学报), 2014, 118: 2507),但是无PBI或ABPBI制备氮掺杂三维石墨烯类催化剂的报道。
发明内容
本发明,发明了一种由ABPBI在模板作用下,热解制备三维氮掺杂石墨烯的方法。通过控制ABPBI与模板的质量百分比、模板粒径、涂覆方式和热解工艺等方法来调控制备的3D氮掺杂石墨烯的孔径、孔隙率、比表面积和生成石墨烯的层数。该材料应用于氧化还原反应催化剂,氧还原催化剂,电解水氧析出催化剂及载体,超级电容器,电解、传感器材料等领域。
ABPBI与以上酚醛树脂、尿醛树脂和三聚氰胺树脂等高分子材料不同点是:ABPBI分子中苯并咪唑环属于芳香性的刚性环,分子中咪唑环上含有咪唑氮,属于富氮的芳香型高分子聚合物。因此,其热解可以得到氮掺杂的碳材料,如果在合适的模板作用下,可以得到多层氮掺杂的石墨烯材料。如果控制分子的芳香环的平面按照一个方向排列,其热解可以得到氮掺杂的石墨烯结构。如果用模板支撑热解可以得到三维氮掺杂的石墨烯结构。与聚苯胺、聚(邻苯二胺)、聚吡咯等高分子材料不同的是:ABPBI类高分子是可溶解在DMAc、DMSO等有机溶剂中,易与模板剂充分混合,不分相,由于其可溶性,其在制备3D氮掺杂石墨烯纳米材料时具有很好的操作性。然而,聚苯胺类、聚吡咯等高分子材料不可溶,无法涂饰到模板剂表面,无法与模板剂共混。
ABPBI为固相法或液相法制备的粘均分子量在1万~3万之间的可以溶解在DMAc,DMF,DMSO,N-甲基吡咯烷酮等溶剂中。分子量太大,ABPBI的溶解性能变差;分子量太小其粘度太小,不能对模板剂进行包覆。
三维氮掺杂的石墨烯的制备方法为:首先制备聚合度适当的ABPBI,把ABPBI溶解在溶剂中形成溶液,向溶液中加入适量的,粒径为5~50nm的SiO2做模板剂,搅拌使其充分混合均匀。在搅拌下,加热,慢慢地蒸出溶剂至近干,转入真空干燥箱中60~120℃下烘干。在研钵内研细,平铺在瓷舟底部,放入管式电炉内,在氩气保护下,在600~1200℃下,热解2~3h。待炉温冷却至室温,取出,用HF酸多次洗涤以去除模板SiO2,抽滤,用去离子水洗净,烘干得产品。
在本发明中,模板剂可以是纳米级的SiO2颗粒,也可以是SiO2溶胶,溶胶的溶剂可以是水,也可以是丙酮和醇类等溶剂或者混合溶剂。能否制备出三维氮掺杂石墨烯,模板剂的粒径和加入量是关键:模板剂的粒径决定了制备的碳材料的孔径;模板剂的加入量决定了制备的石墨烯的层数和性能,加入量太少,只能得到多孔碳材料,加入过多,得到的三维石墨烯太薄,容易塌陷,只能得到破碎的石墨烯碎片。模板剂的颗粒度对加入模板剂的量有一定的影响,颗粒度小,其表面积大,需要的模板剂的量就少;反之,如果颗粒度大,需要的模板剂的量就多。模板剂的用量为:ABPBI与模板剂的质量比为3:1~1:3;比例变化与模板的颗粒度有关。颗粒度从5~50nm。在惰性气体保护下热解,热解温度为:600~1200℃;洗涤用稀HF酸,多次洗涤后,用去离子水洗涤至中性即可。
三维氮掺杂的石墨烯表征方法为:孔径、孔隙率、孔容和比表面积用氮气吸附仪(BET),产品的微观形貌分析用扫描电子显微镜(SEM)和透射电子显微镜(TEM),石墨烯层数可以通过高倍透射电子显微镜(HRTEM)来表征。产品的石墨化程度、石墨烯结构和层数可以用X-射线粉末衍射(XRD)、拉曼光谱来表征。产品的元素组成,价态可以用X-射线光电子能谱(XPS)进行了表征,用旋转圆盘电极(RDE)来测试产品的催化氧还原反应(ORR)性能、水电解氧析出反应(EOR)和产品的电容性能测试可以用循环伏安(CV)、线性伏安(LSV)、塔菲尔曲线和充放电性能来测试。产品作为催化剂的耐久性测试可以使用CV、LSV和计时电流曲线(i-t)。产品的催化性能最终需要组装金属空气电池、氢氧燃料电池、电解水的电解池、超级电容器和传感器来测试其性能。
热解温度很重要,热解温度范围为600~1200℃,优选700~1000℃。温度太低ABPBI不能热解,得到产品的导电性能差;热解温度到达最佳温度后,再升高热解温度其性能不变,所以热解温度不宜过高。
具体实施方式
[实施例1] ABPBI的制备(方法一,固相法):取适量的3,4-二氨基苯甲酸(DABA)于研钵内,充分研磨之后转移到有电动搅拌、惰性气体保护三口烧瓶内,通氮气15min以排尽烧瓶内的空气。N2保护,搅拌下,油浴加热225℃,保持3h。冷却后取出,研细,N2保护下,电炉内加热,随后升温到270-275℃,保持3h。冷却至室温,将产物取出、研细,即得到ABPBI,用乌氏粘度计测定ABPBI的分子量。
[实施例2] ABPBI的制备(方法二,液相法):多聚磷酸 (PPA) (50g) 加入到三口烧瓶中,氮气保护下,160℃、搅拌1 h以除去水分及空气。加入3,4-二氨基苯甲酸(6 g,39.5 mmol) 并将温度升高到190℃,控制N2流速,防止DABA被氧化,继续搅拌3h, 反应过程中分批加入约5g P2O5以吸收反应过程中生成的水。随着反应时间的增加,聚合体系逐渐变得粘稠。反应混合液慢慢转移到去离子水中,抽丝,形成纤维状黑色固体,取出烘干,粉碎,洗涤以除去反应混合物中的多聚磷酸和未反应的原料。得到ABPBI产品。用乌氏粘度计测定ABPBI的分子量。
[实施例3]用粒径30nm的SiO2为模板剂与ABPBI混合,热解制备三维多孔氮掺杂石墨烯。以ABPBI与SiO2模板剂质量比为1:1为例:在250mL的烧杯中,加入1g的ABPBI(粘均分子量2~3万)和20mL DMAc,加热、搅拌使其溶解,在搅拌下慢慢加入1g SiO2粒径为30nm的纳米颗粒使其分散均匀。得到的粘稠状液体在搅拌下加热浓缩至近干,在真空干燥箱内100℃下干燥,固体在研钵内研细,转移到瓷舟内,在氩气保护下,在高温电炉内900℃热解2-3h,待炉温降至室温,取出,研细,得到黑色粉末状固体,转移到250mL锥形瓶中,加入70mL的氢氟酸,加热、搅拌24h,抽滤,这样用氢氟酸洗涤三次、水洗至中性,干燥得到黑色粉末状固体产品0.67g。BET测试表明,其孔径分布为20~30nm,比表面积为998.6 m2 g-1,SEM测试表明,得到的产品为多孔泡沫状碳材料,TEM和HRTEM分析表明,产品为三维石墨烯结构碳材料,孔径为30nm,石墨烯彀回表明为2~4层石墨烯。XRD和拉曼光谱测试表明,产品为2~4层的石墨烯结构;XPS分析表明,产品氮含量为7.4%,且氮为吡啶型氮和吡咯型氮。说明,产品是氮掺杂的三维石墨烯结构的材料。其0.1mol/LKOH下催化氧还原性能,氧气起始还原电位为0.96V vs RHE,电子转移数为3.97,耐久性良好;镁空气电池性能达98 mW/cm2。用于氢氧燃料电池其峰功率为540.2mW/cm2,0.5mol/L的硫酸溶液中氧析出起始电位为1.54V vs RHE,极限电流密度达到110mA/cm2。超级电容器比电容为338F g-1,可循环10000 次仍保持电容值的95%。
[实施例4] 按实施例3的方法,其它条件相同,只是ABPBI与二氧化硅的质量变为2:1,同样得到黑色的固体粉末。BET测试表明,其孔径分布仍为30nm,但是其比表面积则降为803 m2 g-1,其SEM和TEM测试表明,其内部为多孔结构的碳材料,表面为多层石墨烯结构,XRD和拉曼数据表明,其石墨烯的层数7~8层。XPS数据与实施例3的产品类似。其0.1mol/LKOH下催化氧还原性能,氧气起始还原电位为0.83V vs RHE,电子转移数为3.63,耐久性良好;镁空气电池性能达67mW/cm2。用于氢氧燃料电池其峰功率为379mW/cm2,0.5mol/L的硫酸溶液中氧析出起始电位为1.57V vs RHE,极限电流密度达到40 mA/cm2。超级电容器比电容为227F g-1,可循环10000 次仍保持电容值的90%。
[实施例5] 按实施例3的方法,其它条件相同,只是ABPBI与二氧化硅的质量变为1:2,同样得到黑色的固体粉末。BET测试表明,其孔径分布范围10~30nm,但是其比表面积则降为847 m2 g-1,其SEM和TEM测试表明,其内部为多孔结构的碳材料,表面为多层石墨烯结构,XRD和拉曼数据表明,其石墨烯的层数7~8层。XPS数据与实施例3的产品类似。其0.1mol/LKOH下催化氧还原性能,氧气起始还原电位为0.84V vs RHE,电子转移数为3.63,耐久性良好;镁空气电池性能达77mW/cm2。用于氢氧燃料电池其峰功率为279mW/cm2,0.5mol/L的硫酸溶液中氧析出起始电位为1.57V vs RHE,极限电流密度达到40mA/cm2。超级电容器比电容为247 F g-1,可循环10000 次仍保持电容值的92%。
[实施例6] 按实施例3的方法,其它条件相同,只是热解温度分别为700℃,1100℃,制备的产品与实施例3的类似,只是各方面性能比实施例3的产品稍差。
[实施例7] 按实施例3的方法,其它条件相同,只是用粒径为5nm SiO2颗粒做模板剂,这时,由于模板剂的粒径变小,其表面积增大,ABPBI的用量增加,则ABPBI与模板剂的质量比改为为3:1,得到的产品与实施例3相似,只是其孔径分布在5~10nm,比表面积为2018m2 g-1,为3~5层的三维氮掺杂石墨烯材料,其0.1mol/LKOH下催化氧还原起始电位为0.91Vvs RHE,电子转移数为3.95,耐久性良好;镁空气电池性能达95mW/cm2。用于氢氧燃料电池其峰功率为471.6mW/cm2,0.5mol/L的硫酸溶液中氧析出起始电位为1.56V vs RHE,极限电流密度达到80mA/cm2。超级电容器比电容为345F g-1,可循环10000 次仍保持电容值的94%。
[实施例8] 按实施例3的方法,其它条件相同,只是用粒径为50nm SiO2颗粒做模板剂,这时由于模板剂的粒径增大,其表面积减小,ABPBI的用量减少,则ABPBI与模板剂的质量比改为为1:3,得到的产品与实施例3相似,只是其孔径分布在50nm,比表面积为765 m2g-1,为3~5层的三维氮掺杂石墨烯材料,其0.1mol/LKOH下催化氧还原起始电位为0.84V vsRHE,电子转移数为3.76,耐久性良好;镁空气电池性能达69mW/cm2。用于氢氧燃料电池其峰功率为268mW/cm2,0.5mol/L的硫酸溶液中氧析出起始电位为1.59V vs RHE,极限电流密度达到50mA/cm2。超级电容器比电容为148F g-1,可循环10000 次仍保持电容值的91%。
[实施例9]用SiO2水溶胶为模板剂,粒径为30纳米。其他实验条件同实施例3。ABPBI与模板剂的质量比为1:1。其结果与实施例3类似。产品为三维石墨烯结构碳材料,孔径为20~30nm,988.3 m2 g-1,为2~4层石墨烯。氮含量为6.7%,且氮为吡啶型氮和吡咯型氮。说明,产品是氮掺杂的三维石墨烯结构的材料。其0.1mol/LKOH下催化氧还原性能,氧气起始还原电位为0.95V vs RHE,电子转移数为3.93,耐久性良好;镁空气电池性能达86mW/cm2。用于氢氧燃料电池其峰功率为373.5mW/cm2,0.5mol/L的硫酸溶液中氧析出起始电位为1.56V vs RHE,极限电流密度达到90 mA/cm2。超级电容器比电容为368F g-1,可循环10000次仍保持电容值的96%。
[实施例10]用SiO2丙酮溶胶为模板剂,粒径为30纳米。其他实验条件同实施例3。ABPBI与模板剂的质量比为1:1。其结果与实施例3类似。孔径为20~30nm,974.9 m2 g-1,为2~4层石墨烯。氮含量为6.6%,且氮为吡啶型氮和吡咯型氮。说明,产品是氮掺杂的三维石墨烯结构的材料。其0.1mol/LKOH下催化氧还原性能,氧气起始还原电位为0.94V vs RHE,电子转移数为3.91,耐久性良好;镁空气电池性能达82mW/cm2。用于氢氧燃料电池其峰功率为365.7mW/cm2,0.5mol/L的硫酸溶液中氧析出起始电位为1.55V vs RHE,极限电流密度达到69mA/cm2。超级电容器比电容为337F g-1,可循环10000 次仍保持电容值的96%。
Claims (6)
1.一种制备三维氮掺杂石墨烯的方法,其特征在于:用可溶解的聚2,5-苯并咪唑(ABPBI)溶液与模板剂纳米SiO2混合均匀,蒸干,在氩气保护下,热解、去除模板剂等工艺制备三维氮掺杂石墨烯;ABPBI是可溶性的,其高分子链是由芳香性的刚性苯并咪唑组成,且分子中含有富含氮元素的咪唑环和端氨基,氩气保护下热解,易形成氮掺杂石墨烯结构,分子中的羧基热解时脱酸起到造孔作用; ABPBI溶液与不同粒径SiO2模板剂采用不同质量比混合、搅拌、蒸出溶剂、真空干燥、研磨,在高温炉内,氩气保护下热解2h,待冷却后,取出,用稀氢氟酸洗涤(去除模板剂)和活化工艺制备得到的三维氮掺杂石墨烯。
2.根据权利要求1所述的ABPBI,其特征在于,聚合物粘均分子量在1~3万之间的可以溶解在二甲基乙酰胺(DMAc),二甲基甲酰胺(DMF),二甲基亚砜(DMSO),N-甲基吡咯烷酮,二甲苯等有机溶剂中的ABPBI聚合物。
3.根据权利要求1所述的模板剂纳米SiO2为,其特征在于,粒径在5~50nm,可以是凝胶也可以是纳米颗粒;溶胶的溶剂可以是水、丙酮和混合溶剂。
4.根据权利要求1所述的ABPBI与纳米SiO2模板剂的质量比为3:1~1:3;混合方式为:ABPBI溶液与SiO2溶胶溶液或纳米SiO2颗粒混合,搅拌混合均匀后,搅拌下加热蒸出溶剂至近干,真空干燥,研细,热解后,用氢氟酸酸洗涤以去除模板剂。
5.根据权利要求1所述的热解温度为600~1200℃,优选700~1000℃。
6.根据权利要求1所述的得到的三维氮掺杂石墨烯,应用于催化氧还原反应的催化剂,用在金属空气电池、燃料电池;也可用于催化电解水氧析出反应的催化剂;还可用于超级电容器的电极材料。
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