CN112246264B - 一种碳化钼金属钼碳化硅三元复合材料、及其制备方法以及在光催化产氢上的作用 - Google Patents
一种碳化钼金属钼碳化硅三元复合材料、及其制备方法以及在光催化产氢上的作用 Download PDFInfo
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Abstract
本发明属于光催化材料技术领域，具体涉及一种碳化钼金属钼碳化硅三元复合材料、及其制备方法以及在光催化产氢上的作用。通过水热形成前驱体，然后通过H2氛围中还原形成Mo2C/Mo微米球；将Mo2C/Mo微米球颗粒和碳化硅分散于乙醇中，然后将乙醇蒸发，最后通过煅烧得到Mo2C/Mo@SiC复合材料。本发明通过简单水热煅烧合成了碳化钼金属钼碳化硅三元复合材料的光催化材料，制备原材料便宜易得，不含贵金属和污染环境的重金属，用于光解水制氢气，而氢气是高热能、无污染、可再生的能源。
Description
技术领域
本发明属于光催化材料技术领域，具体涉及一种碳化钼金属钼碳化硅三元复合材料、及其制备方法以及在光催化产氢上的作用。
背景技术
当今世界能源短缺与环境问题日益严峻，开发清洁能源迫在眉睫。氢能是公认的低碳和零碳能源一直备受瞩目。目前世界各国正在研究如何能大量而廉价的生产氢。利用太阳能光解水产氢是一个主要研究方向，在光的作用下将水分解成氢气和氧气，关键在于找到一种合适的催化剂。
半导体光催化剂就是可利用的材料之一。在半导体光催化分解水过程中，当光照波长等于或者大于半导体禁带宽度时，价带上的电子激发跃迁到导带，同时在价带上留下空穴，在经历过俘获和复合两个竞争的过程后，光致空穴具有很强的氧化性，光致电子具有很强的还原性，H2O分子被电子还原成H2，被空穴氧化成O2。除此，还需满足导带电势要比H+/H2 (0 V vs. NHE)还原电位更负，价带电势比H2O/O2的氧化电位(1.23 V)更正。SiC被公认是一种廉价又稳定且有前景的半导体光催化材，其可被可见光激发且导带电位很负（-1.10eV），足以把H2O还原到H2，实际中SiC光催化产氢效率并不完美，原因在于电子和空穴的分离效率低。贵金属或类金属负载被认为是提高光生电子空穴分离效率的手段之一。
我们发现目前的该类材料的合成大都存在一些问题，例如原料贵金属昂贵、合成过程复杂、合成条件苛刻。中国专利CN106268874A公开了一种金/硫化钼/氧化锌高效光催化制氢纳米材料及其制备方法，其结构为金纳米颗粒为核，硫化钼为壳，氧化锌纳米棒生长在硫化钼表面。但其合成制备过程较为复杂，而且成本相对较高，涉及到贵金属金；中国专利CN107715859A公开了一种石墨烯钙钛矿复合型光催化制氢催化剂的制备方法，包括：称取硝酸盐、钛酸四丁酯和络合剂溶解在乙醇溶液中，加入石墨烯悬浮液，配制出混合溶液；将所述混合溶液搅拌至变为干凝胶；将所述干凝胶焙烧除去有机物后进行真空煅烧，得到所述催化剂。该催化剂制备涉及到一些有机物，同时石墨烯制备较为困难，成本较高；中国专利CN108927222A公开了一种CdS-PAN/石墨烯复合纳米纤维的制备方法，但其制备方法比较复杂，反应条件比较苛刻，且反应中涉及到CdS，有重金属参与，不够环保，石墨烯制备较为困难，成本较高；中国专利CN101760272A公开了一种金属有机凝胶负载Pt的催化剂制备及其在光催化制氢上的应用，但其制备条件较为苛刻，而且Pt源成本比较高，反应过程中涉及有机物不够环保。
发明内容
针对现有技术的不足，本发明的目的在于提供一种碳化钼金属钼碳化硅三元复合材料、及其制备方法以及在光催化产氢上的作用。该制备方法实验条件较为简便，主要通过水热煅烧即可，而且制备过程中不涉及污染环境的物质，原料便宜易得。
为达此目的，本发明采用以下技术方案 ：
一种用于光催化产氢碳化钼金属钼碳化硅三元复合材料的制备方法，包括以下步骤：
1)将一定量的(NH4)6Mo7O24·4H2O与C6H6O6溶于去离子水中，充分搅拌混合均匀，制成混合溶液；
2)将混合溶液置于水热反应，冷却，再经过过滤、洗涤、干燥处理；
3)称取步骤2)所得样品研磨混合均匀，在氢气气氛下煅烧；
4)称取一定量的SiC和步骤3)所得样品超声分散于乙醇中；
5)将4)所得混合液室温搅拌，然后于一定条件下将乙醇蒸发；
6)将步骤5）所得样品于氩气条件下煅烧，获得Mo2C/Mo@SiC复合材料。
所述步骤1) (NH4)6Mo7O24·4H2O与C6H6O6物质的量之比12 ։ 7。
步骤2)所述水热温度为180℃，反应时间为12-24h，干燥处理为60℃下干燥。
步骤3)所述煅烧温度为850℃，氢气为含量为5vol%的氩氢混合气，升温速率为5℃/min，煅烧时间为3h。
步骤4)所述SiC加入量为200 mg，步骤3)所得样品加入量为2 mg至10 mg，超声分散时间为30 min。
步骤5)所述搅拌时间为24 h，真空烘箱蒸发，蒸发温度为60 ℃。
步骤6)煅烧时间为1h升温速率为5 ℃/min，煅烧温度300-500℃。
本发明提出在先水热形成前驱体，然后通过H2氛围中还原形成Mo2C/Mo微米球。然后将Mo2C/Mo纳米颗粒和一定量碳化硅分散于乙醇中，于一定温度下将乙醇蒸发，最后通过煅烧得到样品。
碳化钼金属钼碳化硅三元复合材料的光催化材料的光催化活性是通过在紫外灯照射下以甲醇为牺牲剂对水光解进行测试的。
碳化钼金属钼碳化硅三元复合材料的光催化材料的物理性能表征方法：用X射线衍射（XRD）光谱分析产物物质组成及结构情况，用场发射扫描电镜（FESEM）观察产物的形貌。
本发明的优点在于：该方案实验条件较为简便，主要通过水热煅烧即可，而且制备过程中不涉及污染环境的物质，原料便宜易得。
与现有技术相比，本发明的有益效果为：
本发明通过简单水热煅烧合成了碳化钼金属钼碳化硅三元复合材料的光催化材料，制备原材料便宜易得，不含贵金属，和污染环境的重金属，用于光解水制氢气，而氢气是高热能、无污染、可再生的能源。
附图说明
图1为实施例1合成方法所制得Mo2C/Mo产物的XRD谱图。
图2为实施例1合成方法所制得3% Mo2C/Mo@SiC复合材料的XRD谱图。
图3为实施例1合成方法所制得Mo2C/Mo纳米颗粒的SEM照片。
图4为实施例1合成方法所制得3% Mo2C/Mo@SiC复合材料的SEM照片。
图5为实施例1所得催化剂制氢效果图。
图6为实施例1紫外光催化水分解的反应器示意图。
图7为实施例1光解水反应装置图。
具体实施方式
下面结合实施例进一步说明本发明，该实例只用于说明本发明，并不限制本发明。
实施例1
在磁力搅拌下，将1 g (NH4)6Mo7O24·4H2O与93.5 mg C6H6O6一起溶解在50毫升去离子水中30分钟。随后，将混合物转移到不锈钢高压釜中，密封并保持在180℃12小时，冷却至室温，将湿沉淀物彻底洗涤并在真空炉中干燥。最后，得到的固体粉末在850℃氩气/氢气中处理3小时，得到Mo2C/Mo纳米粒子。将0.006 mg Mo2C/Mo纳米粒子和0.2 g SiC分散在20ml乙醇中。通过超声处理30min和连续搅拌24h获得均匀的溶液。随后，在80℃蒸发乙醇。真空管式炉中300℃加热1h，得到Mo2C/Mo与SiC质量比为3%的3%Mo2C/Mo@SiC的目标产物。使用相同的方法，获得了一系列杂化材料。
从Mo2C/Mo纳米粒子的XRD图（如图1）可以看出用这种方法合成的Mo2C/Mo纳米粒子具有较高的结晶度，其XRD图与标准卡片完全吻合，不含有其它杂质，从Mo2C/Mo纳米粒子的SEM图（如图3）可以看出其形貌均一，为直径20-60 nm的微米球。从3% Mo2C/Mo@SiC复合材料的XRD图（图2），可以看出用上述方案方法合成的Mo2C/Mo纳米粒子在复合前后两相的晶型并没有发生变化。从图4的3% Mo2C/Mo@SiC复合材料的SEM照片可以看出碳化硅纳米颗粒比较大，Mo2C/Mo纳米粒子能比较均匀地附着在碳化硅纳米颗粒上，形成复合结构。从所得催化剂制氢效果图（图5）可以看出，Mo2C/Mo纳米粒子与碳化硅复合后对SiC的制氢活性有所提升。当Mo2C/Mo的质量百比为3%时活性最优，产氢效率为235.2 µmol·g-1h-1，是SiC单一组分产氢速率（73.1µmol·g-1h-1）的3倍多，是同等条件下Pt/TiO2的1.5倍。
应用例1
光催化分解水实验，具体步骤如下：
所制备的一系列三元材料复合样品的光催化水分解活性测试是在如图6所示的反应装置中进行，其操作步骤如下：将20 mg的本发明制备的三元材料催化剂放在反应器中，随后再加入150 mL的水（有甲醇作为牺牲剂的反应：10 mL无水甲醇、150 mL H2O）。
然后将反应器用真空封脂将其密封，将其连接到光解水反应系统中，使用温度为5℃的循环冷凝水，用图7反应装置对体系进行抽真空处理，直至体系在真空状态下维持30min。最后用125 W的高压汞灯光源照射150 min后，每隔30 min进一次样，定量环内气体混合11 min，用FL9790气相色谱来检测反应体系的产氢量。整个反应过程都是保持在同一个搅拌速度（500 r/s）下进行的。
Claims (6)
1.一种碳化钼金属钼碳化硅三元复合材料的制备方法，其特征在于，通过水热形成前驱体，然后通过在H2氛围中还原形成Mo2C/Mo微米球；将Mo2C/Mo微米球颗粒和碳化硅分散于乙醇中，然后将乙醇蒸发，最后通过煅烧得到Mo2C/Mo@SiC复合材料；所述Mo2C/Mo微米球具体制备包括以下步骤：
1)将一定量的(NH4)6Mo7O24·4H2O与C6H6O6溶于去离子水中，充分搅拌混合均匀，制成混合溶液；
2)将混合溶液水热反应，冷却，再经过滤、洗涤、干燥处理；
3)称取步骤2)所得样品研磨混合均匀，在氢气气氛下煅烧，获得Mo2C/Mo微米球；
所述步骤1) (NH4)6Mo7O24·4H2O与C6H6O6物质的量之比12 ։ 7；
步骤2)所述水热温度为180 ℃，反应时间为12-24 h，干燥处理为60 ℃干燥；
步骤3)所述煅烧温度为850 ℃，氢气为含量为5 vol%的氩氢混合气，升温速率为5℃/min，煅烧时间为3 h。
2.根据权利要求1所述的一种碳化钼金属钼碳化硅三元复合材料的制备方法，其特征在于，将Mo2C/Mo微米球颗粒和碳化硅分散于乙醇中，然后将乙醇蒸发，其中所述SiC加入量为200 mg；Mo2C/Mo微米球颗粒加入量为2 mg至10 mg，超声分散时间为30 min。
3.根据权利要求1所述的一种碳化钼金属钼碳化硅三元复合材料的制备方法，其特征在于，将Mo2C/Mo微米球颗粒和碳化硅分散于乙醇中分散搅拌时间为24 h，将乙醇进行蒸发，使用真空烘箱蒸发，蒸发温度为60 ℃。
4.根据权利要求1所述的一种碳化钼金属钼碳化硅三元复合材料的制备方法，其特征在于，所述乙醇蒸发后，通过煅烧得到Mo2C/Mo@SiC复合材料，其中煅烧时间为1 h，升温速率为5 ℃/min，煅烧温度300-500℃。
5.一种如权利要求1-4任一项所述制备方法获得的碳化钼金属钼碳化硅三元复合材料。
6.一种如权利要求1-4任一项所述制备方法获得的碳化钼金属钼碳化硅三元复合材料在光催化产氢上的应用。
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