CN107824172A - 一种表面富含缺陷位的纳米氧化铝载体的制备方法 - Google Patents
一种表面富含缺陷位的纳米氧化铝载体的制备方法 Download PDFInfo
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Abstract
本发明提供了一种表面富含缺陷位的纳米氧化铝载体的制备方法，将无机铝盐和沉淀剂按照一定摩尔比溶解于水‑乙二醇混合溶剂中，搅拌得到透明溶液，将溶液转移至水热釜中；反应结束后，反应物料经过滤、洗涤、干燥、焙烧得到富含表面缺陷的纳米氧化铝载体。本发明采用简便的溶剂热—热解法制备表面富含缺陷位的纳米氧化铝材料。以该材料作为催化剂载体制备负载型纳米贵金属催化剂具有优异的热稳定性及催化活性。本发明合成工艺简单、成本低，适用于负载型催化剂的制备技术领域。
Description
技术领域
本发明涉及一种表面富含缺陷位的纳米氧化铝载体及其制备方法，以及此材料在负载型催化剂中的应用。
背景技术
氧化铝是最常用的工业原料之一，在陶瓷、耐火材料、医药、催化等领域有着极其重要的应用。氧化铝比表面积大、孔容和孔径分布可调、机械强度良好、热稳定性好、价格低廉，同时其具有多种不同的晶相结构，表面存在不同性质的酸中心。因此，氧化铝是石油工业中应用最广泛的催化剂载体。
中国专利【CN 106276992 A】公开了一种叶片状γ-氧化铝载体的制备方法，该方法采用无机铝源和尿素为原料，水热反应后，物料经过滤、洗涤和干燥得到一水软铝石前驱体，焙烧后得到叶片状纳米γ-氧化铝载体。
中国专利【CN 10311287A】公开了一种氧化铝载体的制备方法，该方法利用溶胶凝胶和水热合成法，制备的氧化铝比表面积最高可达400m2/g。
中国专利【CN 104085909 A】公开了一种大孔氧化铝载体的制备方法，该方法将聚乙烯醇溶解于胶溶液中，与大孔干胶粉和含硼化合物均匀混合，经混捏、成型后干燥焙烧制得孔径集中度高、孔容大的氧化铝载体。
中国专利【CN 103896318 A】公开了一种富含B酸(酸)介孔氧化铝的制备方法，该方法采用廉价的拟薄水铝石为原料，加入酸性改性剂进行改性，后加入水溶性聚合物和氟硼酸铵，加热回流，得到的混合物经陈化，干燥，粉碎，焙烧得到富B酸氧化铝。
目前，人们对氧化铝载体的调控普遍局限于形貌、比表面积、孔容孔径、表面酸碱性等，但对表面缺陷的认知不够深入。Ja Hun Kwak等(Science，2009，325，1670-1673)揭示了γ-氧化铝表面配位不饱和的Al3+可以锚定贵金属，增强金属载体之间相互作用。然而商业氧化铝表面缺陷位不足，鲜有合成表面富含缺陷氧化铝的技术文献，因此发明一种表面富含缺陷位氧化铝载体的制备方法对于负载型催化剂应用十分必要。
发明内容
本发明拟提供一种表面富含缺陷位纳米氧化铝载体及其制备方法。该氧化铝载体材料的制备采用廉价的无机铝盐、沉淀剂、乙二醇及水为原料，制备过程简单、无需模板剂，产物易于分离，生产成本低，有利于大规模生产制备。
本发明的技术方案：
一种表面富含缺陷位的纳米氧化铝载体的制备方法，步骤如下：
(1)将无机铝盐和沉淀剂按照一定摩尔比溶解于水-乙二醇混合溶剂中，搅拌得到透明溶液，将溶液转移至水热釜中；
(2)反应结束后，反应物料经过滤、洗涤、干燥、焙烧得到富含表面缺陷的纳米氧化铝载体。
所述的无机铝盐为硝酸铝或硫酸铝，其中Al3+的浓度是0.01～6.5M。
所述的沉淀剂为尿素、碳酸铵、碳酸氢铵中的一种，尤其优选尿素。
所述的无机铝离子与沉淀剂的摩尔比为1:5～1:9。
所述的水-乙二醇混合溶剂中水与乙二醇的体积比为1:1—5:1。
所述的水热反应温度是100～200℃，反应时间为12～48h。
所述的干燥温度为60～90℃，干燥时间为6～12h。
所述的焙烧温度为500～900℃，焙烧时间为2～8h。
所述的纳米氧化铝载体的比表面积为150～400m2/g，孔容为0.34～0.62cm3/g，且表面富含缺陷位。
本发明的有益效果：本发明采用简便的溶剂热—热解法制备表面富含缺陷位的纳米氧化铝材料。以该材料作为催化剂载体制备负载型纳米贵金属催化剂具有优异的热稳定性及催化活性。本发明合成工艺简单、成本低，适用于负载型催化剂的制备技术领域。
附图说明
图1(a)是实施例1所制备的氧化铝材料在5μm条件下的扫描电镜照片。
图1(b)是实施例1所制备的氧化铝材料在500nm条件下的扫描电镜照片。
图2是实施例1所制备的氧化铝材料的氮吸附等温曲线。
图3是实施例2所制备的PtSn/Al2O3催化剂的透射电镜照片。
图4是实施例3所制备的Au/Al2O3催化剂的透射电镜照片。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
实施例1
将0.02mol Al(NO3)3·9H2O和0.12mol尿素置于烧杯中，烧杯置于恒温水浴锅内，用量筒量取25mL去离子水和5mL乙二醇缓慢加入烧杯中，匀速搅拌，温度保持在30℃；将上述溶液转移到50mL水热釜中，在100℃烘箱中水热反应24h，自然冷却到室温，经离心洗涤至中性后，将产物置于80℃烘箱干燥过夜。所得白色沉淀在马弗炉内800℃焙烧2h，升温速率为1℃/min，得到纳米棒状氧化铝载体，其扫描电镜如图1所示。氮吸附测试结果表明比表面积约为230m2/g，孔容为0.40cm3/g，其氮吸附等温曲线如图2所示。
实施例2
将13.27mg H2PtCl6·6H2O和14.94mg SnCl2·2H2O前驱物溶解到330μL乙醇溶液，将上述溶液等体积浸渍到1g实施例1中所制备的载体上，浸渍后样品室温静置2h，50℃烘箱干燥过夜，所得样品在20％O2/N2气氛中，500℃下焙烧4h，得到丙烷脱氢制丙烯的PtSn/Al2O3催化剂。
实施例3
取实施例1中所制备氧化铝载体120mg均匀分散于6mL去离子水中，搅拌条件下加入735μL HAuCl4(4.9g/L)溶液，搅拌十分钟后加入200μL沉淀剂(0.5M碳酸铵溶液)，待体系稳定后，将混合液置于60℃水浴锅中反应2h。离心洗涤(去离子水洗4次，乙醇洗1次)除去氯离子。最后真空干燥过夜(干燥剂为P2O5)，即得一氧化碳氧化的Au/Al2O3催化剂。
实施例4
作为对比，用商业氧化铝作为载体，用13.27mg H2PtCl6·6H2O、14.94mgSnCl2·2H2O、50μL乙醇配制成溶液，将1g商业氧化铝在等体积该溶液中浸渍120min；除去表面水分；50℃烘箱干燥过夜；500℃马弗炉焙烧4h，得到PtSn/Al2O3催化剂样品。
实施例5
作为对比，以专利【CN 104451954A】纤维状纳米氧化铝为载体，称取120mg均匀分散于6mL子水中，搅拌条件下加入735μL HAuCl4(4.9g/L)溶液，搅拌十分钟后加入200μL沉淀剂(0.5M碳酸铵溶液)，待体系稳定后，将混合液置于60℃水浴锅中反应2h。离心洗涤(去离子水洗4次，乙醇洗1次)除去氯离子。最后真空干燥过夜(干燥剂为P2O5)，得到Au/Al2O3催化剂。
采用本发明实施例2和实施例4催化剂催化丙烷脱氢制丙烯，具体方法为：取100mg催化剂置于丙烷脱氢制丙烯用固定床反应器内，常压条件下，通入H2和N2，控制流速分别为8mL/min、10mL/min，然后以10℃/min的速率将温度由室温升至590℃，还原2h后，调节H2流量为10mL/min，30min后通入丙烷气体，在常压下进行丙烷催化脱氢制丙烯的反应。本发明实施例2和实施例4中氧化铝载体的织构性质及对应催化剂催化丙烷脱氢制丙烯的催化剂性能如表1所示。
采用本发明实施例3和实施例5催化剂催化CO氧化，具体方法为：将制得的催化剂在马弗炉内250℃焙烧2h后，取50mg催化剂置于CO氧化用固定床反应器内，测定催化活性。催化反应气配比为1％CO、20％O2、79％N2，反应空速80000mL·h-1·gcat -1。本发明实施例3和实施例5中氧化铝载体的织构性质及对应催化剂催化一氧化碳氧化性能如表2所示。
表1实施例2和实施例4氧化铝载体织构性质及对应催化剂催化丙烷脱氢制丙烯的催化性能
由表1可知，采用商业氧化铝为载体时，制备的催化剂活性较低，并且选择性也不理想；而实施例2中催化剂具有优异的活性和选择性，由于较强的金属载体相互作用的存在，载体中丰富的缺陷位可以有效分散和固定Pt-Sn纳米团簇，提高了催化剂在高温下抗积碳和抗烧结能力。
表2实施例3和实施例5氧化铝载体织构性质及对应催化剂催化一氧化碳氧化的催化性能
由表2可知，采用专利【CN 104451954 A】纤维状纳米氧化铝为载体，在210℃下CO才可以完全转化；而实施例3中催化剂在低温下即可实现CO的完全转化，主要是由于载体表面富含缺陷位可以锚定Au颗粒实现活性组分高分散，其中Au颗粒粒径约为2nm。
Claims (10)
1.一种表面富含缺陷位的纳米氧化铝载体的制备方法，其特征在于，步骤如下：
(1)将无机铝盐和沉淀剂按照摩尔比为1:5～1:9溶解于水-乙二醇混合溶剂中，搅拌得到透明溶液，将溶液转移至水热釜中；所述的水热反应温度是100～200℃，反应时间为12～48h；
(2)反应结束后，反应物料经过滤、洗涤、干燥、焙烧得到富含表面缺陷的纳米氧化铝载体，其比表面积为150～400m2/g，孔容为0.34～0.62cm3/g。
2.根据权利要求1所述的制备方法，其特征在于，所述的水-乙二醇混合溶剂中水与乙二醇的体积比为1:1～5:1。
3.根据权利要求1或2所述的制备方法，其特征在于，所述的无机铝盐为硝酸铝或硫酸铝，其中，Al3+的浓度是0.01～6.5M。
4.根据权利要求1或2所述的制备方法，其特征在于，所述的沉淀剂为尿素、碳酸铵、碳酸氢铵中的一种。
5.根据权利要求3所述的制备方法，其特征在于，所述的沉淀剂为尿素、碳酸铵、碳酸氢铵中的一种。
6.根据权利要求1、2或5所述的制备方法，其特征在于，所述的干燥温度为60～90℃，干燥时间为6～12h。
7.根据权利要求3所述的制备方法，其特征在于，所述的干燥温度为60～90℃，干燥时间为6～12h。
8.根据权利要求4所述的制备方法，其特征在于，所述的干燥温度为60～90℃，干燥时间为6～12h。
9.根据权利要求1、2、5、7或8所述的制备方法，其特征在于，所述的焙烧温度为500～900℃，焙烧时间为2～8h。
10.根据权利要求6所述的制备方法，其特征在于，所述的焙烧温度为500～900℃，焙烧时间为2～8h。
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