CN114892214B - 一种铜基导电核壳结构催化剂及其制备方法和应用 - Google Patents
一种铜基导电核壳结构催化剂及其制备方法和应用 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000010949 copper Substances 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 39
- 239000011258 core-shell material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 13
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- 238000000034 method Methods 0.000 claims abstract description 13
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- 229910018274 Cu2 O Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提出了采用多步法合成铜基导电核壳结构催化剂,催化活性位点均匀分散在铜纳米线与表面生长的导电配位聚合物产生的界面上,解决现有技术中合成成本高、催化剂活性差、选择性低、过电势高等问题。通过先合成形貌均匀、尺寸均一的铜纳米线,再在铜纳米线表面生长出一薄层铜的导电配位聚合物,形成了具有高催化活性的界面效应。本发明提供的方法,原料价廉易得、条件温和,在能源转化与存储领域,新能源电动汽车,合成气及环保等领域具有广阔的应用前景。
Description
技术领域
本发明涉及催化剂材料技术领域,具体是涉及一种铜基导电核壳结构催化剂及其制备方法和应用。
背景技术
从工业革命以来,随着工业化进程的推进,化石燃料不断被消耗并伴随着大量二氧化碳的排放,导致温室效应并造成环境不断恶化。目前,为了减缓温室效应,减少大气中CO2的浓度,世界各国均在积极落实全球气候变化协定并开发新技术,在直接减少CO2排放的同时提高化石燃料的燃烧技术,提升能源利用率,但技术的革新在短时间内难以实现。近些年来,CO2的捕获和储存技术受到了研究者的广泛关注和重点研究。主要体现为两种方式:1)将CO2直接捕获并海底封存;2)将CO2通过化学方法转化为其他多碳产物,实现能源再利用。显然后者更具有可持续性发展的理念。
现阶段成熟的CO2催化还原途径主要有三类,即光催化还原,热催化还原,电催化还原。光催化CO2还原是基于植物对光合作用的模拟,在常温常压下,利用光的驱动,将CO2催化还原为可再生碳氢化学品,主要产物为一氧化碳、甲烷、甲酸、甲醇等。但由于催化剂激活需要的能量高,电子和空穴容易复合等原因,反应活性和选择性低,难以实现大规模工业化。热催化CO2还原是以一定比例的CO2和H2为反应气,在加热或加压的情况下,在反应炉中将CO2转化为可再生碳氢燃料,主耍产物为甲烷、甲醇、乙醇等;目前已经达到了工业水平。而电催化CO2还原是以清洁能源电能为驱动能源,在常温常压下于水溶液中进行反应。对比光催化CO2和热催化CO2反应,其反应条件简单且温和,能耗低,环境友好,是最为理想的CO2化学转化途径。
在众多CO2电催化剂中,Cu是非常特殊的,它是唯一能够大量生成碳氢产物和醇类的催化剂。但是它又具有非常大的过电位和比较差的产物选择性,这就为它的实际应用带来了很大的障碍。
发明内容
本发明的目的在于克服现有技术存在的不足,提供一种铜基导电核壳结构催化剂及其制备方法和应用。
为了实现以上目的,本发明的技术方案为:
一种铜基导电核壳结构催化剂的制备方法,包括以下步骤:
1)合成直径为100~200nm的铜纳米线;
2)将铜纳米线分散在乙醇和水的混合溶液中,然后加入可与铜配位的含氮有机物配体分散均匀,搅拌状态下在空气中反应4~6h于铜纳米线表面生长含氮有机物层,将反应液离心,离心后产物清洗、干燥后真空保存;其中含氮有机物与铜纳米线的摩尔比为1:5~50。
可选的,所述含氮有机物配体是氨基苯类盐酸盐,包括苯四胺四盐酸盐、六氨基三苯六盐酸盐。
此外,其他可与铜配位的含氮有机物配体,例如N,N-二甲基乙二胺、4,4-联吡啶等也适用。
可选的,所述步骤1)中,铜纳米线的合成方法为:以浓度为6~8mol/L的氢氧化钠为反应溶液,加入浓度为0.05-0.15mol/L的铜盐、络合剂和还原剂,在70-90℃的油浴锅中反应0.5~2h,冷却后离心得到的铜纳米线清洗、干燥后真空保存。
可选的,所述络合剂是乙二胺,所述还原剂是水合肼,所述铜盐、络合剂和还原剂的体积比为5mL:2~3mL:100~150ul。
可选的,所述步骤2)中,反应温度为常温。
一种上述制备方法制备的铜基导电核壳结构催化剂,包括铜纳米线和包覆于铜纳米线表面的含氮有机层。
进一步的,其活性位点为铜纳米线与表面生长的含氮有机层产生的界面效应。
上述铜基导电核壳结构催化剂在二氧化碳电催化还原反应的应用。
一种流动扩散电解池,采用上述铜基导电核壳结构催化剂作为二氧化碳电还原催化剂,可以极大程度提高液相产物的选择性,降低过电势。从而能够高效、绿色的生产乙醇、甲酸等化工品。。
本发明的有益效果为:
1)将铜纳米线与可与铜配位的含氮有机物配体反应,在铜纳米线表面生长出含氮有机物层,从而得到核壳结构,构筑出一种界面效应作为催化剂的活性位点,作为二氧化碳电催化还原反应催化剂具有优异的选择性、极低的过电势和高效产液相的优点,对于降低碳排放具有重要意义,在清洁、绿色能源可持续发展及环境领域具有广阔应用前景。
2)原料易获取,反应条件温和,无需高温烧结,合成成本低,适于实际生产应用。
附图说明
图1是本发明实施例1中制备的催化剂扫描电子显微镜谱图;
图2是本发明比较例1、2中制备的催化剂扫描电子显微镜谱图;
图3是本发明实施例1中制备的催化剂透射电子显微镜谱图;
图4是本发明实施例1,比较例1、2中制备的催化剂的XRD衍射谱图;
图5是本发明实施例1中制备的催化剂红外测试谱图;
图6是本发明实施例1中制备的催化剂XPS谱图;
图7是本发明比较例1、2中制备的催化剂XPS谱图;
图8是本发明实施例1,比较例1、2中制备的催化剂经循环伏安CV扫描稳定后的LSV谱图;
图9是本发明实施例1中制备的催化剂经多步电位测试的法拉第效率谱图;
图10是本发明比较例1、2中制备的催化剂经多步电位测试的法拉第效率谱图;
图11是本发明实施例1中制备的催化剂在-1.2V vs SCE下电解3h后的液相产物的核磁谱图。
具体实施方式
以下结合附图和具体实施例对本发明做进一步解释。
实施例1
1)合成铜纳米线:首先配制好浓度为7mol/L的氢氧化钠溶液、浓度为0.1mol/L的硝酸铜溶液;合成采用油浴的方法,将温度设置为80℃等待升温完毕。而后将配制好的浓度为7mol/L的氢氧化钠溶液取150mL加入到容量为250mL的三颈烧瓶中,此时打开磁力搅拌,取5mL浓度为0.1mol/L的硝酸铜溶液加入其中,而后取2.5mL的乙二胺(99wt%)缓慢滴加到上述溶液中,最后迅速取125ul的水合肼(80wt%)加入混合液中,可观察到溶液迅速由天蓝色变为白色浑浊液而后转变为澄清溶液。此时关闭搅拌,使得整个溶液体系在80℃的油浴中静置反应1h。反应完毕,冷却后离心得到的铜纳米线在0.5mol/L的HCL中浸泡酸洗5min。而后经过两次水洗和一次乙醇洗后,置于80℃的真空干燥箱干燥10h得到最终产物CuNWs,产物真空保存防止氧化。
2)合成铜纳米线外层均匀生长含氮有机层的导电材料:称取上述制备好的CuNWs25.6mg,加入到含有9ml乙醇溶液的体积为20ml的样品瓶中,超声分散5min,使得纳米线在乙醇中均匀分散;而后取1ml的去离子水加入其中,超声5min;而后称取3.8mg的TAB粉末加入到分散好的铜纳米线的乙醇和水的混合溶液中,超声分散5min使得TAB粉末分散均匀;之后用滤纸盖住反应容器(防止杂质引入的同时,使得反应在空气中进行),将样品瓶置于磁力搅拌器,使其在100r/min的状态下反应5h。反应完毕后,将所得反应液离心,采用水溶液清洗离心3次,乙醇溶液清洗离心1次。最后将离心后产物置于70℃烘箱干燥10h得到最终产物CuTAB5h@Cu。产物真空保存。
比较例1
按照实施例1的方法合成出CuNWS,取50mg CuNWs于小瓷舟中,而后放入马弗炉进行加热氧化处理。程序设置为:以10℃/min的升温速率将温度升至150℃,并在150℃下保温90min后自然降温,冷却后得到最终产物Cu2O@Cu。
比较例2
按照实施例1的方法合成出CuNWS,称取上述制备好的CuNWs 25.6mg,加入到含有9ml乙醇溶液的体积为20ml的样品瓶中,超声分散5min,使得纳米线在乙醇中均匀分散;而后取1ml的去离子水加入其中,超声5min;而后称取3.8mg的TAB粉末加入到分散好的铜纳米线的乙醇和水的混合溶液中,超声分散5min使得TAB粉末分散均匀;之后用滤纸盖住反应容器(防止杂质引入的同时,使得反应在空气中进行),将样品瓶置于磁力搅拌器,使其在100r/min的状态下反应24h。反应完毕后,将所得反应液离心,采用水溶液清洗离心3次,乙醇溶液清洗离心1次。最后将离心后产物置于70℃烘箱干燥10h得到最终产物CuTAB24h@Cu2O。产物真空保存。
称取一定量实施例1,比较例1、2中制备的样品在扫描电子显微镜下观察,参见图1和图2,由图1中可见,实施例1得到的铜纳米线,尺寸约为100~200nm,形貌均匀,尺寸均一;包覆的壳层均匀生长于铜纳米线上且没有破坏纳米线的整体结构,形貌和尺寸均有良好的保持;由图2可见当反应时间延长至24h,过量反应导致纳米线的坍塌;Cu2O对照样则明显生长在铜纳米线的表层与实施例1相比过量反应导致有机配位聚合物无法均匀的生长在纳米线的表面,并且会腐蚀纳米线导致结构的坍塌。
称取一定量实施例1中制备的催化剂在透射电镜下观察得到图像,参见图3,由图中可见,实施例1为明显的核壳结构,外层生长的有机配体的尺寸约为20~50nm。
称取一定量实施例1,比较例1、2中制备的催化剂测试XRD,参见图4,由图中可见,实施例1中并未发现明显的CuTAB峰,表明其实无定型的结构;比较例1中的Cu峰较实施例1明显减弱,表明铜纳米线此时已经基本被腐蚀,核壳结构遭到破坏;实施例2中也发现了明显的Cu2O峰,表明了表面Cu2O的成功制备。
称取一定量实施例1中制备的催化剂粉末进行红外表征,参见图5,由图中可见,位于2900左右NH-峰的明显减弱甚至消失以及1200左右CN-振动峰的偏移可以说明Cu-N的成功配位,表明了CuTAB的成功制备……。
称取一定量实施例1中制备的催化剂测试XPS,参见图6,由图中可见,铜的价态分别分为纳米线中的0价以及表层配位聚合物的Cu2+,这和XRD图谱可以很好的印证CuTAB在铜纳米线的成功制备。
称取一定量比较例1、2中制备的催化剂测试XPS,参见图7,由图中可见,铜的价态表现为Cu2O和CuTAB与实施例1相比0价的Cu峰消失,这与XRD图谱很好的对应,表明了过量的反应导致了铜纳米线结构的坍塌,界面效应瓦解。
将实施例1和比较例1、2制备的铜纳米线外层均匀生长含氮有机层的导电材料用于电化学性能测试:将5mg催化剂分散在含有700ul异丙醇,270ul去离子水,30ul的nafion溶液当中,将其超声30min混合均匀;然后将100ul催化剂浆液滴在抛光研磨干净的玻碳电极表面,放在通风橱内自然风干;以饱和甘汞电极为参比电极和玻片电极作为对电极进行电化学性能测试;电势参考饱和甘汞电极(SCE):ERHE=ESCE+0.242+0.059×pH(0.1M饱和KHCO3溶液)。在二氧化碳饱和的0.1M KHCO3溶液中以5mV s-1的扫描速率进行4圈的循环伏安CV扫描(-0.5V~-1.4V),进行催化剂的活化,然后在循环伏安扫描稳定后得到LSV极化曲线,参见图8,由图中可见,比较例1中的电还原电流明显高于比较例1、2,表明其界面效应活性位点的增多促进了二氧化碳电还原反应。
随后进行多步电位测试,每隔30min一个电位,反应15min后进样进行色谱分析,测试结果见图9、图10。所有电极电势数据都进行了85%的IR补偿。由图中可见,实施例1在-1~-1.4V(Vs.SCE)的电势范围内均有极高的液相产物法拉第效率,尤其在-1.2V(Vs.SCE)时,液相产物法拉第效率达到了100%,很好的抑制了析氢副反应的发生。相较于图10中比较例1、2,其法拉第效率均有极大的提高。
按照上述电化学性能测试方法,使得实施例1的催化剂在-1.2Vvs.SCE的电势下电解3h,而后收集H池阴极室中的电解后溶液700ul于核磁管中,加入35ul的标样(14ml的重水中加入10ul的DMSO),而后进行核磁测试,得到的谱图参见图11,由图中可见,二氧化碳电还原的液相产物包括甲酸、甲醇和乙醇。
实施例1的催化剂表现优异的CO2RR性能,其在-0.55V vs RHE,液相产物的法拉第效率可达100%,交换电流密度可达9.864mA/cm2,具备有极低的过电势。
上述实施例仅用来进一步说明本发明的一种铜基导电核壳结构催化剂及其制备方法和应用,但本发明并不局限于实施例,凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均落入本发明技术方案的保护范围内。
Claims (8)
1.一种铜基导电核壳结构催化剂的制备方法,其特征在于,包括以下步骤:
1)合成直径为100~200 nm的铜纳米线;
2)将铜纳米线分散在乙醇和水的混合溶液中,然后加入可与铜配位的含氮有机物配体分散均匀,搅拌状态下在空气中反应4~6h于铜纳米线表面生长含氮有机物层,将反应液离心,离心后产物清洗、干燥后真空保存;其中含氮有机物与铜纳米线的摩尔比为1:5~50;所述含氮有机物配体包括苯四胺四盐酸盐或六氨基三苯六盐酸盐。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤1)中,铜纳米线的合成方法为:以浓度为6~8 mol/L的氢氧化钠为反应溶液,加入浓度为0.05-0.15mol/L的铜盐、络合剂和还原剂,在70-90℃的油浴锅中反应0.5~2h,冷却后离心得到的铜纳米线清洗、干燥后真空保存。
3.根据权利要求2所述的制备方法,其特征在于:所述络合剂是乙二胺,所述还原剂是水合肼,所述铜盐、络合剂和还原剂的体积比为5 mL:2~3 mL:100~150 ul。
4.根据权利要求1所述的制备方法,其特征在于:所述步骤2)中,反应温度为常温。
5.一种权利要求1~4任一项所述制备方法制备的铜基导电核壳结构催化剂,其特征在于:包括铜纳米线和包覆于铜纳米线表面的含氮有机层。
6.根据权利要求5所述的铜基导电核壳结构催化剂,其特征在于:活性位点为铜纳米线与表面生长的含氮有机层产生的界面效应。
7.权利要求5所述铜基导电核壳结构催化剂在二氧化碳电催化还原反应的应用。
8.一种流动扩散电解池,其特征在于:使用权利要求5所述的铜基导电核壳结构催化剂。
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