CN113648993B - 一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法 - Google Patents
一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法 Download PDFInfo
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Abstract
本发明属于纳米材料制备技术领域,公开了一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法。包括配制含有氧化石墨烯粉末和一定浓度的钯前驱体的混合液体;在大气压冷等离子体石英反应器中处理含有氧化石墨烯粉末和钯前驱体的混合液体;对大气压冷等离子体处理后的混合液体进行离心、洗涤、烘干得到氧化石墨烯负载钯催化材料。大气压冷等离子体在液相中只还原钯而不还原氧化石墨烯,简化制备步骤,提升催化性能,节约制备资源。
Description
技术领域
本发明属于纳米材料制备技术领域,具体涉及一种溶液中氧化石墨烯负载钯(Pd/GO)的制备方法。
背景技术
对硝基苯酚(4-NP)是工业废水中常见的难降解物,已被国际上列为环境优先控制污染物之一。将4-NP还原为对氨基苯酚(4-AP),不仅可有效解决水资源污染问题,其还原产物4-AP还可用于农药、染料、表面活性剂、医药和化妆品等领域,实现资源再利用。因此,制备高效催化材料,将污染物4-NP转化为有价值的4-AP成为研究热点。
碳材料表面含有丰富的含氧官能团,如羟基(OH)和烷氧基(O-C)等。这些含氧官能团可改善金属活性组分的分布,并可与其发生协同作用,从而提高催化活性。石墨烯基载钯催化材料已被广泛用于催化还原对硝基苯酚(4-NP)。
石墨烯基载钯催化材料的制备方法很多,如化学还原法和氢气热还原法等。专利“石墨烯负载钯镍/氧化铈纳米复合材料、制备方法以及氨硼烷催化分解方法”(CN106378150A)公开的那样,将氧化石墨烯、十六烷基三甲基溴化铵溶于超纯水中,超声后将贵金属盐加入体系中,搅拌下向混合溶液中迅速加入还原剂硼氢化钠。最后用无水乙醇超声离心洗涤三次、真空干燥制得纳米复合材料。专利“一种石墨烯负载钯纳米颗粒复合材料催化剂的制备方法”(CN111589443A)公开的那样,将氧化石墨烯投入氯化钯溶液中浸渍后喷雾干燥成粉末,然后在H2气氛下高温还原收得含钯的石墨烯粉末,再浸渍之后化学还原制得石墨烯负载钯纳米颗粒催化剂。研究人员开发了各种制备方法,获得了高性能的碳材料载钯催化材料。但化学还原法需要使用过量有毒化学试剂;氢气热还原法需要高温、能耗较高,且易造成Pd纳米粒子团聚,从而降低催化性能。需要强调的是,这些方法在还原钯离子过程中,会将氧化石墨烯(GO)载体还原为还原氧化石墨烯(rGO),不利于催化性能的提升。如果能开发一种简单、绿色的方法,在还原钯离子的同时,不还原GO,且能产生较多活性缺陷,将具有重要意义。
等离子体是具有一定带电粒子密度,宏观持电中性的粒子聚集态。它被称为除固态、液态和气态之外的物质第四态。通常根据热力学平衡将等离子体分为非热力学平衡等离子体(冷等离子体)、局部热力学平衡等离子体(热等离子体)、完全热力学平衡等离子体(高温等离子体)。冷等离子体是典型的非热力学平衡体系,其 其Te高达1-10eV,而Tg与Ti可接近室温,因此被称为非热力学平衡等离子体。冷等离子体的产生方式有多种,例如介质阻挡放电、辉光放电、电晕放电等。冷等离子体是由电子、离子、自由基、激发态物种等组成,这些活性物种在许多方面应用广泛。如专利“大气压冷等离子体方式制备金属纳米颗粒的方法”(CN103008684A)公开的那样,采用大气压下直流放电产生冷等离子体,来还原制备金属纳米颗粒。
发明内容
为了克服现有技术的不足,本发明提供一种利用大气压表面介质阻挡放电冷等离子体,在溶液中制备氧化石墨烯负载钯的方法,该方法不需要任何其他还原性化学试剂,在还原钯离子的同时不还原氧化石墨烯载体,且使氧化石墨烯表面产生较多缺陷,从而使制备的氧化石墨烯负载钯表现出优异的催化还原对硝基苯酚活性。
本发明的上述目的是通过以下技术方案实现的:一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法,具体包括以下步骤:
1.配制含有氧化石墨烯粉末和一定浓度的钯前驱体的混合液体;
2.在大气压冷等离子体石英反应器中处理含有氧化石墨烯粉末和钯前驱体的混合液体;
3.对混合液体进行离心、洗涤、烘干得到氧化石墨烯负载钯催化材料。
其中,所述步骤1具体为:称取0.1g氧化石墨烯粉末放入玻璃瓶中,然后使用移液枪转移一定体积的钯前驱体溶液于玻璃瓶中,摇匀。
所述步骤2具体为:将含有氧化石墨烯粉末和钯前驱体的混合液体倒入大气压等离子体石英反应器中,调整石英反应器与电极间距,调节大气压冷等离子体放电频率及放电电压,通入一定成分的气体,设置磁力搅拌器的转速对混合液体进行处理。
所述步骤3具体为:将处理后的混合液体倒入50ml离心管中,在7000r·min-1转速下离心5min,倒掉上清液,去离子水洗涤离心三次后放入烘箱100℃下干燥4h。
所述步骤1中的钯前驱体为Pd(NO3)2或PdCl2,混合溶液中钯前驱体的浓度范围是2.35-7.27mM。
所述步骤3中氧化石墨烯负载钯中钯的负载量范围0.1-5.0wt%。
所述步骤2中大气压等离子体采用大气压表面介质阻挡放电冷等离子体,被处理混合液体与电极不直接接触,液面距电极2-4mm,混合液体深3-5mm。
所述步骤2中大气压等离子体施加频率为8.3-12.3kHz,正弦峰峰值为4.0-8.0kV的交流电压,处理溶液时间为6-12min。
所述步骤2通入的气体为氩氢混合气体,混合气体中氢气占比为10-100%,气体总流量为50-150ml·min-1。
本发明与现有技术相比的有益效果是:采用大气压表面介质阻挡放电冷等离子体技术,以氩气和氢气的混合气体为工作气体,处理钯前驱体与氧化石墨烯的混合液体,制备氧化石墨烯载钯催化材料(Pd/GO),其具有优异的催化还原对硝基苯酚(4-NP)活性;大气压冷等离子体在液相中只还原钯而不还原氧化石墨烯,简化制备步骤,提升催化性能,节约制备资源。
附图说明
图1:GO,Pd/GO-H2/Ar-G,Pd/GO和Pd/GO-Ar-L催化材料的XRD图;
图2:GO载体与Pd/GO催化材料的Raman光谱图;
图3:GO载体与Pd/GO催化材料(a)C1s和(b)O1s的XPS能谱图;
图4:GO载体与Pd/GO催化材料的FT-IR光谱图;
图5:GO,Pd/GO-H2/Ar-G,Pd/GO和Pd/GO-Ar-L还原4-NP在400nm处At/A0随时间变化曲线图;
图6:Pd/GO-H2/Ar-G,Pd/GO和Pd/GO-Ar-L催化材料还原4-NP反应动力学图。
具体实施方式
下面通过具体实施例详述本发明,但不限制本发明的保护范围。如无特殊说明,本发明所采用的实验方法均为常规方法,所用实验器材、材料、试剂等均可从商业途径获得。
实施例1
液相中氩氢等离子体制备Pd/GO催化材料:
液相中氩氢等离子体制备Pd/GO催化材料,具体步骤为:首先配制1.28g·L-1的Pd(NO3)2溶液;称取0.1g的GO粉末放入玻璃瓶中,再用移液枪转移4ml配制的Pd(NO3)2溶液至玻璃瓶中,摇匀备用。将制备的混合液体倒入石英反应器中(直径3cm,深度4mm)。调整石英反应器高度,使液面距电极2mm,将装置密封后连接好电路,用示波器调节放电频率为10.3kHz,放电电压为6.0kV。通入H2/Ar混合气体(VH2:VAr=1:1)10min,气体流量为100ml·min-1。放电时间为9min,设置磁力搅拌器为500r·min-1。放电结束后关闭电源,关闭气路。将处理混合溶液倒入50ml离心管中,7000r·min-1离心5min。倒掉上清液,去离子水洗涤离心三次后放入烘箱100℃干燥4h,将制得样品记为Pd/GO。Pd的质量分数为2.0wt%。
实施例2
液相中氩等离子体制备Pd/GO-Ar-L催化材料:
液相中氩等离子体制备Pd/GO-Ar-L,具体步骤与实施例1相似,仅将放电气氛改为纯氩气,气体流量为100ml·min-1,将制得样品记为Pd/GO-Ar-L。Pd的质量分数为2.0wt%。
实施例3
气相中氩氢等离子体制备Pd/GO-H2/Ar-G催化材料:
气相中氩氢等离子体制备Pd/GO-H2/Ar-G催化材料,具体步骤为:称取0.1g的GO粉末放入样品瓶中,再用移液枪转移适量H2PdCl4溶液至玻璃瓶容器中过量浸渍一夜。将浸渍完成的样品在120℃烘箱中干燥2小时后备用。将干燥后的样品放入板-板式介质阻挡放电装置中,通入H2/Ar混合气体(VH2:VAr=1:1)10min,气体流量为100ml·min-1,放电频率为11.8kHz,放电电压为11.0kV。放电时间为6min,将处理完成样品记为Pd/GO-H2/Ar-G。Pd的质量分数为2.0wt%。
XRD图分析:
如图1可见,GO样品在2θ=11°出现尖锐的衍射峰,此峰为GO(001)晶面的特征衍射峰。液相中氩氢等离子体制备Pd/GO样品,在2θ=11°处特征衍射峰向右偏移至12.4°,这是由于等离子体处理增强其表面缺陷所致(图2Raman结果可证实),与液相中氩等离子体制备Pd/GO-Ar-L样品结果相同,未检测到还原氧化石墨烯(rGO)的特征衍射峰。而气相中氩氢等离子体制备Pd/GO-H2/Ar-G样品,在2θ=24.8°观察到rGO特征衍射峰。从图中还可以看出,液相中氩氢等离子体制备Pd/GO样品和气相中氩氢等离子体制备Pd/GO-H2/Ar-G,在2θ=40.2°处均可观察到较为明显的衍射峰,对应于面心立方晶体结构Pd(111)晶面(PDF#01-075-6724)。而液相中氩等离子体制备Pd/GO-Ar-L样品,即没有出现rGO的特征衍射峰,也没有出现金属Pd的特征衍射峰。
Raman光谱分析:
采用拉曼光谱对GO和Pd/GO的表面结构和缺陷进行研究,结果如图2所示。两个样品均在约1348与1573cm-1处出现两个明显的谱峰,分别对应于GO的D和G波段。G带峰是由于石墨烯2D六边形晶格中sp2碳原子的切向振动,而D带则是由于石墨烯sp3缺陷的存在。通常用ID:IG来反映碳材料的缺陷密度,该值越高缺陷密度越大。与GO相比,Pd/GO的G带强度降低,D带强度增加,说明液相氩氢等离子体可使GO产生较多缺陷,这与XRD中GO特征衍射峰的偏移结果相一致。
XPS能谱分析:
采用X射线光电子能谱(XPS)对GO和Pd/GO表面的碳物种和氧物种进行了研究,结果如图3所示。图3a为GO和Pd/GO中C1s的XPS能谱图。对两个样品的C1s能谱峰进行分峰拟合得到四个能谱峰,在284.65,286.82,288.30和289.70eV结合能为中心的解卷积峰分别对应C-C,C–O(C-O-C),C=O和O-C=O官能团。此外,与GO载体相比,等离子体制备Pd/GO样品的C1s能谱峰没有明显变化,说明等离子体处理未破坏GO表面含氧官能团。这些结果与XRD结果相一致。图3b为GO和Pd/GO中O1s的XPS能谱图。如图可见,两个样品在以530.97,531.77,532.60和533.33eV结合能为中心的解卷积峰分别对应O-C=O,C=O,C-OH和C-O-C官能团。此外,从图3b还可以看出,与GO的O1s能谱峰相比,Pd/GO样品中保留了较多的烷氧基(C-O)和羟基(O-H)等含氧官能团,这也体现了液相Ar/H2等离子体未还原GO载体的特性。
FT-IR光谱分析:
图4为GO和Pd/GO的FT-IR光谱。如图可见,GO样品在3405和1617cm-1处有明显的吸收峰,这对应于O-H的伸缩振动。在1720cm-1处的吸收峰,对应于COOH中的C=O羰基伸缩振动。此外,从图中还可观察到GO的其他官能团,例如C-O(1051cm-1),C-O-C(1220cm-1)和O=C-O(1402cm-1)。与GO载体相比,Pd/GO样品中含氧官能团的吸收峰强度降低很少,具有较多烷氧基(C-O)和羟基(O-H)。这是由于液相Ar/H2等离子体制备未破坏含氧官能团,与XPS结果相一致。
催化活性分析:
图5为催化还原4-NP在400nm处吸光度随时间变化曲线图。由图可知,只加入GO条件下,反应200s后400nm吸收峰没有明显降低,证明GO几乎没有反应活性。Pd/GO-H2/Ar-G以及Pd/GO-Ar-L样品在反应过程中表现出一定活性。液相中氩氢等离子体制备Pd/GO表现出优异的催化活性,150s后几乎反应完全。
为了更加直观体现三种样品活性,对其催化还原4-NP的反应动力学进行研究。采用图5在400nm处的吸光度数据,以-ln(At/A0)对时间t作图,并进行线性拟合。如图6所示,根据拟合线计算斜率,可得反应表观速率常数k。Pd/GO-Ar-L和Pd/GO-H2/Ar-G催化还原4-NP的k值分别为0.579和0.517min-1,Pd/GO的k为1.394min-1。Pd/GO的k约为Pd/GO-Ar-L和Pd/GO-H2/Ar-G的2.4和2.7倍。
结论:
综上所述,液相中氩等离子体不能还原钯离子和氧化石墨烯,活性较差。气相中氩氢等离子体制备方法还原能力较强,在还原钯离子的同时也将GO载体还原,减少了载体上的含氧官能团,降低了载体吸附4-NP的能力,所以活性较差。而液相中氩氢等离子体制备方法,在还原溶液中钯离子的同时未还原GO载体,且使载体表面产生较多活性缺陷位点,提高了催化还原4-NP的活性。
以上所述实施方式仅为本发明的优选实施例,而并非本发明可行实施的全部实施例。对于本领域一般技术人员而言,在不背离本发明原理和精神的前提下对其所作出的任何显而易见的改动,都应当被认为包含在本发明的权利要求保护范围之内。
Claims (5)
1.一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法,其特征在于,具体包括以下步骤:
(1)配制含有氧化石墨烯粉末和一定浓度的钯前驱体的混合液体,混合液体中钯前驱体为Pd(NO3)2或PdCl2,浓度范围是2.35-7.27 mM;
(2)在大气压冷等离子体石英反应器中处理含有氧化石墨烯粉末和钯前驱体的混合液体;
(3)对大气压冷等离子体处理后的混合液体进行离心、洗涤、烘干得到氧化石墨烯负载钯催化材料,催化材料中钯的负载量范围0.1-5.0wt%;
所述步骤(2)具体为:将含有氧化石墨烯粉末和钯前驱体的混合液体倒入大气压等离子体石英反应器中,调整石英反应器与电极间距,调节大气压冷等离子体放电频率及放电电压,通入氩氢混合气体,设置磁力搅拌器的转速对混合液体进行处理,其中,大气压等离子体采用大气压表面介质阻挡放电冷等离子体,被处理混合液体与电极不直接接触,混合液体液面距电极2-4 mm,混合液体深3-5 mm,所述氩氢混合气体中氢气占比至少为10%,气体总流量为50-150 mL·min-1。
2.根据权利要求1所述的一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法,其特征在于,所述步骤(1)具体为:称取0.1g氧化石墨烯粉末放入玻璃瓶中,然后使用移液枪转移一定体积的钯前驱体溶液于玻璃瓶中,摇匀。
3.根据权利要求1所述的一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法,其特征在于,所述步骤(3)具体为:将处理后的混合液体倒入50mL离心管中,在7000 r∙min-1转速下离心5 min,倒掉上清液,去离子水洗涤离心三次后放入烘箱100℃下干燥4h。
4.根据权利要求3所述的一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法,其特征在于,所述步骤(2)中大气压冷等离子体施加频率为8.3-12.3 kHz,正弦峰峰值为4.0-8.0 kV的交流电压,处理时间为6-12 min。
5.根据权利要求1所述的一种液相中大气压冷等离子体制备氧化石墨烯负载钯的方法,其特征在于,所述步骤1的混合液体中钯前驱体为Pd(NO3)2。
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