CN107349937B - 一种石墨烯基双金属硫化物纳米复合光催化剂的制备方法 - Google Patents
一种石墨烯基双金属硫化物纳米复合光催化剂的制备方法 Download PDFInfo
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- CN107349937B CN107349937B CN201710508676.5A CN201710508676A CN107349937B CN 107349937 B CN107349937 B CN 107349937B CN 201710508676 A CN201710508676 A CN 201710508676A CN 107349937 B CN107349937 B CN 107349937B
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Abstract
本发明公开了一种石墨烯基双金属硫化物纳米复合光催化剂的制备方法，通过简单温和的一步水热法合成一系列的石墨烯基双金属硫化物复合光催化剂，通过控制水热反应温度、反应时间、石墨烯添加量和金属盐化合物在复合体系中的含量来调控双金属硫化物的形貌尺寸大小和在石墨烯表面的取向生长；此外，本发明所述的制备方法工艺操作简单，原料价格低廉，适合规模化工业生产。
Description
技术领域
本发明属于光催化技术领域，具体涉及一种以石墨烯为载体的双金属硫化物纳米复合光催化剂及其制备方法与光催化水解制氢应用。
背景技术
环境污染和能源短缺已成为21世纪人类社会面临的严峻挑战。因此，开发利用一种新型的、无污染的，且经济的可再生能源对人类社会可持续发展有着深远意义。氢气是一种超清洁二次能源，具有能量密度高、可再生、无污染、可储存、可运输等优点。此外，氢气作为一种重要的化工原料和工业保护气体，广泛应用在冶金工业、精细有机合成、航空航天、石油化工行业等。而目前氢能的来源主要为水煤气转化、烃类裂解、电解水制氢等，这些方法消耗了大量的不可再生资源，而且还造成了污染。氢能的经济、绿色生产成为一种迫切的技术需求。自1972年，日本学者Fujishima和Honda成功利用TiO2光阳极材料将水催化分解成H2和O2以来，太阳能光催化分解水制氢已成为当前最具应用前景的制氢技术之一，具有极大的社会经济价值。因此，大力发展高性能、低成本、绿色环保的太阳能光催化材料是目前太阳能光催化分解水制氢技术领域亟待解决的关键课题之一。在过去的近半个世纪里，人们开发出了多种具有产氢活性的氧化物、硫化物、磷化物、卤化物以及氮化物等半导体光催化材料。然而，由于这些半导体材料自身存在的物理化学性质的缺陷，如：材料本身禁带宽度较大、光生电子-空穴对易复合以及催化剂难以回收等，致使半导体光催化材料催化剂难以有效利用太阳光且光催化水解制氢活性不高，进而限制了其在大规模工业生产中的实际应用。因此，实现光催化水解制氢的规模化工业应用的关键在于开发获得具有高太阳光利用率和高光量子转化效率的新型光催化剂。
在众多的半导体催化材料中，硫化物，特别是CdS，成为研究最为广泛的光催化剂。由于其较窄的禁带宽度，在可见光照射下，CdS具有较高的制氢活性。但是其在光解水制氢反应过程中极易发生光腐蚀和自氧化反应现象，进而导致整个光催化体系的活性及稳定性不高，极大地限制了CdS的在光水解制氢领域的应用。通过深入探索半导体光催化材料水解制氢的反应机理和影响催化活性的内在因素，人们已经发现了多种有效途径解决上述限制光催化效率提高的瓶颈问题，包括单一离子掺杂或者共掺杂，基于能带理论的半导体复合，表面光敏化和负载贵金属助催化剂，其目的是构建具有窄带隙的复合半导体光催化材料，实现光生生电子-空穴对的有效分离且在催化剂表面形成大量的反应活性中心，最终提高催化剂的光解水制氢催化活性。然而，综合大量文献报道表明，基于上述改进方法合成的硫化物半导体光催化剂并未表现出显著的光催化分解水制氢活性。此外，由于大量贵金属助催化剂如Pt、Au等的使用，反而加大了硫化物半导体光催化剂的制备成本，不利于规模化工业应用。
因此，将多组分半导体纳米材料与石墨烯复合是提高光催化剂可见光区光催化水解制氢的有效策略之一。这是由于石墨烯不仅具有更为优良的导电和导热等性能，其表面存在众多的含氧基团及缺陷不仅会带来许多化学活性位点，也会为金属离子提供锚定位点；此外，石墨烯在光催化剂体系中可起到结构支撑和导电通道作用，进而极大提高了光催化系统中光生电荷的定向分离和传输效率。最后，石墨烯大的比表面积和良好的稳定性还可有效提高催化剂的光吸收效率和使用寿命。
发明内容
本发明的目的之一是以导电性能优良的二维材料石墨烯为基底，在其表面原位生长双金属硫化物，进而构筑石墨烯基双金属硫化物纳米复合光催化剂。通过耦合石墨烯的大比表面积和高导电率，不同维度的异质结材料的高载流子迁移率以强光子捕获和吸收能力，建立光生载流子高速传输的纳米通道，进而构筑新型高效的光催化体系，实现该体系光生电荷分离效率和可见光区量子效率的显著提高。
本发明的目的之二是提供了一种简单、温和、高效且适合规模化生产的石墨烯基双金属硫化物纳米复合光催化剂制备方法。与现有石墨烯基催化剂制备方法相比，反应温度较低，反应时间短，双金属硫化物均匀分散在石墨烯表面且尺寸大小可调，整个合成过程绿色可控。此外，本发明使用廉价的非贵金属硫化物代替贵金属pt、Au等，在大幅度降低催化剂生产成本的同时，也显著提高了光催化剂的光解水制氢催化活性。此外，本发明所制备的石墨烯基双金属硫化物复合光催化剂展示出优异的循环使用性能，具有潜在的商业化开发前景。
本发明一种石墨烯基双金属硫化物纳米复合光催化剂的制备方法，包括以下步骤：
步骤一，首先采用改性的Hummer's方法制备出氧化石墨粉末，再称取0.1-1.0g的上述氧化石墨粉末分散到水中，配制成浓度为1-10mg·mL-1的氧化石墨溶液，通过超声剥离方法制备均匀分散的氧化石墨烯(GO)纳米片悬浮液，其中，超声波功率为100-800W，超声时间为2-8h；
步骤二，将双金属硫化物的金属盐前驱体：锡盐化合物和镉盐化合物(或钼盐化合物和镉盐化合物；或镍盐化合物、锌盐化合物和镉盐化合物)按照一定的摩尔比分别加入到60mL去离子水中；再量取1-10mL的GO水溶液滴加到上述混合金属盐水溶液中，超声分散均匀，形成混合溶液A；之后，向上述混合溶液A中分别加入0-0.6mg的一水合柠檬酸、0-0.8mg的无水葡萄糖，0-1mg的聚乙烯吡咯烷酮和0-0.6mg的十六烷基三甲基溴化铵，形成混合溶液B；最后，将混合溶液B在常温下磁力搅拌6小时，待用；
其中，步骤二中所述的双金属硫化物的金属盐前驱体镉盐化合物和锡盐化合物的摩尔比范围为6～1:3；钼盐化合物和镉盐化合物的摩尔比范围为0.01～0.3:1；镍盐化合物、锌盐化合物和镉盐化合物的摩尔比范围为0.05～1:1:4。
步骤三，称取1.0-8.0mmoL的L-半胱氨酸加入步骤二中的混合溶液B中，超声溶解，形成混合溶液C并在常温下磁力搅拌1h；之后将混合溶液C转移至100mL内衬为聚四氟乙烯的不锈钢反应釜中，在120-220℃下水热反应1-20h，待反应终止且反应温度自然冷却至室温，将得到的相应石墨烯基双金属硫化物纳米复合光催化剂在转速为4000r/min离心机上离心5min，并分别用水和乙醇对产物进行多次洗涤，将离心洗涤分离后的产物在60℃下干燥24h，最终得到相应的石墨烯基双金属硫化物纳米复合光催化剂。
步骤四，称取0.05g步骤三中合成的石墨烯基双金属硫化物复合光催化剂超声分散到50mL水中，再加入5-20mL的有机酸或有机胺作为空穴牺牲剂，氮气吹扫5min；以300W的氙灯作为光源，同时采用滤光片过滤掉波长小于420nm的紫外光和远紫外光，进行可见光催化分解水制氢反应，采用气相色谱仪检测氢气生成量。
其中，有机酸可为乳酸、苹果酸或者柠檬酸中的任意一种，而有机胺可为二乙醇胺、正丙醇胺或三乙醇胺中的任意一种；并且空穴牺牲剂的加入量与水的体积比范围为0.1～0.5:1。
本发明与现有技术相比具有以下优点：
(1)石墨烯基双金属硫化物纳米复合光催化剂的制备方法简单有效且具有普适性。通过简单温和的一步水热法合成一系列的石墨烯基双金属硫化物复合光催化剂，通过控制水热反应温度、反应时间、石墨烯添加量和金属盐化合物在复合体系中的含量来调控双金属硫化物的形貌尺寸大小和在石墨烯表面的取向生长；此外，本发明所述的制备方法工艺操作简单，原料价格低廉，适合规模化工业生产；
(2)石墨烯基双金属硫化物纳米复合光催化剂的设计思路合理新颖。本发明结合当前的光催化水解制氢的研究热点和难点问题，从半导体能带理论出发，以晶体学理论为切入点，以具有大比表面积和高导电率且富含含氧官能团的GO为导电基底和电子传输通道，在其表面锚定生长均匀分散的双金属硫化物复合光催化剂。光吸收活性中心产生的光激发电子可经电子传输通道石墨烯转最终移到电子受体，实现光生电子-空穴对的空间分离和转移，最大限度的提高复合催化剂的光水解制氢活性；此外，该策略抑制了金属硫化物在反应过程中的团聚和光腐蚀现象，确保石墨烯基双金属硫化物复合光催化剂的结构稳定性和高效的催化循环活性；
(3)通过引入少量的非贵金属硫化物(如：Sn2S3，NiS，Ni3S4，Ni7S6，MoS2和ZnS等)取代常用的贵金属Pt，Au等作为助催化剂，不仅提高了催化剂的光催化性能，在一定程度上大大节约了催化剂的制备成本，有利于该系列产品实现规模化光解水制氢实际应用。
附图说明
图1(a)是本发明制备的Sn2S3-CdS/rGO复合纳米薄片光催化剂的SEM图；
图1(b)是本发明制备的Sn2S3-CdS/rGO复合纳米薄片光催化剂的TEM图；
图2是本发明水热法制备的纯Sn2S3、纯CdS和Sn2S3-CdS/rGO复合纳米薄片光催化剂的XRD图；
图3(a)是本发明水热法制备催化剂样品的可见光水解制氢速率图(λ>420nm)；
图3(b)是本发明制备的Sn2S3-CdS/rGO复合纳米薄片可见光水解制氢循环活性图(λ>420nm)；
图4(a)是本发明制备的NiSx/Cd0.8Zn0.2S/rGO复合纳米薄片的SEM图；
图4(b)是本发明制备的NiSx/Cd0.8Zn0.2S/rGO复合纳米薄片的TEM图；
图5(a)是本发明水热法制备的NiSx/rGO样品的XRD图；
图5(b)是本发明水热法制备的NiSx/Cd0.8Zn0.2S/rGO样品的XRD图；
图5(c)是本发明水热法制备的Cd0.8Zn0.2S样品XRD图；
图6(a)是本发明水热法制备催化剂样品的可见光水解制氢速率图(λ>420nm)；
图6(b)是本发明制备的NiSx/Cd0.8Zn0.2S/rGO复合纳米薄片可见光水解制氢循环活性图(λ>420nm)；
图7(a)是本发明制备的MoS2/CdS/rGO复合纳米薄片催化剂的SEM图；
图7(b)是本发明制备的MoS2/CdS/rGO复合纳米薄片催化剂的TEM图；
图8(a)是本发明水热法制备的MoS2/CdS/rGO样品的XRD图；
图8(b)是本发明水热法制备的纯CdS样品的XRD图；
图8(c)是本发明水热法制备的纯MoS2样品XRD图；
图9(a)是本发明水热法制备催化剂样品的可见光水解制氢活性图(λ>420nm)；
图9(b)是本发明制备的MoS2/CdS/rGO复合纳米薄片可见光水解制氢循环活性图(λ>420nm).
具体实施方式
下面通过实施例进一步详细说明石墨烯基双金属硫化物纳米复合光催化剂的制备方法。但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
(1)称取60mg干燥的氧化石墨粉末超声分散至20mL去离子水中，采用功率为800W的超声破碎仪超声4h，制得浓度为3mg·mL-1的氧化石墨烯水溶液；
(2)分别称取0.2g葡萄糖、0.11g五水合四氯化锡和0.24g 2.5水合氯化镉置于洁净的100mL小烧杯中，再向其中加入60mL去离子水中，超声溶解，形成混合溶液A；之后，向上述混合溶液A中加入4mL 3mg·mL-1的氧化石墨烯水溶液，常温下磁力搅拌4h，形成混合溶液B；
(3)称取0.56g的L-半胱氨酸加入到上述的混合溶液B中，超声溶解，形成混合溶液C并在常温下磁力搅拌1h；之后将混合溶液C转移至100mL内衬为聚四氟乙烯的不锈钢反应釜中，在180℃下水热反应2h。待反应终止且反应温度自然冷却至室温，将得到的沉淀物在转速为4000r/min离心机上离心5min，并分别用水和乙醇对产物进行多次洗涤，将离心洗涤分离后的产物在60℃下干燥24h，最终得到Sn2S3-CdS/rGO复合纳米薄片光催化剂；
(4)称取0.05g步骤(3)中合成的Sn2S3-CdS/rGO复合纳米薄片光催化剂超声分散至50mL水中，再向上述悬浊液中分别加入5mL的乳酸和质量分数为3.0％的Pt作为空穴牺牲剂和助催化剂；氮气吹扫5min，以300W的氙灯作为光源，同时采用滤光片过滤掉波长小于420nm的紫外光和远紫外光，进行可见光催化分解水制氢反应，采用气相色谱仪检测氢气生成量。
图1显示合成的“岛状”Sn2S3-CdS共生纳米晶体均匀分散在还原氧化石墨烯(rGO)纳米薄片表面，Sn2S3-CdS共生纳米晶体的尺寸大小在16.7nm到27.8nm之间。
图2XRD图谱显示制备的样品高度结晶，且合成的CdS为六方晶相，而Sn2S3为斜方晶相。此外，该图也进一步表明通过简单的一锅水热法成功合成了Sn2S3-CdS/rGO复合纳米薄片光催化剂。
图3a表明：与纯Sn2S3、Sn2S3/rGO以及CdS/rGO复合纳米材料相比，合成的Sn2S3-CdS/rGO复合纳米薄片光催化剂具有最高的可见光催化分解水制氢能力，可见光照射6h，其产氢量高达994.4μmol·g-1。此外，由图3b可以看出Sn2S3-CdS/rGO复合纳米薄片具有持续增加的制氢循环活性，可见光照射60h，其产氢速率仍高达1671μmol·h-1·g-1，表明Sn2S3-CdS/rGO复合纳米薄片具有优良的可见光催化水解制氢性能和高的稳定性。
实施例2
(1)称取60mg干燥的氧化石墨粉末超声分散至20mL去离子水中，采用功率为520W的超声破碎仪超声6h，制得浓度为3mg·mL-1的氧化石墨烯水溶液；
(2)分别称取0.2g葡萄糖、0.01g六水合硝酸镍、0.06g六水合硝酸锌和0.18g 2.5水合氯化镉置于洁净的100mL小烧杯中，再向其中加入60mL去离子水中，超声溶解，形成混合溶液A；之后，向上述混合溶液A中加入5mL 3mg·mL-1的氧化石墨烯水溶液，常温下磁力搅拌6h，形成混合溶液B；
(3)称取0.54g的L-半胱氨酸加入到上述的混合溶液B中，超声溶解，形成混合溶液C并在常温下磁力搅拌1h；之后将混合溶液C转移至100mL内衬为聚四氟乙烯的不锈钢反应釜中，在160℃下水热反应2h。待反应终止且反应温度自然冷却至室温，将得到的沉淀物在转速为4000r/min离心机上离心5min，并分别用水和乙醇对产物进行多次洗涤，将离心洗涤分离后的产物在60℃下干燥24h，最终得到NiSx/Cd0.8Zn0.2S/rGO复合纳米薄片光催化剂；
(4)称取0.05g步骤(3)中合成的NiSx/Cd0.8Zn0.2S/rGO复合纳米薄片光催化剂超声分散至50mL水中，再向上述悬浊液中分别加入5mL的乳酸作为空穴牺牲剂；氮气吹扫5min，以300W的氙灯作为光源，同时采用滤光片过滤掉波长小于420nm的紫外光和远紫外光，进行可见光催化分解水制氢反应，采用气相色谱仪检测氢气生成量。
图4显示合成的零维NiSx/Cd0.8Zn0.2S复合纳米微球牢固的锚定在还原氧化石墨烯(rGO)纳米薄片表面，NiSx/Cd0.8Zn0.2S复合纳米微球尺寸均一且分散性好，微球尺寸大小在30nm到60nm之间。
图5XRD图谱显示制备的样品高度结晶，且合成的Cd0.8Zn0.2S为六方晶相，而NiSx包含立方晶相Ni3S4和斜方晶相Ni7S6。此外，该图也进一步表明通过简单的一锅水热法成功合成了三元NiSx/Cd0.8Zn0.2S/rGO复合纳米薄片光催化剂。
图6表明：与纯NiSx、Cd0.8Zn0.2S、NiSx/rGO和Cd0.8Zn0.2S/rGO相比较，NiSx/Cd0.8Zn0.2S/rGO复合纳米薄片光催化剂具有最高的可见光催化分解水制氢能力，可见光照射5h，其产氢速率高达7.84mmol·h-1·g-1，明显高于Cd0.8Zn0.2S/rGO+Pt催化剂的产氢速率(5.84mmol·h-1·g-1)，表明助催化剂NiSx完全可以替代贵金属Pt。同时，NiSx/Cd0.8Zn0.2S/rGO复合纳米薄片光催化剂具有稳定的可见光催化水解制氢性能，可见光照射25h，产氢量仍高达36.79mmol·g-1。
实施例3
(1)称取60mg干燥的氧化石墨粉末超声分散至20mL去离子水中，采用功率为520W的超声破碎仪超声6h，制得浓度为3mg·mL-1的氧化石墨烯水溶液；
(2)分别称取0.2g葡萄糖、0.2g一水合柠檬酸、0.2g十六烷基三甲基溴化铵、0.072g二水合钼酸钠和0.46g 2.5水合氯化镉置于洁净的100mL小烧杯中，再向其中加入60mL去离子水中，超声溶解，形成混合溶液A；之后，向上述混合溶液A中加入3mL 3mg·mL-1的氧化石墨烯水溶液，常温下磁力搅拌4h，形成混合溶液B；
(3)称取0.54g的L-半胱氨酸加入到上述的混合溶液B中，超声溶解，形成混合溶液C并在常温下磁力搅拌1h；之后将混合溶液C转移至100mL内衬为聚四氟乙烯的不锈钢反应釜中，在200℃下水热反应12h。待反应终止且反应温度自然冷却至室温，将得到的沉淀物在转速为4000r/min离心机上离心5min，并分别用水和乙醇对产物进行多次洗涤，将离心洗涤分离后的产物在60℃下干燥24h，最终得到MoS2/CdS/rGO复合纳米薄片光催化剂；
(4)称取0.05g步骤(3)中合成的MoS2/CdS/rGO复合纳米薄片光催化剂超声分散至50mL水中，再向上述悬浊液中分别加入5mL的乳酸作为空穴牺牲剂和助催化剂；氮气吹扫5min，以300W的氙灯作为光源，同时采用滤光片过滤掉波长小于420nm的紫外光和远紫外光，进行可见光催化分解水制氢反应，采用气相色谱仪检测氢气生成量。
图7显示合成的零维MoS2/CdS复合纳米微球牢固的锚定在还原氧化石墨烯(rGO)纳米薄片表面，MoS2/CdS复合纳米微球尺寸均一且分散性好，微球尺寸大小在125nm到235nm之间。
图8XRD图谱显示制备的样品高度结晶，且合成的CdS为立方晶相，而助催化剂MoS2为斜方晶相。此外，该图也进一步表明通过简单的一锅水热法成功合成了三元MoS2/CdS/rGO复合纳米薄片光催化剂。
图9表明：与纯MoS2、CdS相比较，MoS2/CdS/rGO复合纳米薄片光催化剂具有最高的可见光催化分解水制氢能力，可见光照射5h，其产氢量高达8.1mmol·g-1。同时，MoS2/CdS/rGO复合纳米薄片光催化剂具有稳定的可见光催化水解制氢性能，可见光照射30h，产氢量仍高达7.7mmol·g-1。
Claims (3)
1.一种石墨烯基双金属硫化物纳米复合光催化剂的制备方法，其特征在于，制备步骤如下：
(1)首先采用改性的Hummer's方法制备出氧化石墨粉末，再称取0.1-1.0g的上述氧化石墨粉末分散到水中，配制成浓度为1-10mg﹒mL-1的氧化石墨溶液，通过超声剥离方法制备均匀分散的氧化石墨烯纳米片悬浮液，其中，超声波功率为100-800W，超声时间为2-8h；
(2)将双金属硫化物的金属盐前驱体：锡盐化合物和镉盐化合物；或钼盐化合物和镉盐化合物；或镍盐化合物、锌盐化合物和镉盐化合物按照摩尔比分别加入到60mL去离子水中；再量取1-10mL的氧化石墨烯水溶液滴加到混合金属盐水溶液中，超声分散均匀，形成混合溶液A；之后，向混合溶液A中分别加入0-0.6mg的一水合柠檬酸、0-0.8mg的无水葡萄糖，0-1mg的聚乙烯吡咯烷酮和0-0.6mg的十六烷基三甲基溴化铵，形成混合溶液B；最后，将混合溶液B在常温下磁力搅拌6小时，待用；双金属硫化物的金属盐前驱体镉盐化合物和锡盐化合物的摩尔比为6～1:3；钼盐化合物和镉盐化合物的摩尔比为0.01～0.3:1；镍盐化合物、锌盐化合物和镉盐化合物的摩尔比为0.05～1:1:4；
(3)称取1.0-8.0mmoL的L-半胱氨酸加入步骤(2)中的混合溶液B中，超声溶解，形成混合溶液C并在常温下磁力搅拌1h；之后将混合溶液C转移至100mL内衬为聚四氟乙烯的不锈钢反应釜中，在120-220℃下水热反应1-20h，待反应终止且反应温度自然冷却至室温，将得到的相应石墨烯基双金属硫化物纳米复合光催化剂在转速为4000r/min的离心机上离心5min，并分别用水和乙醇对产物进行多次洗涤，将离心洗涤分离后的产物在60℃下干燥24h，最终得到相应的石墨烯基双金属硫化物纳米复合光催化剂；
(4)称取0.05g步骤(3)中合成的石墨烯基双金属硫化物复合光催化剂超声分散到50mL水中，再加入5-20mL的有机酸或有机胺作为空穴牺牲剂，氮气吹扫5min；以300W的氙灯作为光源，同时采用滤光片过滤掉波长小于420nm的紫外光和远紫外光，进行可见光催化分解水制氢反应，采用气相色谱仪检测氢气生成量。
2.根据权利要求1所述的一种石墨烯基双金属硫化物纳米复合光催化剂的制备方法，其特征在于，在步骤(2)中，金属硫化物的金属盐前驱体锡盐化合物为四氯化锡；镉盐化合物为硫酸镉、碳酸镉、硝酸镉或乙酸镉中的一种或多种；钼盐化合物为钼酸铵、钼酸铋、七钼酸铵、钼酸钾或钼酸钠中的一种或多种；镍盐化合物为氯化镍、硝酸镍、乙酸镍、硫酸镍铵或氨基磺酸镍中的一种或多种；锌盐化合物为、硫酸锌、乙酸锌或硝酸锌中的一种或多种。
3.根据权利要求1所述的一种石墨烯基双金属硫化物纳米复合光催化剂的制备方法，其特征在于，在步骤(4)中，选取有机酸或有机胺作为空穴牺牲剂，其中，有机酸为乳酸、苹果酸或者柠檬酸中的任意一种，而有机胺为二乙醇胺、正丙醇胺或三乙醇胺中的任意一种；并且空穴牺牲剂的加入量与水的体积比范围为0.1～0.5:1。
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