CN108187692A - 一种负载双金属的二氧化钛纳米多孔陶瓷催化剂及其制备方法和应用 - Google Patents
一种负载双金属的二氧化钛纳米多孔陶瓷催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种负载双金属的二氧化钛纳米多孔陶瓷催化剂及其制备方法和应用。所述的催化剂以二氧化钛纳米多孔陶瓷膜为载体,以金铜双金属纳米颗粒为活性组分;所述催化剂的制备方法包括步骤:1)钛酸纳米带通过压滤、烧结制得二氧化钛纳米多孔陶瓷膜;2)采用一步沉积沉淀法将金铜双金属纳米颗粒负载到陶瓷膜上,经过H2还原,制得负载金铜双金属的二氧化钛纳米多孔陶瓷催化剂。本发明制备得到的负载双金属的二氧化钛纳米多孔陶瓷催化剂,催化活性金属颗粒分布均匀,成分组成量化可控,催化剂多孔结构均匀、孔隙率高,具有高催化活性、选择性和稳定性,易于回收和重复利用,适合大规模的产业化应用。
Description
技术领域
本发明涉及一种负载双金属的二氧化钛纳米多孔陶瓷催化剂及其制备方法,以及该催化剂在苯甲醇、甲醇等醇类的选择性氧化反应中的应用,属于催化剂技术领域。
背景技术
双金属纳米结构催化剂具有比单金属催化剂更为优异的催化活性、选择性以及稳定性,是目前催化材料合成领域的研究热点之一。为了进一步提高双金属纳米材料的催化活性和稳定性,通常需要将其固载于催化剂载体的表面。中国专利(CN104525220A)介绍了一种Au-CuO/TiO2微球催化剂,其载体为水热法制备的海胆状TiO2微球,适用于可见光下空气中CO的脱除和燃料电池中富氢气氛下CO的去除。中国专利(CN103433058A)介绍了一种Au-Cu/TiO2-NBs双金属纳米结构整体式催化剂及制备方法,该方法是先通过原位置换法制备双金属负载催化剂,再将其组装为纳米纸材料。其中Cu纳米颗粒以Cu2O的形成存在,未烧结的纳米纸催化剂,机械强度差,不宜应用于实际的催化反应过程。
对于负载贵金属催化剂,载体的结构是影响催化剂活性和催化反应过程的重要因素。因此,研究和发展新型载体是构建新型高效催化反应体系途径之一。二氧化钛纳米带是一种热稳定性强、比表面积高、表面平滑的一维纳米材料,在光催化、催化、传感等领域均具有广泛应用。由于二氧化钛纳米带具有高的长径比和比表面积,容易集成组装为多孔膜结构,经过高温烧结后可形成纳米多孔陶瓷膜。这种膜具有均匀的孔结构和高孔隙率,作为催化剂载体用于非均相催化反应过程,将具有良好的流体力学性能。该纳米陶瓷多孔膜还具有高比表面积和均匀的孔壁表面微结构,将其作为载体负载双金属催化剂,可以有效提高金属纳米颗粒的分散性及金属的原子利用率,进而提高催化活性和选择性。
目前,基于钛酸纳米带烧结制备的二氧化钛纳米多孔陶瓷膜,以及应用这种陶瓷膜做载体负载双金属纳米颗粒制备催化剂均尚未见报道。
发明内容
为了解决现有技术的不足,本发明提供一种负载双金属的二氧化钛纳米多孔陶瓷催化剂及其制备方法和应用。该催化剂以二氧化钛纳米多孔陶瓷膜为载体,陶瓷膜具有均匀的多孔结构和高孔隙率,高气体渗透性和良好的流体力学性能,其上负载的金属纳米颗粒高度分散,尺寸均匀,成分组成量化可控。所述催化剂具有高催化活性、高选择性和高稳定性,易于回收和重复利用,可用于苯甲醇、甲醇等醇类的催化氧化反应。
本发明的技术方案如下:
一种负载双金属的二氧化钛纳米多孔陶瓷催化剂,所述的催化剂以二氧化钛纳米多孔陶瓷膜为载体,以金铜双金属纳米颗粒为活性组分;所述的纳米多孔陶瓷膜的直径为5~50mm,厚度为0.5~2mm,平均孔径为100~500nm;所述催化剂的制备方法包括步骤:1)钛酸纳米带通过压滤、烧结制得二氧化钛纳米多孔陶瓷膜;2)采用一步沉积沉淀法将金铜双金属纳米颗粒负载到陶瓷膜上,经过H2还原,制得负载金铜双金属的二氧化钛纳米多孔陶瓷催化剂。
根据本发明,铜的负载量为0.05~10wt%,金的负载量为0.01~5wt%。
根据本发明,优选的,铜的负载量为0.05~2wt%,金的负载量为0.01~2wt%。
根据本发明,一种负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法,包括步骤:
(1)将钛酸纳米带压滤成膜,压力为1~5MPa,之后放入马弗炉中煅烧1~6h使其烧结,煅烧温度为800~1000℃,升温速率为1~10℃/min,得到二氧化钛纳米多孔陶瓷膜;
(2)将二氧化钛纳米多孔陶瓷膜放入加有HAuCl4溶液和Cu(CH3COO)2溶液的混合溶液中,避光静置沉积1~5h,再加入尿素溶液调节pH为8~9,在60~100℃下避光反应2~8h,待反应结束,取出陶瓷膜,并用超纯水洗涤、干燥,然后在H2氛围下进行还原处理,得到负载双金属的二氧化钛纳米多孔陶瓷催化剂。
根据本发明优选的,步骤(2)中,所述HAuCl4溶液的浓度为5~20g/L,所述Cu(CH3COO)2溶液的浓度为0.01~1mol/L;根据本发明优选的,步骤(2)中,二氧化钛纳米多孔陶瓷膜放入加有HAuCl4溶液和Cu(CH3COO)2溶液的混合溶液后,使Cu2+与Au3+的摩尔比例为(0.5~10):1,优选(0.5~3):1。
根据本发明优选的,所述的还原处理是指在H2流速为30~60mL/min的氛围下进行还原,还原温度为300~600℃,时间为2~5h;升温速率为5~10℃/min。
本发明的方法步骤(1)中,所述钛酸纳米带的制备可按现有技术。本发明优选的方案如下:
钛酸纳米带的制备步骤包括:将二氧化钛均匀分散在摩尔浓度为5~15M的氢氧化钠溶液中,置于150~250℃的恒温干燥箱内反应24~72h,冷却至室温后,用超纯水洗涤,得到钛酸钠纳米带,然后将钛酸钠纳米带放入摩尔浓度为0.05~0.15M的盐酸溶液中进行离子交换,得到的产物经过抽滤、超纯水洗涤,放于烘箱内干燥8~12h,即得到钛酸纳米带。其中,进一步优选的,氢氧化钠溶液的溶度为8~12M,恒温干燥箱中反应温度为180~220℃,反应时间为48-72h;盐酸溶液的浓度为0.08~0.12M。
所述的二氧化钛是锐钛矿二氧化钛纳米颗粒,二氧化钛与所述氢氧化钠的质量体积比为(1~20):200,单位为g/mL。
所述盐酸溶液与所述氢氧化钠溶液的体积比为(1~50):1,优选(1~10):1。
本发明负载双金属的二氧化钛纳米多孔陶瓷催化剂应用于苯甲醇催化氧化制取苯甲醛或甲醇催化氧化制取甲醛反应。
本发明具有以下优点:
(1)本发明所制备的负载双金属的二氧化钛纳米多孔陶瓷催化剂,其纳米多孔陶瓷载体具有均匀的多孔结构和高孔隙率、高气体渗透性和良好的流体力学性能,使得催化剂在负载量很小的情况下,便具有良好的催化活性;
(2)本发明所制备的负载双金属的二氧化钛纳米多孔陶瓷催化剂,是经过压滤、烧结形成的纳米多孔陶瓷膜,机械强度好,能够宏观独立存在,且易于回收循环利用;
(3)本发明所制备的负载双金属的二氧化钛纳米多孔陶瓷催化剂,制备工艺简单,操作方便,可重复性好;
(4)本发明所制备的负载双金属的二氧化钛纳米多孔陶瓷催化剂,其表面金属颗粒分布均匀、负载量可调可控,可以简单通过改变溶液中Au、Cu组成比例和溶液的pH来提高催化剂的催化活性与稳定性;
(5)本发明所制备的负载双金属的二氧化钛纳米多孔陶瓷催化剂改善了负载单一金属活性低、稳定性差的缺点,在苯甲醇催化氧化转化为苯甲醛的实验中,负载双金属的二氧化钛纳米多孔陶瓷催化剂表现出了优异的催化活性、选择性和稳定性。
附图说明
图1为本发明实施例1所涉及的扫描电子显微镜(SEM)照片,图1a为实施例1步骤(1)得到的钛酸纳米带的SEM照片,图1b为纯二氧化钛纳米多孔陶瓷膜的SEM照片,图1c、d分别为实施例1制得的负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的截面和表面的SEM照片。
图2为本发明实施例1制得的负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的X射线光电子能谱(XPS)图。
图3为本发明实施例1制得的负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的光学照片。
图4为本发明实施例1制得的负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂在立式石英管反应器中的光学照片。
图5为本发明空白二氧化钛纳米多孔陶瓷膜、对比例1、对比例2、实施例1制得的催化剂催化苯甲醇氧化实验结果比较图。
图6为本发明实施例1制得的负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂对苯甲醇气相催化氧化的结果曲线。
具体实施方式
下面结合实施例及说明书附图对本发明的技术方案做进一步说明,但本发明所保护范围不限于此。
实施例中所述二氧化钛购自上海阿拉丁公司;
实施例1
一种负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的制备方法,包括步骤如下:
(1)将2.5g二氧化钛均匀分散于500mL浓度为10mol/L的氢氧化钠溶液中,放于200℃的恒温干燥箱中反应72h,得到钛酸钠纳米带,然后将样品放入1000mL浓度为0.1mol/L的盐酸溶液中离子交换24h,得到钛酸纳米带,得到的钛酸纳米带的扫描电子显微镜SEM照片如图1a所示。
取上述钛酸钠米带0.04g,在压力为4MPa的情况下进行压滤成膜。将得到的样品放入马弗炉内1000℃煅烧2h,得到二氧化钛纳米多孔陶瓷膜。
(2)在含有40mL去离子水的循环套管中同时加入10g/L的HAuCl4溶液174μL和0.1mol/L的Cu(CH3COO)2溶液97μL,搅拌均匀后,将步骤(2)制得的二氧化钛纳米多孔陶瓷膜放入混合液中避光静置沉积2h,再用尿素溶液调节pH为8,80℃恒温水浴条件下老化4h,之后用超纯水洗涤、干燥,得到的催化剂初品在400℃下进行3h的H2还原预处理,随后自然冷却至室温后取出,得到负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂。
制备得到的二氧化钛纳米多孔陶瓷膜以及负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的电镜照片如图1b、c、d所示。从图中可以看出,二氧化钛纳米多孔陶瓷膜具有良好的烧结效果以及均匀的多孔结构和高的孔隙。比较图1b和d说明,双金属纳米颗粒均匀的分散负载于二氧化钛纳米多孔陶瓷膜表面。负载双金属的二氧化钛纳米多孔陶瓷催化剂的XPS图如图2所示,从图上可以看到显著的金属金和铜的特征峰,说明Au-Cu纳米颗粒被成功负载于纳米多孔陶瓷膜表面。该催化剂的光学照片见图3。
对比例1
负载铜纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的制备方法,步骤如下:
(1)将2.5g二氧化钛均匀分散于500mL浓度为10mol/L的氢氧化钠溶液中,放于200℃的恒温干燥箱中反应72h,得到钛酸钠纳米带,然后将样品放入1000mL浓度为0.1mol/L的盐酸溶液中离子交换24h,得到钛酸纳米带。
取上述钛酸钠米带0.04g,在压力为4MPa的情况下进行压滤成膜。将得到的样品放入马弗炉内1000℃煅烧2h,得到二氧化钛纳米多孔陶瓷膜。
(2)在含有40mL去离子水的循环套管中加入0.1mol/L的Cu(CH3COO)2溶液97μL,搅拌均匀后,将步骤(2)制得的二氧化钛纳米多孔陶瓷膜放入溶液中避光静置沉积2h,再用尿素溶液调节pH为8,80℃恒温水浴条件下老化4h,之后用超纯水洗涤、干燥,得到的催化剂初品在400℃下进行3h的H2还原预处理,随后自然冷却至室温后取出,得到负载铜纳米颗粒的二氧化钛纳米多孔陶瓷催化剂。
对比例2
负载金纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的制备方法,步骤如下:
(1)将2.5g二氧化钛均匀分散于500mL浓度为10mol/L的氢氧化钠溶液中,放于200℃的恒温干燥箱中反应72h,得到钛酸钠纳米带,然后将样品放入1000mL浓度为0.1mol/L的盐酸溶液中离子交换24h,得到钛酸纳米带。
取上述钛酸钠米带0.04g,在压力为4MPa的情况下进行压滤成膜。将得到的样品放入马弗炉内1000℃煅烧2h,得到二氧化钛纳米多孔陶瓷膜。
(2)在含有40mL去离子水的循环套管中加入10g/L的HAuCl4溶液174μL,搅拌均匀后,将步骤(2)制得的二氧化钛纳米多孔陶瓷膜放入溶液中避光静置沉积2h,再用尿素溶液调节pH为8,80℃恒温水浴条件下老化4h,之后用超纯水洗涤、干燥,得到的催化剂初品在400℃下进行3h的H2还原预处理,随后自然冷却至室温后取出,得到负载金纳米颗粒的二氧化钛纳米多孔陶瓷催化剂。
实施例2
一种负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的制备方法,包括步骤如下:
(1)将2.5g二氧化钛均匀分散于500mL浓度为10mol/L的氢氧化钠溶液中,放于200℃的恒温干燥箱中反应72h,得到钛酸钠纳米带,然后将样品放入1000mL浓度为0.1mol/L的盐酸溶液中离子交换24h,得到钛酸纳米带。
取上述钛酸钠米带0.04g,在压力为2MPa的情况下进行压滤成膜。将得到的样品放入马弗炉内800℃煅烧4h,得到二氧化钛纳米多孔陶瓷膜。
(2)在含有40mL去离子水的循环套管中同时加入10g/L的HAuCl4溶液87μL和0.1mol/L的Cu(CH3COO)2溶液21μL,搅拌均匀后,将步骤(2)制得的二氧化钛纳米多孔陶瓷膜放入混合液中避光静置沉积2h,再用尿素溶液调节pH为8.5,70℃恒温水浴条件下老化6h,之后用超纯水洗涤、干燥,得到的催化剂初品在420℃下进行2.5h的H2还原预处理,随后自然冷却至室温后取出,得到负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂。
实施例3
一种负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂的制备方法,包括步骤如下:
(1)将2.5g二氧化钛均匀分散于500mL浓度为10mol/L的氢氧化钠溶液中,放于200℃的恒温干燥箱中反应72h,得到钛酸钠纳米带,然后将样品放入1000mL浓度为0.1mol/L的盐酸溶液中离子交换24h,得到钛酸纳米带。
取上述钛酸钠米带0.04g,在压力为5MPa的情况下进行压滤成膜。将得到的样品放入马弗炉内900℃煅烧3h,得到二氧化钛纳米多孔陶瓷膜。
(2)在含有60mL去离子水的循环套管中同时加入10g/L的HAuCl4溶液87μL和0.01mol/L的Cu(CH3COO)2溶液629μL,搅拌均匀后,将步骤(2)制得的二氧化钛纳米多孔陶瓷膜放入混合液中避光静置沉积3h,再用尿素溶液调节pH为9,90℃恒温水浴条件下老化3h,之后用超纯水洗涤、干燥,得到的催化剂初品在440℃下进行2h的H2还原预处理,随后自然冷却至室温后取出,得到负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂。
催化性能测试
实验测试方法:
苯甲醇催化氧化制备苯甲醛的反应是在小型气相催化反应装置中进行,以苯甲醇催化氧化制备苯甲醛的转化率和苯甲醛的选择性为标准。在常压下,液态苯甲醇以18.68μL/min的速率由注射泵供应进入220℃预热炉,O2和N2按空气比例分别以9.2mL/min、34.8mL/min的速率进入预热炉,经充分汽化、混合后,三种气体进入240℃装有40mg陶瓷催化剂的反应炉中。反应后,混合物通过冷阱进行冷凝回收,用气相色谱进行检测。催化结果如图5、6所示。
图5为空白二氧化钛纳米多孔陶瓷膜、对比例1、对比例2、实施例1制备的催化剂的催化性能比较,上述催化剂分别为空白二氧化钛纳米多孔陶瓷膜、负载铜纳米颗粒的二氧化钛纳米多孔陶瓷催化剂、负载金纳米颗粒的二氧化钛纳米多孔陶瓷催化剂和负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂,在240℃,常压下,反应8h所得的苯甲醇的转化率和苯甲醛的选择性。
由图5中数据可以看出:与其他催化剂相比,负载双金属的二氧化钛纳米多孔陶瓷催化剂的转化率较高,达到了50%左右,经ICP测定,两种金属的实际负载量分别为金0.05wt%,铜0.09wt%,说明这种纳米多孔陶瓷膜负载双金属催化剂在金属负载量极低的情况下,就可以获得良好的催化性能。
图6为实施例1制得的负载金铜双金属纳米颗粒的二氧化钛纳米多孔陶瓷催化剂应用于苯甲醇气相催化氧化的催化性能。从图中可以看出,经过2h初始反应活化后,苯甲醇的氧化转化率基本保持稳定在50%左右。可知负载双金属的二氧化钛纳米多孔陶瓷催化剂具有高催化活性和稳定性,是一种极具应用前景的新型催化剂。
Claims (10)
1.一种负载双金属的二氧化钛纳米多孔陶瓷催化剂,其特征在于,所述的催化剂以二氧化钛纳米多孔陶瓷膜为载体,以金铜双金属纳米颗粒为活性组分;所述的纳米多孔陶瓷膜的直径为5~50mm,厚度为0.5~2mm,平均孔径为100~500nm;所述催化剂的制备方法包括步骤:1)钛酸纳米带通过压滤、烧结制得二氧化钛纳米多孔陶瓷膜;2)采用一步沉积沉淀法将金铜双金属纳米颗粒负载到陶瓷膜上,经过H2还原,制得负载金铜双金属的二氧化钛纳米多孔陶瓷催化剂。
2.根据权利要求1所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂,其特征在于,铜的负载量为0.05~10wt%,金的负载量为0.01~5wt%。
3.根据权利要求1所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法,其特征在于,所述制备方法包括步骤:步骤(1):将钛酸纳米带压滤成膜,压力为1~5MPa,之后放入马弗炉中煅烧1~6h使其烧结,煅烧温度为800~1000℃,升温速率为1~10℃/min,得到二氧化钛纳米多孔陶瓷膜;步骤(2):将二氧化钛纳米多孔陶瓷膜放入加有HAuCl4溶液和Cu(CH3COO)2溶液的混合溶液中,避光静置沉积1~5h,再加入尿素溶液调节pH为8~9,在60~100℃下避光反应2~8h,待反应结束,取出陶瓷膜,并用超纯水洗涤、干燥,然后在H2氛围下进行还原处理,得到负载双金属的二氧化钛纳米多孔陶瓷催化剂。
4.根据权利要求3所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法,其特征在于,步骤(2)中,所述HAuCl4溶液的浓度为5~20g/L,所述Cu(CH3COO)2溶液的浓度为0.01~1mol/L。
5.根据权利要求3所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法,其特征在于,步骤(2)中,二氧化钛纳米多孔陶瓷膜放入加有HAuCl4溶液和Cu(CH3COO)2溶液的混合溶液后,使Cu2+与Au3+的摩尔比例为(0.5~10):1。
6.根据权利要求3所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法,其特征在于,所述的还原处理是指在H2流速为30~60mL/min的氛围下进行还原,还原温度为300~600℃,时间为2~5h,升温速率为5~10℃/min。
7.根据权利要求3所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法,其特征在于,所述钛酸纳米带的制备步骤包括:将二氧化钛均匀分散在摩尔浓度为5~15M的氢氧化钠溶液中,置于150~250℃的恒温干燥箱内反应24~72h,冷却至室温后,用超纯水洗涤,得到钛酸钠纳米带,然后将钛酸钠纳米带放入摩尔浓度为0.05~0.15M的盐酸溶液中进行离子交换,得到的产物经过抽滤、超纯水洗涤,放于烘箱内干燥8~12h,即得到钛酸纳米带。
8.根据权利要求7所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法,其特征在于,所述的二氧化钛是锐钛矿二氧化钛纳米颗粒,二氧化钛与所述氢氧化钠的质量体积比为(1~20):200,单位为g/mL。
9.根据权利要求7所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法,其特征在于,所述盐酸溶液与所述氢氧化钠溶液的体积比为(1~50):1。
10.权利要求1-2任一项所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂或权利要求3-9任一项所述的负载双金属的二氧化钛纳米多孔陶瓷催化剂的制备方法制备得到的负载双金属的二氧化钛纳米多孔陶瓷催化剂应用于苯甲醇催化氧化制取苯甲醛或甲醇催化氧化制取甲醛等反应。
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