CN110479239A - 一种厚度为1.5nm铋纳米线及其制备方法和应用 - Google Patents
一种厚度为1.5nm铋纳米线及其制备方法和应用 Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 47
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 31
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000007788 liquid Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001914 filtration Methods 0.000 claims description 5
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- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
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- 229910052697 platinum Inorganic materials 0.000 claims description 3
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Abstract
本发明提供一种厚度为1.5nm铋纳米线及其制备方法和应用,属于纳米线制备方法技术领域。该方法将氯化铋加入到乙二醇乙醚溶液中,超声搅拌均匀直至溶液澄清,放置于油浴中,在惰性气体的保护下,升温反应,然后加入NaI溶液,再升温反应,冷却至常温后,放置于超声仪器中搅拌超声,同时快速加入NaBH4还原液,得到厚度为1.5nm铋纳米线。本发明还提供上述制备方法得到的厚度为1.5nm铋纳米线。本发明还提供上述厚度为1.5nm铋纳米线在电催化还原CO2中的应用。本发明的Bi纳米线材料在宽谱窗口‑0.48V vs.RHE~‑0.98V vs.RHE下,生成甲酸的法拉第效率均能维持在85%以上。
Description
技术领域
本发明属于纳米线制备方法技术领域,具体涉及一种厚度为1.5nm铋纳米线及其制备方法和应用。
背景技术
随着工业的快速发展,大量的化石燃料的使用导致了大气中二氧化碳浓度的急剧升高,由此引发一系列环境问题,如温室效应、沙漠化、全球变暖等。电化学二氧化碳还原反应(CO2RR)用可再生能源(如太阳能,风能和潮汐能等)产生电能驱动反应,将二氧化碳转化为高附加值的化学产品,如甲烷、甲酸、乙醇等,是减轻相关环境危机的最具前景的方法之一,有利于实现真正意义的碳循环。然而,受限于反应物CO2本身的惰性、缓慢的多电子转移动力学以及析氢竞争反应,使得大多数电催化剂的催化活性和选择性均较低。因此,开发经济、稳定、高效的CO2还原电催化材料是实现电化学CO2还原技术大规模应用的关键所在。
CO2还原反应路径复杂,产物众多。从市场价格上来说,含有两个碳原子以上的C2+产物(如乙烯,乙醇,丙醇等)具有更高的工业价值,但根据目前最先进的技术水平来看,含有多个碳原子的长链产物的反应选择性太低,远远不能满足工业生产的要求。因此,通过电化学CO2还原技术生产小分子的化学产品如一氧化碳或甲酸是目前最具实用性的方案。其中,甲酸(或甲酸盐)是CO2还原的重要液体产物,反应路径简单,只涉及两个电子的转移。此外,甲酸也是重要的储氢材料和一种关键的化学中间体,具有重要的工业意义。然而,高能量效率和可规模化的电催化CO2技术要求催化剂在低过电位下具有高反应活性和选择性;可是目前大多数的催化剂都面临高的过电位和低的法拉第效率等问题,导致实际工作中的能源转化效率低下,不能满足工业化的需求。
发明内容
本发明的目的是为了解决现有的CO2催化剂存在高的过电位和低的法拉第效率的问题,而提供一种厚度为1.5nm铋纳米线及其制备方法和应用。
本发明首先提供一种厚度为1.5nm铋纳米线的制备方法,该方法包括:
称取氯化铋加入到乙二醇乙醚溶液中,超声搅拌均匀直至溶液澄清,放置于油浴中,在惰性气体的保护下,升温至60-80℃搅拌反应,然后加入NaI溶液,再升温至140-160℃反应,冷却至常温后,放置于超声仪器中搅拌超声,同时快速加入NaBH4还原液形成黑灰色的分散液,然后将产物经过滤洗涤和干燥,得到厚度为1.5nm铋纳米线。
优选的是,所述的氯化铋、NaI溶液和NaBH4还原液的摩尔为(1-3):0.05:(50-60)。
优选的是,所述的在80℃下反应时间为30-40min。
优选的是,所述的在160℃下反应时间为30-40min。
本发明还提供上述制备方法得到的厚度为1.5nm铋纳米线。
本发明还提供上述厚度为1.5nm铋纳米线在电催化还原CO2中的应用。
优选的是,所述的应用方法为:在被质子交换膜分隔成的三电极电解池中,将上述得到的铋纳米线粉末与乙醇、Nafion溶液混合,超声分散,均匀涂在碳纸上作为工作电极,以铂片为对电极,饱和甘汞电极为参比电极,在阴极槽和阳极槽中分别装入电解质溶液,并通入CO2至饱和,然后在连续通入CO2的条件下恒电位还原CO2,所述恒电位还原过程中的电位控制范围为-0.18V~-1.18V vs.RHE,电解还原时间为100h。
优选的是,所述的电解质溶液为NaHCO3、KHCO3或者Na2SO4溶液。
本发明的有益效果
本发明提供一种厚度为1.5nm铋纳米线及其制备方法和应用,该厚度为1.5nm铋纳米线是采用阶梯升温降温,在惰性气体的保护下,以乙二醇乙醚为溶剂,采用高浓度的NaBH4还原得到了厚度仅为1.5nm的Bi纳米线结构。该制备工艺流程简单且环境友好,整个过程都在常压下进行。
本发明的Bi纳米线材料表现出了优异的CO2催化还原性能,其在宽谱窗口(-0.48Vvs.RHE~-0.98V vs.RHE)下,生成甲酸的法拉第效率均能维持在85%以上,在-0.58Vvs.RHE达到最大值为99%,稳定性长达100小时,且没有其他副产物;同时其能源转换效率高达68.4%,解决了目前CO2电还原催化剂向大规模工业化转型面临的高过电位和低的法拉第效率等问题。本催化剂电催化还原CO2生成的甲酸是一种重要的储氢材料和关键的化学中间体,具有重要的工业意义。
附图说明
图1为本发明实施例1合成的铋纳米线的不同放大倍数透射电子显微镜图;
图2为本发明实施例1合成的超薄铋纳米线催化剂的原子力显微镜图(a)和相对应的厚度分布图(b);
图3为本发明实施例1合成的厚度为1.5nm的Bi纳米线在不同电位下将CO2还原至甲酸的法拉第效率图;
图4为本发明实施例1合成的1.5nm厚的Bi纳米线催化剂还原CO2的线性扫描伏安比较图;
图5为本发明实施例1合成1.5nm厚的Bi纳米线在不同电位下还原CO2至甲酸的能源效率转换图;
图6为本发明实施例1合成1.5nm厚的Bi纳米线在-0.58V下运行100小时的电流效率图;
图7为本发明实施例1合成的Bi纳米线在-0.68V下催化CO2还原生成甲酸的核磁检测图。
具体实施方式
下面结合具体实施例对本发明做进一步的说明,实施例中涉及到的原料均为商购。
实施例1
称取1mmol的氯化铋,加入到100mL的乙二醇乙醚溶液中,超声搅拌均匀直至溶液澄清,放置于油浴中;之后在惰性气体的保护下,升温至80℃搅拌反应30min,加入0.05mmolNaI溶液,再升温至160℃反应30min,冷却至常温后,放置于超声仪器中搅拌超声,同时快速加入50mmol高浓度NaBH4还原液形成黑灰色的分散液;之后用乙醇和水过滤洗涤3次收集,最后置于50℃的真空干燥箱中过夜干燥,得到1.5nm厚Bi纳米线。
图1为本发明实施例1合成的铋纳米线的不同放大倍数透射电子显微镜图,该图可以看出该方法合成出的材料呈现超薄的纳米线结构。
图2为本发明实施例1合成的超薄铋纳米线催化剂的原子力显微镜图(a)和相对应的厚度分布图(b),从图中可以看出该片层的厚度为1.5nm。
实施例2
称取1mmol的氯化铋,加入到100mL的乙二醇乙醚溶液中,超声搅拌均匀直至溶液澄清,放置于油浴中;之后在惰性气体的保护下,升温至60℃搅拌反应30min,加入0.05mmolNaI溶液,再升温至140℃反应30min,冷却至常温后,放置于超声仪器中搅拌超声,同时快速加入50mmol高浓度NaBH4还原液形成黑灰色的分散液;之后用乙醇和水过滤洗涤3次收集,最后置于50℃的真空干燥箱中过夜干燥,得到1.5nm厚Bi纳米线。
实施例3
称取3mmol的氯化铋,加入到200mL的乙二醇乙醚溶液中,超声搅拌均匀直至溶液澄清,放置于油浴中;之后在惰性气体的保护下,升温至80℃搅拌反应40min,加入0.05mmolNaI溶液,再升温至160℃反应40min,冷却至常温后,放置于超声仪器中搅拌超声,同时快速加入60mmol高浓度NaBH4还原液形成黑灰色的分散液;之后用乙醇和水过滤洗涤3次收集,最后置于50℃的真空干燥箱中过夜干燥,得到1.5nm厚Bi纳米线。
实施例4铋纳米线材料用于高效电催化还原二氧化碳生成甲酸的方法的具体步骤:
在被质子交换膜分隔成的三电极电解池中,将实施例1制备得到的5mg铋纳米线粉末与950uL乙醇、50uL Nafion溶液混合、超声分散、均匀涂在碳纸上、作为工作电极,铂片为对电极,饱和甘汞电极为参比电极,在阴极槽和阳极槽中分别装入电解质溶液,并通入CO2至饱和,然后在连续通入CO2的条件下恒电位还原CO2,所述恒电位还原过程中的电位控制范围为-0.18V~-1.18V vs.RHE,电解还原时间为100h。上述电解质溶液为NaHCO3、KHCO3或者Na2SO4溶液。
图3为本发明实施例1合成的厚度为1.5nm的Bi纳米线在不同电位下将CO2还原至甲酸的法拉第效率图。从图中可以看出在宽谱窗口(-0.48V vs.RHE~-0.98V vs.RHE)下,生成甲酸的法拉第效率均能维持在85%以上,在-0.58V vs.RHE达到最大值为99%。
图4为本发明实施例1合成的1.5nm厚的Bi纳米线催化剂还原CO2的线性扫描伏安比较图。该图说明该材料对CO2的电流响应大。
图5为本发明实施例1合成1.5nm厚的Bi纳米线在不同电位下还原CO2至甲酸的能源效率转换图。从图中可以看出,在在-0.58V vs.RHE达到最大值为68.4%,基本满足了工业化的需求。
图6为本发明实施例1合成1.5nm厚的Bi纳米线在-0.58V下运行100小时的电流效率图,从该图可以看出该催化剂在运行100小时内,电流基本没有任何衰减,生成甲酸的法拉第效率保持不变为99%,这也说明该催化剂超高的稳定性。
图7为本发明实施例1Bi纳米线在-0.68V下催化CO2还原生成甲酸的核磁检测图。该图说明:通过核磁NMR(AV 500)氢谱的检测,确实检测到了甲酸,如图标识所示;并以DMSO作为内标进行定量。
Claims (8)
1.一种厚度为1.5nm铋纳米线的制备方法,其特征在于,该方法包括:
称取氯化铋加入到乙二醇乙醚溶液中,超声搅拌均匀直至溶液澄清,放置于油浴中,在惰性气体的保护下,升温至60-80℃搅拌反应,然后加入NaI溶液,再升温至140-160℃反应,冷却至常温后,放置于超声仪器中搅拌超声,同时快速加入NaBH4还原液形成黑灰色的分散液,然后将产物经过滤洗涤和干燥,得到厚度为1.5nm铋纳米线。
2.根据权利要求1所述的一种厚度为1.5nm铋纳米线的制备方法,其特征在于,所述的氯化铋、NaI溶液和NaBH4还原液的摩尔为(1-3):0.05:(50-60)。
3.根据权利要求1所述的一种厚度为1.5nm铋纳米线的制备方法,其特征在于,所述的在80℃下反应时间为30-40min。
4.根据权利要求1所述的一种厚度为1.5nm铋纳米线的制备方法,其特征在于,所述的在160℃下反应时间为30-40min。
5.权利要求1-4任何一项所述的制备方法得到的厚度为1.5nm铋纳米线。
6.权利要求5所述的厚度为1.5nm铋纳米线在电催化还原CO2中的应用。
7.根据权利要求6所述的厚度为1.5nm铋纳米线在电催化还原CO2中的应用,其特征在于,所述的应用方法为:在被质子交换膜分隔成的三电极电解池中,将上述得到的铋纳米线粉末与乙醇、Nafion溶液混合,超声分散,均匀涂在碳纸上作为工作电极,以铂片为对电极,饱和甘汞电极为参比电极,在阴极槽和阳极槽中分别装入电解质溶液,并通入CO2至饱和,然后在连续通入CO2的条件下恒电位还原CO2,所述恒电位还原过程中的电位控制范围为-0.18V~-1.18V vs.RHE,电解还原时间为100h。
8.根据权利要求7所述的厚度为1.5nm铋纳米线在电催化还原CO2中的应用,其特征在于,所述的电解质溶液为NaHCO3、KHCO3或者Na2SO4溶液。
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