CN113351202A - 一种降解污染物的二氧化钛/钌单原子贵金属纳米催化材料其制备方法 - Google Patents
一种降解污染物的二氧化钛/钌单原子贵金属纳米催化材料其制备方法 Download PDFInfo
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Abstract
本发明公开了一种降解污染物的二氧化钛/钌单原子贵金属纳米催化材料及其制备方法,该制备方法以RuPc,2‑甲基咪唑和硝酸锌为前体制备出一种钌单原子金属材料,然后通过溶剂热处理将其与二氧化钛原位复合,最终制备出一种二氧化钛/钌单原子贵金属纳米催化材料,其展示出优异的光催化降解性能。
Description
技术领域
本发明涉及单原子金属催化剂以及光催化技术领域,特别是涉及一种降解污染物的二氧化钛/钌单原子贵金属纳米催化材料及其制备方法。
背景技术
在工业生产中,催化剂发挥着重要的作用,所以如何提高催化剂的化学转化效率来推动工业的发展一直是研究者们探索的重要工作。近年来,单原子催化剂(SACs)相关的研究被看作是催化领域的一个新的前沿方向。由于单原子催化剂具有独特的电子结构、丰富的表面和传质通道以及最大的原子利用效率,其表现出优异的催化活性和特定的催化位点。因此,单原子催化剂的独特性质致使其成为设计高效金属催化剂的候选材料,并被广泛开发用于光催化产氢以及污染物降解等领域。CN111013626A公开了一种基于针状焦的单原子金属石墨烯催化剂及其制备方法,该催化剂以氧化石墨烯为载体,通过金属盐与功能化石墨烯基团配位以及高温热解制得一种氮掺杂石墨烯负载的单原子金属催化剂,用于水处理降解污染物;该发明制备的功能化的石墨烯虽然具有大比表面积,可以增加其与单金属原子的锚定,但是在以氧化石墨烯为载体制备催化剂时,实际上存在剥离效果差、实验重复性差以及性质不稳定的问题,这并不适用于工业化应用。CN110292927A公开了一种单原子金属催化剂及其制备和在降解空气污染物中的应用,该发明通过热处理将二茂金属负载的介孔碳制成单原子金属催化剂,对空气污染物进行降解;虽然此制备方法较为简单,但所制得催化剂中的单原子金属负载量过低,且仅依靠单原子金属催化剂降解污染物降低了该催化剂对空气污染物的降解效果,使得该材料只能在较长的时间里完成对空气污染物的有效降解。
发明内容
本发明主要目的是为了解决上述问题,提供了一种降解污染物的二氧化钛/钌单原子贵金属纳米催化材料及其制备方法。本发明所采用的技术方案如下:
一种二氧化钛/钌单原子贵金属纳米催化材料的制备方法,包括如下步骤:
(1)在磁力搅拌下,将六水合硝酸锌和酞菁钌-4,4'联吡啶络合物(RuPc(bipy)2)溶于适量的甲醇,搅拌均匀;然后在高速搅拌下,加入2-甲基咪唑/甲醇液,配制成均一的溶液,搅拌12-24h;然后将获得的产物用甲醇清洗3-5次,再转移至真空干燥箱中干燥,即获得RuPc(bipy)2/ZIF-8前驱体;
(2)将步骤(1)制得的RuPc(bipy)2/ZIF-8前驱体转移到管式炉中,通入惰性气体,进行高温热解;待冷却至室温后,将获得的产物用4mol/L的硫酸浸泡并搅拌1-2h,用去离子水清洗,最后在70℃下真空干燥箱中干燥,即获得一种钌单原子金属材料(Ru SAs);
(3)将步骤(2)制备的Ru SAs分散在无水乙醇中,然后在磁力搅拌下,将钛酸异丙酯与Ru SAs/乙醇分散液混合搅拌10-20min,然后加入稀盐酸,持续搅拌0.5-1h,最后将其转移至反应釜中,进行溶剂热处理,待冷却到室温后,对产物进行洗涤、过滤、干燥,即获得一种二氧化钛/钌单原子贵金属纳米催化材料(TiO2/Ru SACs)。
优选地,步骤(1)中所述的六水合硝酸锌、酞菁钌-4,4'联吡啶络合物和甲醇的质量体积比为(0.5-2)g:(0.02-0.1)g:50mL。
优选地,步骤(1)所述的高速搅拌为在600-800rpm/min转速下搅拌。
优选地,步骤(1)所述的酞菁钌-4,4'联吡啶络合物与2-甲基咪唑的质量体积比为(0.01-0.05)g:20mL,其中2-甲基咪唑/甲醇液的浓度为0.2mol/L。
优选地,步骤(2)所述的高温热解为在800-1000℃下热解1-3h。
优选地,步骤(3)所述的钛酸异丙酯与Ru SAs/乙醇分散液的体积比为5:(1-8),其中Ru SAs/乙醇分散液的浓度为0.02-0.6g/L。
优选地,步骤(3)所述的溶剂热处理为在180-200℃加热6-12h。
根据上述方法制备得到的二氧化钛/钌单原子贵金属纳米催化材料,具有优异的光催化降解性能,可以应用于降解污染物。
与现有技术相比,本发明的技术方案具有如下有益效果:
(1)本发明提供了一种降解污染物的二氧化钛/钌单原子贵金属纳米催化材料的制备方法,该方法具有工艺简单,生产设备要求低,适于量产的特点,并且得到的产物性能卓越,具有优异的光催化降解性能,应用范围广。
(2)本发明制备的材料是一种复合二氧化钛的钌单原子贵金属纳米催化材料。其中单原子贵金属催化剂具有性质均一、催化活性高的特点,二氧化钛具有稳定的化学性质和物理结构,既作为氮原子贵金属的载体,同时也是一种良好的光催化剂。通过采用溶剂热的方法实现两种组分的均匀复合,金属原子和二氧化钛载体以最大程度进行接触,保留了两种组分各自的优点,实现了其催化性能的高效合作和较高的结构稳定性,因而得到的产物在催化中占有极大地优势,能够大幅度提升污染物的光催化降解性能。
附图说明
图1为实施例1制备的Ru-SAs透射电镜图(TEM)。
图2为实施例1制备的TiO2/Ru-SACs扫描电镜图(SEM)
图3为实施例1-2和对比例1制备材料对染液降解的性能图。
具体实施方式
为能进一步了解本发明的发明内容、特征及其优点,通过以下实施例以及对比例来进一步阐述。
实施例1
本发明实施例1提供了一种降解污染物的二氧化钛/钌单原子贵金属纳米催化材料及其制备方法,其具体步骤如下:
(1)在磁力搅拌下,将1g六水合硝酸锌和0.1g酞菁钌-4,4'联吡啶络合物(RuPc(bipy)2)溶于50mL甲醇,搅拌均匀;然后在700rpm/min的转速下搅拌24h,再加入20mL 2-甲基咪唑/甲醇液,配制成均一的溶液,搅拌24h;然后将获得的产物用甲醇清洗5次,再转移至真空干燥箱中干燥,即获得RuPc(bipy)2/ZIF-8前驱体;
(2)将步骤(1)制得的RuPc(bipy)2/ZIF-8前驱体转移到管式炉中,通入惰性气体,在900℃下热解5h;待冷却至室温后,将获得的产物用4mol/L的硫酸浸泡及清洗,最后在70℃下真空干燥箱中过夜干燥,即获得一种钌单原子贵金属材料(Ru SAs);
(3)将步骤(2)制备的Ru SAs分散在50mL无水乙醇中,然后在磁力搅拌下,将10mL钛酸异丙酯与10mL,0.4g/L的Ru SAs/乙醇分散液混合搅拌20min,然后加入稀盐酸,持续搅拌1h,最后将其转移至反应釜中,在180℃下进行12h的溶剂热处理,待冷却到室温后,对产物进行洗涤、过滤、干燥,即可获得一种二氧化钛/钌单原子贵金属纳米催化材料(TiO2/RuSACs)。
我们还对以RuPc,2-甲基咪唑和硝酸锌为前体制备的Ru-SAs以及复合二氧化钛后的TiO2/Ru SACs进行了表征。图1显示了Ru-SAs的TEM,制备的Ru-SAs的平均尺寸约为95nm,具有与ZIF-8类似的十二面体结构;图2显示了TiO2/Ru SACs的SEM,其与Ru-SAs呈相似的结构。
实施例2
本发明实施例2提供了一种降解污染物的二氧化钛/钌单原子贵金属纳米催化材料及其制备方法,其具体步骤如下:
(1)在磁力搅拌下,将2g六水合硝酸锌和0.05g酞菁钌-4,4'联吡啶络合物(RuPc(bipy)2)溶于50mL甲醇,搅拌均匀;然后在700rpm/min的转速下搅拌24h,再加入20mL 2-甲基咪唑/甲醇液,配制成均一的溶液,搅拌24h;然后将获得的产物用甲醇清洗5次,再转移至真空干燥箱中干燥,即获得RuPc(bipy)2/ZIF-8前驱体;
(2)将步骤(1)制得的RuPc(bipy)2/ZIF-8前驱体转移到管式炉中,通入惰性气体,在900℃下热解5h;待冷却至室温后,将获得的产物用4mol/L的硫酸浸泡及清洗,最后在70℃下真空干燥箱中过夜干燥,即获得一种钌单原子贵金属材料(Ru SAs);
(3)将步骤(2)制备的Ru SAs分散在50mL无水乙醇中,然后在磁力搅拌下,将10mL钛酸异丙酯与5mL,0.2g/L的Ru SAs/乙醇分散液混合搅拌20min,然后加入稀盐酸,持续搅拌1h,最后将其转移至反应釜中,在180℃下进行12h的溶剂热处理,待冷却到室温后,对产物进行洗涤、过滤、干燥,即可获得一种二氧化钛/钌单原子贵金属纳米催化材料(TiO2/RuSACs)。
对比例1
本发明对比例1与实施例1的区别在于未与二氧化钛复合,即仅制备出一种钌单原子纳米催化材料(Ru SACs)。
罗丹明B染液降解测试:
配制浓度为10-4mol/L的罗丹明B染液作为降解试液;采用上述实施例1-2和对比例1所制备的材料作为光催化剂;采用300W的氙灯作为光源;然后辅以磁力搅拌器、转子以及可密封遮光的烧杯一起开展实验,其具体测试步骤如下:
(1)取50mg光催化剂分散于10-4mol/L的罗丹明B染液,倒入密封遮光的烧杯中,超声分散5min;然后将烧杯取出,在下方固定好磁力搅拌器,以450rpm/min的转速进行搅拌;并在上方固定好氙灯,使反应液界面与氙灯光源的垂直距离保持在12cm;然后在匀速搅拌下,进行0.5h的暗室吸附过程;
(2)在450rpm/min的转速下持续搅拌,将氙灯开关打开,然后每隔6min用移液枪取1.5mL染液,再经离心取上清液进行紫外吸光度检测;
(3)设置紫外分光光度计的吸收光范围为200-800nm,然后以去离子水为参比样品,将其与上述采样后的离心染液一同放入紫外分光光度计中进行测试;即可得到一系列罗丹明B溶液的吸收峰,然后将最高峰吸收波长处(554nm)的吸光度记录下来,即可得到如图3所示的罗丹明B染液降解曲线。
如图3所示,对比例1制备的二氧化钛催化材料对染液具有优异的降解性能,可在36min里降解85%左右;然而实施例1-2制备的TiO2/Ru SACs对罗丹明B染液具有更为优异的降解效率,可在24min内将染液降解近85%,可在30min里将染液完全降解,这体现出复合催化剂的优势。
本发明所列举的各种原料,以及本发明各原料的上下区间取值,以及工艺参数(如温度、时间等)的上下区间取值都能实现本发明,在此不一一列举实施例。以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些都属于本发明的保护范围。这些改进和变动也视为本发明的保护范围。
Claims (7)
1.一种二氧化钛/钌单原子贵金属纳米催化材料的制备方法,其特征在于,所述制备方法包括如下步骤:
(1)在磁力搅拌下,将六水合硝酸锌和酞菁钌-4,4'联吡啶络合物(RuPc(bipy)2)溶于适量的甲醇,搅拌均匀;然后在高速搅拌下,加入2-甲基咪唑/甲醇液,配制成均一的溶液,搅拌12-24h;然后将获得的产物用甲醇清洗3-5次,再转移至真空干燥箱中干燥,即获得RuPc(bipy)2/ZIF-8前驱体;
(2)将步骤(1)制得的RuPc(bipy)2/ZIF-8前驱体转移到管式炉中,通入惰性气体,进行高温热解;待冷却至室温后,将获得的产物用4mol/L的硫酸浸泡及清洗以去除未反应的钌纳米粒子,最后在70℃下真空干燥箱中过夜干燥,即获得一种钌单原子金属材料(Ru SAs);
(3)将步骤(2)制备的Ru SAs分散在无水乙醇中,然后在磁力搅拌下,将钛酸异丙酯与Ru SAs/乙醇分散液混合搅拌10-20min,然后加入稀盐酸,持续搅拌0.5-1h,最后将其转移至反应釜中,进行溶剂热处理,待冷却到室温后,对产物进行洗涤、过滤、干燥,即可获得一种二氧化钛/钌单原子贵金属纳米催化材料(TiO2/Ru SACs)。
2.根据权利要求1所述的一种二氧化钛/钌单原子贵金属纳米催化材料的制备方法,其特征在于,步骤(1)中所述的六水合硝酸锌、酞菁钌-4,4'联吡啶络合物和甲醇的质量体积比为(0.5-2)g:(0.02-0.1)g:50mL。
3.根据权利要求1所述的一种二氧化钛/钌单原子贵金属纳米催化材料的制备方法,其特征在于,步骤(1)所述的高速搅拌为在600-800rpm/min转速下搅拌12-24h。
4.根据权利要求1所述的一种二氧化钛/钌单原子贵金属纳米催化材料的制备方法,其特征在于,步骤(1)所述的酞菁钌-4,4'联吡啶络合物与2-甲基咪唑的质量体积比为(0.01-0.05)g:20mL,其中2-甲基咪唑/甲醇液的浓度为0.2mol/L。
5.根据权利要求1所述的一种二氧化钛/钌单原子贵金属纳米催化材料的制备方法,其特征在于,步骤(2)所述的高温热解为在800-1000℃下热解1-3h。
6.根据权利要求1所述的一种二氧化钛/钌单原子贵金属纳米催化材料的制备方法,其特征在于,步骤(3)所述的钛酸异丙酯与Ru SAs/乙醇分散液的体积比为5:(1-8),其中RuSAs/乙醇分散液的浓度为0.02-0.6g/L。
7.根据权利要求1所述的一种二氧化钛/钌单原子贵金属纳米催化材料的制备方法,其特征在于,步骤(3)所述的溶剂热处理为在180-200℃加热6-12h。
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