CN112547059A - 一种具有良好稳定性的Ru/3DOM SnO2催化剂的制备方法及应用 - Google Patents
一种具有良好稳定性的Ru/3DOM SnO2催化剂的制备方法及应用 Download PDFInfo
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Abstract
一种具有良好稳定性的Ru/3DOM SnO2催化剂的制备方法及应用,属于功能材料合成技术领域。首先利用聚甲基丙烯酸甲酯(PMMA)胶晶模板制备三维有序大孔二氧化锡(3DOM SnO2)载体,然后利用聚乙烯醇(PVA)保护的硼氢化钠还原法将Ru纳米粒子负载到3DOM SnO2载体表面,烘干、焙烧后得到xRu/3DOM SnO2催化剂。本发明操作工艺简单,所制备的xRu/3DOM SnO2催化剂具有高比表面积,对三氯乙烯氧化反应表现出优异的催化活性和稳定性。
Description
技术领域
本发明涉及一种Ru/3DOM SnO2催化剂的制备方法及其应用,即以聚甲基丙烯酸甲酯(PMMA)为硬模板,采用聚乙烯醇(PVA)保护的NaBH4还原法制备Ru粒子并将其负载到三维有序大孔SnO2(3DOM SnO2)载体表面,随后烘干、焙烧得到xRu/3DOM SnO2(x=0.09-1.65wt%)催化剂,最终达到三氯乙烯的高效催化氧化。属于功能材料合成技术领域。
背景技术
近些年来机械制造、石化、制药、喷涂工业中排放的含氯挥发性有机化合物(CVOCs)不仅破坏大气臭氧层、形成光化学烟雾和产生全球变暖等,而且对人类健康构成巨大威胁。研究表明,催化燃烧法是一种比传统物理和其它化学法更有前途且经济的方法。目前,用于消除CVOCs的催化剂主要有三种,即贵金属催化剂、过渡金属氧化物催化剂和沸石催化剂。其中,负载贵金属催化剂以其高活性和优异的抗毒性能备受关注。例如,Wang等(Y.Lao,et al.,Catalysis Science&Technology 8(2018)4797-4811)研究了1,2-二氯苯在Ru/Co3O4催化剂上的氧化反应机理,发现Ru的加入可提高活性氧的利用率,从而改善催化活性。 Wang课题组研究了Ru/CeO2(H.Huang,et al.,Applied Catalysis B:Environmental 158-159(2014)96-105)、Ru/CexAly(Y.Gu,et al.,ACS Omega 3(2018)8460-8470)、 Ru/SBA-15(Q.Dai,et al.,Applied Catalysis B:Environmental 126(2012)64-75)催化剂对CVOCs降解的影响。结果表明,Ru作为一种稳定性较好的活性组分,由此制得的负载Ru催化剂具有优异的催化性能。
SnO2的表面具有丰富的氧空位、酸性物种和活性氧物种,已用于催化领域,如CO氧化、甲烷燃烧、甲苯氧化和NH3选择性还原NOx等。研究人员研究了决定催化剂活性的关键因素。Kamiuchi等(N.Kamiuchi,H.Muroyama,T.Matsui, R.Kikuchi,K.Eguchi,AppliedCatalysis A:General 379(2010)148-154)发现, Pd/SnO2催化剂的核壳结构变化导致催化活性产生差异。经还原或氧化处理后 Pt/SnO2的活性中心重新分散也是导致催化活性产生差异的重要因素(N. Kamiuchi,K.Taguchi,T.Matsui,R.Kikuchi,K.Eguchi,AppliedCatalysis B: Environmental 89(2009)65-72)。Liu等(Y.Liu,et al.,Industrial&Engineering Chemistry Research 57(2018)14052-14063)研究表明,甲苯的深度氧化是由于更多的表面活性氧和酸位暴露所致。
近年来,我们研究了不同形貌的催化剂对苯、甲苯、甲烷、三氯乙烯等不同VOCs氧化的催化性能。三维有序大孔(3DOM)结构由于其独特的孔结构和高比表面积,对VOCs催化氧化表现出优良的催化活性。然而,很少有研究将 SnO2材料应用于CVOCs催化氧化。目前还没有文献报道过Ru/3DOM SnO2对三氯乙烯氧化的催化氧化。
发明内容
本发明的目的是提供一种具有高比表面积、操作简便、且能高效催化三氯乙烯氧化的Ru/3DOM SnO2催化剂的制备方法。
本发明通过聚甲基丙烯酸甲酯(PMMA)胶晶模板法合成3DOM SnO2,采用聚乙烯醇(PVA)保护的NaBH4还原法制备Ru粒子,并将其负载到3DOM SnO2载体表面,随后烘干、焙烧得到xRu/3DOM SnO2催化剂;其中质量百分含量负载量x的取值范围为0%<x≤2%。
具体包括以下步骤:将氯化亚锡溶于去离子水中,搅拌至完全溶解;将上述溶液置于冰浴中,然后滴加H2O2溶液,溶液由透明变为黄绿色,接着又变为透明;当温度到室温时,将PMMA模板渗透到上述前驱体溶液中一段时间。经真空抽滤及室温干燥后,在氮气气氛中以5℃/min的速率升至280-350℃,优选 300℃,保持2h;待冷却到室温后,在空气气氛中(150mL/min)以5℃/min的速率升温至480-520℃优选500℃,保持6h,得到3DOM SnO2载体;
采用PVA保护的NaBH4还原法制备Ru/3DOM SnO2催化剂:将RuCl3水溶液加入冰水浴的PVA溶液中,Ru/PVA质量比=1.0:1.2,30分钟后,将溶解在去离子水中的NaBH4快速加入到上述溶液中,剧烈搅拌30分钟;然后加入 3DOM SnO2;此时,降低搅拌速率以防止对载体大孔结构的破坏。待缓慢搅拌 6h后,真空抽滤,在60℃下干燥12h,在空气气氛中以5℃/min的速率升至 450-550℃,优选500℃,保持2h,得到Ru/3DOM SnO2催化剂。
本发明制得的xRu/3DOM SnO2催化剂对三氯乙烯氧化反应表现出优异的催化性能。
附图说明
图1为所制得催化剂的XRD谱图。其中曲线(a,c-e)为xRu/3DOM SnO2催化剂(x=0,0.19wt%,0.58wt%,0.98wt%)的XRD谱图,曲线(f)、(b)分别为实施例1、实施例2的XRD谱图。
图2为所制得3DOM SnO2的SEM照片。
图3为所制得xRu/3DOM SnO2的TEM照片。其中,(a)、(b)、(c)为3DOM SnO2的TEM照片,(d)、(e)、(f)为0.98Ru/3DOM SnO2的TEM照片。
图4为所制得催化剂对三氯乙烯氧化的催化活性。反应条件为1000ppm三氯乙烯、O2浓度为20vol%、N2为平衡气,空速为40000mL/(g h)。
具体实施方式
为进一步阐述本发明,下面结合实施作详细说明。
实施例1
将8.4g无水氯化亚锡溶于20mL去离子水中,搅拌至完全溶解。将上述溶液置于冰浴中,然后通过注射器滴加6.0g H2O2溶液(质量分数为30wt%的水溶液),溶液由透明变为黄绿色,接着又变为透明。当冷却到室温时,将5.0g PMMA模板渗透到上述前驱体溶液中约4h。经真空抽滤及室温干燥48h后,在氮气气氛(200mL/min)中以5℃/min的速率升至300℃,保持2h。待冷却到室温后,在空气气氛中(150mL/min)以5℃/min的速率升温至500℃,保持6h,得到3DOM SnO2载体。
采用PVA(分子量为10000g/mol)保护的NaBH4还原法制备1.65Ru/3DOM SnO2催化剂(理论负载量为2wt%)。将9.9mL RuCl3(0.010mol/L)水溶液加入冰水浴的6.0mL PVA(2g/L)中(Ru/PVA质量比=1.0:1.2)。30分钟后,将溶解在去离子水中的9.3mL NaBH4(2g/L)快速加入到上述溶液中,剧烈搅拌30分钟。然后加入0.5g 3DOM SnO2。此时,降低搅拌速率以防止对载体大孔结构的破坏。待缓慢搅拌6h后,真空抽滤,在60℃下干燥12h,在空气气氛中以5℃/min 的速率升至500℃,保持2h,得到1.65Ru/3DOM SnO2催化剂。
本发明所得催化剂应用于三氯乙烯的催化氧化,反应主要产物有:二氧化碳、水、HCl、氯气等。在三氯乙烯浓度为1000ppm、O2浓度为20vol%、N2为平衡气以及空速为40000mL/(g h)的条件下,测试了该催化剂的活性及稳定性。该催化剂T50%(三氯乙烯转化率达到50%时所需反应温度)为270℃,T90%(三氯乙烯转化率达到90%时所需反应温度)为300℃,且催化剂T95%(三氯乙烯转化率达到95%时所需反应温度)为320℃时,连续测试30小时内活性稳定,表明该催化剂具有良好的稳定性。
实施例2
采用PVA(分子量为10000g/mol)保护的NaBH4还原法制备0.09Ru/3DOM SnO2催化剂(理论负载量为0.10wt%)。将0.50mL RuCl3(0.010mol/L)水溶液加入冰水浴的0.3mL PVA(2g/L)中(Ru/PVA质量比=1.0:1.2)。30分钟后,将溶解在去离子水中的0.47mL NaBH4(2g/L)快速加入到上述溶液中,剧烈搅拌 30分钟。然后加入0.5g 3DOM SnO2。此时,降低搅拌速率以防止对载体大孔结构的破坏。待缓慢搅拌6h后,真空抽滤,在60℃下干燥12h,在空气气氛中以5℃/min的速率升至500℃,保持2h,得到0.09Ru/3DOM SnO2催化剂。
本发明所得催化剂应用于三氯乙烯的催化氧化。在三氯乙烯浓度为1000 ppm、O2浓度为20vol%、N2为平衡气以及空速为40000mL/(g h)的条件下,该催化剂的T50%为333℃,T90%为378℃。
本发明操作工艺简单,所制备催化剂具有高比表面积,且xRu/3DOM SnO2催化剂对三氯乙烯氧化表现出优异的催化性能。
Claims (3)
1.一种具有良好稳定性的Ru/3DOM SnO2催化剂,其特征在于,通过聚甲基丙烯酸甲酯(PMMA)胶晶模板法合成3DOM SnO2,采用聚乙烯醇(PVA)保护的NaBH4还原法制备Ru粒子,并将其负载到3DOM SnO2载体表面,随后烘干、焙烧得到xRu/3DOM SnO2催化剂;其中质量百分含量负载量x的取值范围为0%<x≤2%。
2.按照权利要求1所述的一种具有良好稳定性的Ru/3DOM SnO2催化剂,其特征在于,其具体制备方法,包括以下步骤:
将氯化亚锡溶于去离子水中,搅拌至完全溶解;将上述溶液置于冰浴中,然后滴加H2O2溶液,溶液由透明变为黄绿色,接着又变为透明;当温度到室温时,将PMMA模板渗透到上述前驱体溶液中一段时间。经真空抽滤及室温干燥后,在氮气气氛中以5℃/min的速率升至280-350℃,优选300℃,保持2h;待冷却到室温后,在空气气氛中以5℃/min的速率升温至480-520℃优选500℃,保持6h,得到3DOM SnO2载体;
采用PVA保护的NaBH4还原法制备Ru/3DOM SnO2催化剂:将RuCl3水溶液加入冰水浴的PVA溶液中,Ru/PVA质量比=1.0:1.2,30分钟后,将溶解在去离子水中的NaBH4快速加入到上述溶液中,剧烈搅拌30分钟;然后加入3DOM SnO2;此时,降低搅拌速率以防止对载体大孔结构的破坏。待缓慢搅拌6h后,真空抽滤,在60℃下干燥12h,在空气气氛中以5℃/min的速率升至450-550℃,优选500℃,保持2h,得到Ru/3DOM SnO2催化剂。
3.权利要求1所述的一种具有良好稳定性的Ru/3DOM SnO2催化剂,的应用,用于对三氯乙烯催化氧化。
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