CN105879919B - Au/ZIF-8-TiO2催化剂及其制备方法与应用 - Google Patents
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Abstract
本发明公开了一种Au/ZIF‑8‑TiO2催化剂及其制备方法与应用，其是将自组装法制得的金属有机骨架材料ZIF‑8（类沸石咪唑酯骨架材料）加入到TiO2的前驱体中，制得ZIF‑8改性后的TiO2载体，而后通过沉积沉淀法，以Au纳米粒子为活性组分，将其分散在ZIF‑8改性后的TiO2载体表面，制得高分散的负载型Au催化剂Au/ZIF‑8‑TiO2。本发明中ZIF‑8的引入提高了所得催化剂可见光下催化氧化CO的活性，使该催化剂适用于空气或其他场合下CO的常温去除；且其制备方法简单易行，有利于推广应用。
Description
技术领域
本发明属于可见光催化氧化CO技术领域，具体涉及一种Au/ZIF-8-TiO2催化剂及其制备方法与应用。
背景技术
CO是典型的易燃、易爆、有毒气体，极易与血液中的血红蛋白（Hb）结合。当空气中含ppm级的CO时，就会引起人体中毒；当空气中CO含量达到400ppm时会使人出现头痛、疲倦、恶心等感觉；当含量达到600ppm时，人发生心悸亢进，并伴有虚脱；当含量大于1000ppm时，人便出现昏睡、痉挛，严重时将窒息而死。在当前研究最多的氢燃料电池中，微量的CO就会使催化剂和电极等中毒，其中最典型的就是质子膜交换燃料电池（PEMFC），在重整气中0.5-1.0 vol%CO就会使PEMFC电极中毒，必须将燃料气中的CO浓度降至100ppm以下。同样，在工业生产中，微量CO的存在能引起一些合成反应的催化剂中毒，对工业生产极为不利，如合成氨工业原料气中含有的微量CO就必须净化脱除。因此，如何高效的去除CO，已经成为当前的主要环境问题之一。
目前，最常用的CO去除方法有物理方法：深冷分离法、变压吸附法、膜分离法、溶剂吸收法等；化学脱除法：低温水煤气变换法、甲烷化法和催化氧化法等。但是由于CO的净化设备要求具有温度低、重量轻、体积小、操作方便、工艺简单、连续工作等特点，故物理净化方法不易采用；而低温水煤气变换反应法是将CO与水蒸汽反应转化为CO2并同时生成H2，其非常适合CO的脱除体系，但是该反应在低温条件下反应速率相对较慢，而且反应还受到热力学平衡的限制，难以达到将CO降到ppm级的要求，所以只适合用于CO浓度较高时的去除。CO甲烷化是一项比较成熟的工艺，但是在反应过程中会消耗掉大量的氢气（去除1摩尔CO要消耗3摩尔的H2），体系内部很可能发生逆水煤气变换反应。因此，研究低（常）温（<100 ℃）CO催化氧化，对消除CO的污染更具有实际意义。
当前，关于催化氧化CO研究最多的就是将活性组分贵金属（Pd, Au, Ag, Rh和Pt等）负载到一定的载体上（Al2O3, SiO2, TiO2等），对CO均表现出一定的催化氧化效果。其中，研究最多的就是Au/TiO2体系。研究发现，当金纳米颗粒高度分散在金属氧化物的载体表面时，不仅对CO的氧化具有极好的催化活性，而且具有良好的抗水性、稳定性和湿度增强效应；而TiO2因其具有合适的禁带宽度、高的光电转换效率、价廉等优势而在光催化氧化CO中受到广大研究者的钟爱。虽然Au/TiO2体系对CO表现出较好的催化氧化活性，但是由于存在稳定性差、易失活、选择性不是很高等缺点而受到限制。因此，如何实现在常温条件下提高Au催化剂高效、低成本的催化氧化CO，迄今为止仍然是研究的热点问题之一。
发明内容
本发明的目的在于提供一种Au/ZIF-8-TiO2催化剂及其制备方法与应用，其针对传统Au负载型催化剂需在较高温度下才能催化氧化CO的问题，通过引入多孔、大比表面积的ZIF-8作为助剂，对载体TiO2进行改性，加强了金属与载体间的相互作用，并使其在可见光区的吸收带边发生红移，以提高Au/TiO2在可见光下催化氧化CO的性能，从而提高此类催化剂的低温活性；且该催化剂制备方法简单易行，有利于推广应用。
为实现上述目的，本发明采用如下技术方案：
一种Au/ZIF-8-TiO2催化剂，是以Au纳米粒子为活性组分，将其均匀分散在经金属有机骨架材料ZIF-8（类沸石咪唑酯骨架材料）改性后的TiO2载体表面，形成的一种高分散负载型催化剂；所得催化剂中ZIF-8的含量为1.0~20.0wt%，Au的含量为0.1~5.0 wt%。
所述Au/ZIF-8-TiO2催化剂的制备方法包括以下步骤：
1）利用自组装法制备ZIF-8；
2）在TiO2的前驱体中加入ZIF-8，通过溶剂热反应，制得ZIF-8改性后的TiO2载体；
3）利用沉积沉淀法在步骤2）制得的ZIF-8改性后的TiO2载体表面负载Au纳米粒子，制得所述催化剂。
其具体操作为：将硝酸锌与2-甲基咪唑在甲醇溶剂中搅拌8~48h后，离心，洗涤，所得沉淀60~100℃真空烘干，得ZIF-8；将制得的ZIF-8加入到TiO2的前驱体溶液中，130~180℃溶剂热反应15~20h，而后离心、洗涤，60~100℃真空干燥，得到ZIF-8改性后的TiO2载体；将ZIF-8改性后的TiO2载体与HAuCl4溶液混合，得到的Au前驱体溶液，用0.5~1.5 mol/LNaOH溶液调节pH值为8~12，反应1h后用含NaOH的NaBH4溶液于室温下搅拌2~7 h进行还原反应，而后离心、洗涤，60~100℃干燥，即制得所述Au/ZIF-8-TiO2催化剂。
其中，所述HAuCl4溶液中Au浓度为0.005~0.02 g/mL；所述含NaOH的NaBH4溶液中，NaBH4的浓度为0.1~0.25 mol/L，NaOH的浓度为0.1~0.25 mol/L。
所得Au/ZIF-8-TiO2催化剂在可见光催化下，能够用于空气或其他场合中CO的常温去除。
本发明的显著优点在于：
（1）本发明以多孔、大比表面积的ZIF-8为助剂，对载体TiO2进行改性，有利于活性组分Au纳米粒子在载体表面的高度分散；同时，因为ZIF-8具有很强的光吸收，可使Au/TiO2在可见光区的吸收带边发生了红移，有利于提高该催化剂在可见光下光催化氧化CO的活性。
（2）ZIF-8与TiO2的结合实现了MOFs与半导体组合，有利于开发其他MOFs半导体材料在催化氧化CO方面的应用。
（3）本发明的制备方法简单易行，有利于推广应用。
附图说明
图1为实施例制得的Au/ZIF-8-TiO2催化剂的透射光谱图，其中，图A为Au纳米粒子在TiO2和ZIF-8中的分散情况，图B为Au和TiO2的晶格条纹。
图2为实施例和对比例1制得的TiO2(a)，Au/TiO2(b)，ZIF-8-TiO2(c)和Au/ZIF-8-TiO2(d)的X射线粉末衍射谱。
图3为实施例和对比例1制得的TiO2(a)，ZIF-8-TiO2(b)，Au/TiO2(c)，Au/ZIF-8-TiO2(d)和ZIF-8(e)的漫反射光谱图。
图4为实施例和对比例制得的Au/ZIF-8(a)，Au/TiO2(b)和Au/ZIF-8-TiO2(c)催化剂样品的光电流图。
图5为光照前后Au/TiO2，Au/ZIF-8-TiO2与Au/ZIF-8样品催化氧化CO性能的结果图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例 Au/ZIF-8-TiO2催化剂的制备
（1）将1.66g六水合硝酸锌与10.6g 2-甲基咪唑依次加入114mL的甲醇溶液中，室温下磁力搅拌48h，而后离心、洗涤，80℃真空干燥12h，得ZIF-8；
（2）将0.1g步骤（1）制得的ZIF-8加入到含14mL三氯化钛和1.68g NaOH的280mL乙醇溶液中，150℃溶剂热反应18h，然后离心、洗涤，80℃干燥12h，得ZIF-8-TiO2载体；
（3）将步骤（2）制得的载体和2 mL含Au浓度为0.01g/mL的HAuCl4溶液（1.0gHAuCl4·3H2O用去离子水溶解、定容至100mL）加入到100 mL水中，用0.1 mol/L NaOH调其pH值为10，搅拌反应1h后，用pH值为10的30mL含NaOH的0.1 mol/L NaBH4溶液于室温下搅拌反应7h进行还原处理，而后离心、洗涤，所得沉淀于80℃烘干，即得Au负载量为1.0 wt%的Au/ZIF-8-TiO2催化剂。
图1为所制得的Au/ZIF-8-TiO2催化剂的透射光谱图。由图1可以看出，ZIF-8成功的长在了TiO2表面上，而Au纳米粒子高度分散在载体表面上。
对比例1 Au/TiO2催化剂的制备
（1）将14mL三氯化钛和1.68g NaOH加入到280mL乙醇溶液中，150℃溶剂热反应18h，然后离心、洗涤，80℃干燥12h，得TiO2载体；
（2）将步骤（1）制得的载体和2 mL含Au浓度为0.01g/mL的HAuCl4溶液（1.0gHAuCl4·3H2O用去离子水溶解、定容至100mL）加入到100 mL水中，用0.5 mol/LNaOH调其pH值为10，搅拌反应1h后用pH值为10的30mL含NaOH的0.1 mol/L NaBH4溶液于室温下搅拌反应7h进行还原处理，而后离心、洗涤，所得沉淀于80℃烘干，即得Au负载量为1.0 wt%的Au/TiO2催化剂。
图2为实施例和对比例1制得的TiO2(a)，Au/TiO2(b)，ZIF-8-TiO2(c)和Au/ZIF-8-TiO2(d)的X射线粉末衍射谱。由图2对比可以看出，ZIF-8的加入和Au的负载并没有改变TiO2的晶型结构。
图3为实施例和对比例1制得的TiO2(a)，ZIF-8-TiO2(b)，Au/TiO2(c)，Au/ZIF-8-TiO2(d)和ZIF-8(e)的漫反射光谱图。由图3可以看出，ZIF-8的引入使Au催化剂在可见光区的吸收带边发生了红移，提高了对可见光的吸收，从而增强了可见光对Au/ZIF-8-TiO2催化氧化CO的促进作用。
对比例2 Au/ZIF-8催化剂的制备
（1）将1.66g六水合硝酸锌与10.6g 2-甲基咪唑依次加入114mL的甲醇溶液中，室温下磁力搅拌48h，而后离心、洗涤，80℃真空干燥12h，得ZIF-8；
（2）将制得的ZIF-8和2 mL含Au浓度为0.01g/mL的HAuCl4溶液（1.0g HAuCl4·3H2O用去离子水溶解、定容至100mL）加入到100 mL水中，用0.5 mol/LNaOH调其pH值为10，搅拌反应1h后用pH值为10的30mL含NaOH的0.1 mol/L NaBH4溶液于室温下搅拌反应7小时进行还原处理，而后离心、洗涤，所得沉淀于80℃烘干，即得Au负载量为1.0 wt%的Au/ZIF-8催化剂。
图4为实施例和对比例制得的Au/ZIF-8(a)，Au/TiO2(b)和Au/ZIF-8-TiO2(c)催化剂样品的光电流图。由图4可以看出，ZIF-8的加入有利于Au催化剂中光生载流子的分离。
催化剂的性能评价
催化剂催化氧化CO的性能评价采用常压连续流动装置进行测定。该常压连续流动装置包括带有进气口和出气口的石英玻璃反应器（长30mm×宽15mm×高1mm），石英玻璃反应器的内腔装填有催化剂，石英玻璃反应器周侧设置有循坏冷凝水装置（配热电偶检测）及用于激发Au产生等离子共振效应带的滤光片(490 nm-760 nm)和氙灯装置，所述氙灯装置发出的光能够透过石英玻璃反应器到达催化剂表面。
测定方法为：取0.5 g催化剂装填在石英玻璃反应器中，催化剂粒径为0.2~0.3 mm（60~80目），反应气中CO和O2的含量分别为0.3 V%及0.3 V%，氦气作为平衡补充气，反应气总流速为100 mL/min。反应温度由带循环冷凝水调控在25℃。采用Agilent 7890D型气相色谱仪定时在线分析气氛中CO、O2和CO2的浓度，检测器为TCD，填充柱为TDX-01，取反应6小时后的结果计算CO转化率，结果见图5。
CO转化率的计算公式为：C=（VinCO-VoutCO）/VinCO×100％，
式中，C为CO的转化率；VinCO和VoutCO分别为进气和出气中的CO含量（V%）。
图5为光照前后Au/TiO2，Au/ZIF-8-TiO2与Au/ZIF-8样品催化氧化CO性能的结果图。由图5结果显示，ZIF-8的引入有效提高了Au/TiO2光催化氧化CO的活性。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (5)
1.一种Au/ZIF-8-TiO2催化剂的制备方法，其特征在于：以Au纳米粒子为活性组分，将其均匀分散在经金属有机骨架材料ZIF-8改性后的TiO2载体表面，形成高分散负载型催化剂；其具体包括以下步骤：
1）利用自组装法制备ZIF-8，即将硝酸锌与2-甲基咪唑在甲醇溶剂中搅拌8~48h后，离心，洗涤，所得沉淀60~100℃真空烘干，得ZIF-8；
2）在TiO2的前驱体中加入ZIF-8，通过溶剂热反应，制得ZIF-8改性后的TiO2载体；
3）利用沉积沉淀法在步骤2）制得的ZIF-8改性后的TiO2载体表面负载Au纳米粒子，制得所述催化剂。
2. 根据权利要求1所述Au/ZIF-8-TiO2催化剂的制备方法，其特征在于：所得催化剂中ZIF-8的含量为1.0~20.0 wt%，Au的含量为0.1~5.0 wt%。
3.根据权利要求1所述Au/ZIF-8-TiO2催化剂的制备方法，其特征在于：步骤2）所述溶剂热反应是在130~180℃反应15~20h，而后离心、洗涤，60~100℃真空干燥，得到所述ZIF-8改性后的TiO2载体。
4. 根据权利要求1所述Au/ZIF-8-TiO2催化剂的制备方法，其特征在于：步骤3）所述沉积沉淀法是将ZIF-8改性后的TiO2载体与HAuCl4溶液混合，得到Au前驱体溶液，然后用NaOH溶液调节pH值为8~12，反应1h后用含NaOH的NaBH4溶液于室温下搅拌2~7 h进行还原反应，而后离心、洗涤，60~100℃干燥。
5. 根据权利要求4所述Au/ZIF-8-TiO2催化剂的制备方法，其特征在于：所述HAuCl4溶液中Au浓度为0.005~0.02 g/mL；
所述含NaOH的NaBH4溶液中，NaBH4的浓度为0.1~0.25 mol/L，NaOH的浓度为0.1~0.25mol/L。
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