CN114984987B - ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂的制备及其应用 - Google Patents
ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂的制备及其应用 Download PDFInfo
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Abstract
本发明公开了一种ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂的制备及其应用,属于催化材料领域。以亲水性强的柔性Ti3C2纳米片为中间桥梁,通过范德华力将2D结构ZnIn2S4和2D结构CuCo2S4紧密复合形成“2D‑2D‑2D”结构ZnIn2S4/Ti3C2/CuCo2S4三元复合型光催化剂。本发明中,2D结构Ti3C2作为中间桥梁,解决了n‑型半导体和p‑型半导体复合时兼容性差的问题,还可同时与其形成三重内建电场,加速了光生电子和空穴的定向移动和分离;2D‑2D‑2D结构增加了反应物接触面积,有效缩短了电荷传输距离,提升了电荷空间分离效率,将所制得ZnIn2S4/Ti3C2/CuCo2S4作为光催化剂展现出优异的光催化重整纤维素制氢性能。
Description
技术领域
本发明属于催化材料技术领域,具体涉及ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂的制备及其光催化重整纤维素制氢的应用。
背景技术
氢能源能量密度高,燃烧时能释放大量能量,对环境无污染,被认为是很有前景的化石燃料替代品。目前氢能源获取方式仍以化石燃料(如天然气、石油和煤炭等)重整/气化为主,生产成本高,对环境污染重。与此相比较,采用含有充足氢元素生物质衍生物(如乙醇、甘油和葡萄糖等)进行光催化重整制取氢能源越来越受到青睐。
在众多生物质中,纤维素含氢量高,在大规模制取氢能源方面显示出优越的经济潜力。在太阳光的照射下,纤维素作为电子和质子的双重供体,通过半导体光催化技术将纤维素重整制取氢能源为解决上述能源和环境问题提供了新思路,具有巨大的工业应用前景。
近年来,三元硫族化合物ZnIn2S4由于其较窄禁带宽度,较宽光吸收范围等优点,在光催化制氢领域引起了极大的关注。然而,单一的ZnIn2S4光催化剂在光催化过程中电子和空穴快速结合,量子效率低,这降低了其光催化活性并严重阻碍了它在工业上的广泛应用。为提高ZnIn2S4光催化剂的活性,研究者们采用构建异质结,助催化剂负载,金属掺杂等各种策略改善光生电子和空穴对的分离性能,进而提升ZnIn2S4光催化剂的活性和稳定性。
然而,在实际应用中,半导体光催化剂较差的催化活性、较低的量子效率和稳定性严重制约了光催化重整纤维素制氢技术在工业上的应用。为了解决上述问题,迫切需要开发和构建具有高催化活性的半导体光催化剂。
发明内容
本发明提供了一种操作简单且易于实现“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂,该复合型光催化剂具有量子效率高,光催化重整纤维素制氢活性好等优点。以2D结构Ti3C2作为中间桥梁,成功将n-型结构ZnIn2S4纳米片和p-型结构CuCo2S4纳米片复合形成“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂并将其应用到光催化重整纤维素制取氢能源方面。
本发明中,2D结构Ti3C2作为中间桥梁,不仅解决了n-型半导体ZnIn2S4和p-型半导体CuCo2S4复合时兼容性差的问题,还可同时与n-型半导体ZnIn2S4和p-型半导体CuCo2S4形成三重内建电场,加速了光生电子和空穴的定向移动和分离;此外,“2D-2D-2D”结构的构建不仅增加了反应物接触面积,同时也有效缩短了电荷传输距离,进一步提升了电荷空间分离效率。基于以上优势,本发明中所制备“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂在光催化重整纤维素制取氢能源方面展现了良好的应用。
本发明所述ZnIn2S4/Ti3C2/CuCo2S4复合型光催化剂,其结构特征在于:催化剂中ZnIn2S4、Ti3C2与CuCo2S4的质量比为1:0.01-0.1:0.01-0.15;XRD中在21.7°、27.8°、31.4°、39.9°、47.5°、52.4°、54.9°、56.0°存在衍射峰;XPS中在1021.97eV、1045.07eV、445.18eV、452.74eV、161.97eV、163.14eV、932.45eV、952.50eV、779.30eV、795.20eV、459.16eV、462.50eV、464.60eV、282.12eV、284.93eV、286.67eV和288.62eV存在结合能。上述数据允许存在上下0.1偏差。
进一步地,在上述技术方案中,该复合型光催化剂以亲水性强的柔性Ti3C2纳米片为中间桥梁,将n-型半导体ZnIn2S4和p-型半导体CuCo2S4复合在一起制得。
XRD数据分析图1中可以明显观察到纯ZnIn2S4在21.6°、27.7°、30.4°、39.8°、47.2°、52.4°、55.6°存在七个衍射峰,分别对应(006)晶面、(102)晶面、(104)晶面、(108)晶面、(110)晶面、(116)晶面和(022)晶面,ZnIn2S4的XRD光谱和标准卡片JCPDS no.65-2023相一致,说明ZnIn2S4样品成功合成。纯CuCo2S4可从图1中很明显观察到在26.6°、31.3°、38.0°、47.0°、50.0°、54.8°存在六个衍射峰,分别对应(022)晶面、(113)晶面、(004)晶面、(224)晶面、(115)晶面和(044)晶面,与之前报道的文献是相吻合。纯Ti3C2可以从图1中很明显观察到在6.3°、34.6°、41.4°、60.5°存在四个衍射峰,分别对应(002)晶面、(111)晶面、(200)晶面和(110)晶面,与之前报道文献是相吻合。复合样品ZnIn2S4/Ti3C2/CuCo2S4 XRD图谱中,除了ZnIn2S4的衍射峰外,还可很明显观察到CuCo2S4(113)、(044)晶面,说明CuCo2S4与ZnIn2S4成功复合。ZnIn2S4/Ti3C2/CuCo2S4样品中存在ZnIn2S4和CuCo2S4衍射峰,但衍射图谱中未观察到Ti3C2衍射峰,这可能是由于Ti3C2含量较低或者Ti3C2衍射峰太弱导致。
XPS分析ZnIn2S4/Ti3C2/CuCo2S4样品中的元素组成,从图2中可以看出Zn2p3/2和Zn2p1/2结合能为1021.97eV和1045.07eV,In 3d5/2和In 3d3/2结合能为445.18eV和452.74eV,图谱中S 2p3/2和S 2p1/2结合能分别为161.97eV和163.14eV,说明样品中包含Zn元素、In元素和S元素。图谱中Cu 2p3/2和Cu 2p1/2结合能为932.45eV和952.50eV,Co 2p3/2和Co 2p1/2结合能为779.30eV和795.20eV,说明样品中包含Cu元素和Co元素。图谱中结合能459.16eV、462.50eV和464.60eV相对应于Ti3C2中C-Ti-F键、Ti3+、TiO2-xFx键中Ti元素峰。图谱中结合能282.12eV、284.93eV、286.67eV和288.62eV相对应于Ti3C2中C-Ti键、C-C键、C-O键、O-C=O键中C元素的峰,说明样品中Ti3C2的存在,同时证明了XRD图谱中由于Ti3C2含量较低或Ti3C2衍射峰太弱导致未检测到Ti3C2衍射峰的原因。XPS图谱观察到三体系复合材料中包含Zn、In、S、Cu、Co、Ti和C元素,进一步证明成功制备出ZnIn2S4/Ti3C2/CuCo2S4复合材料。
ZnIn2S4/Ti3C2/CuCo2S4复合型光催化剂经过了XRD和XPS表征,XRD显示存在ZnIn2S4和CuCo2S4衍射峰,同时未发现其它杂质峰,说明所制备样品纯度很高;同时Ti3C2负载量较小,Ti3C2衍射峰并未检测出。XPS表明所制备ZnIn2S4/Ti3C2/CuCo2S4样品中包含Zn、In、S、Cu、Co、Ti和C元素,进一步证实了所制备样品中有ZnIn2S4、Ti3C2和CuCo2S4存在。
本发明所述“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂的制备方法,包括如下步骤:
1)将醋酸锌、氯化铟、硫代乙酰胺和柔性的Ti3C2纳米片分散于乙醇和水混合溶液中,随后将溶液在160-200℃进行水热反应,得到“2D-2D”结构ZnIn2S4/Ti3C2复合物。
2)将硝酸钴和硝酸铜分散于去离子水中,经搅拌溶解后加入硫脲和乙二胺,然后将所得混合溶液在180-240℃进行水热反应,得到2D结构CuCo2S4纳米片。
3)将ZnIn2S4/Ti3C2复合物和CuCo2S4纳米片分散于水溶液中超声,随后在60-90℃循环回流,得到“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4三元复合型光催化剂。
进一步地,在上述技术方案中,第一步所述醋酸锌、氯化铟与硫代乙酰胺摩尔比为1:2:4;乙醇和水体积比1:0.5-1。
进一步地,在上述技术方案中,第一步所得ZnIn2S4/Ti3C2复合物中ZnIn2S4与Ti3C2质量比为1:0.01-0.1。
进一步地,在上述技术方案中,第二步所述硝酸钴、硝酸铜与硫脲摩尔比为1:0.5:2。
进一步地,在上述技术方案中,第三步所述三元复合催化剂中ZnIn2S4、Ti3C2与CuCo2S4质量比为:1:0.01-0.1:0.01-0.15。
本发明还提供了上述符合催化剂的应用,将上述制备得到“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4三元复合型光催化剂进行光催化重整纤维素制氢实验。
进一步地,在上述技术方案中,操作条件为:操作条件为,光源300W氙灯;催化剂0.05g;去离子水100mL;纤维素0.5-2g。
从图3中可知,纯ZnIn2S4光催化重整纤维素的产氢速率为132μmol g-1h-1,而ZnIn2S4/Ti3C2/CuCo2S4光催化重整纤维素的产氢速率为2856μmol g-1h-1,表现出明显增强的光催化重整纤维素制氢性能。
本发明有益效果:
本发明制备得到为“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4三元复合型光催化剂。
1、亲水性强柔性Ti3C2纳米片引入,解决了n-型半导体ZnIn2S4和p-型半导体CuCo2S4复合时兼容性差问题,还可与n-型半导体ZnIn2S4和p-型半导体CuCo2S4形成三重内建电场,加速了光生电子和空穴定向移动和分离;
2、“2D-2D-2D”结构的构建不仅增加了反应物接触面积,同时也有效缩短了电荷传输距离,进一步提升了电荷空间分离效率,从而使得ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂光催化重整纤维素制氢性能得到极大提升。
附图说明
图1为实施例1所制备ZnIn2S4、Ti3C2、CuCo2S4及ZnIn2S4/Ti3C2/CuCo2S4 XRD图谱;
图2中为实施例1所制备ZnIn2S4/Ti3C2/CuCo2S4复合型光催化剂XPS图谱(a-h);
图3为实施例1所制备ZnIn2S4、ZnIn2S4/Ti3C2、ZnIn2S4/CuCo2S4、ZnIn2S4/Ti3C2/CuCo2S4催化剂光催化重整纤维素制氢效果图。
具体实施方式:
以下结合实施例进一步描述本发明。应该指出,本发明并非局限于下述各实施例。
实施例1
1)ZnIn2S4/Ti3C2制备:依次称取0.4mmol Zn(CH3COO)2、0.8mmol InCl3、1.6mmolCH3CSNH2和0.0085g柔性Ti3C2纳米片分散于24mL含乙醇50vol%水溶液中,室温条件下搅拌30分钟,将溶液转移至100mL聚四氟乙烯高压反应釜中,将反应釜在烘箱中160℃保持1小时,待反应结束并冷却至室温后进行抽滤,先后用去离子水和无水乙醇各清洗三遍,收集的固体样品转移至真空干燥箱中于60℃干燥12小时,得到ZnIn2S4/Ti3C2样品。制备过程中不加Ti3C2纳米片,采用上述同样步骤可制得纯ZnIn2S4样品。
2)CuCo2S4纳米片制备:称取2mmol Co(NO3)2·6H2O、1mmol Cu(NO3)2·3H2O置于30mL水中,室温条件下搅拌10分钟溶解完全,再称取4mmol硫脲加入上述溶液并剧烈搅拌15分钟,随后在搅拌下缓慢加入2mL乙二胺,之后将该溶液转移至50mL聚四氟乙烯高压反应釜中,将反应釜置于烘箱中180℃保持12小时,待反应结束并冷却至室温后进行抽滤,先后用去离子水和无水乙醇各清洗三遍,收集的固体样品转移至真空干燥箱中于60℃干燥12小时,得到CuCo2S4样品。
3)ZnIn2S4/Ti3C2/CuCo2S4复合样品的制备:称取步骤2)所得0.0066g CuCo2S4纳米片和步骤1)所得0.1g ZnIn2S4/Ti3C2纳米片混合分散于50mL水溶液中超声30min,接着在60℃水浴锅中进行循环回流4小时;待反应结束冷却至室温,将得到的产物经过去离子水和无水乙醇抽滤洗涤,真空干燥,得到“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4三元复合型光催化剂。
从图1中可明显看出制备的ZnIn2S4/Ti3C2/CuCo2S4样品中存在ZnIn2S4和CuCo2S4衍射峰,同时未发现其它物质衍射峰,说明所制备的ZnIn2S4和CuCo2S4样品纯度比较高。但衍射图谱中未观察到Ti3C2衍射峰,这可能是由于Ti3C2含量较低或者Ti3C2纳米片衍射峰太弱导致。Ti3C2纳米片的成功负载可以通过XPS进一步证实。
从图2中可以明显看出所制备的ZnIn2S4/Ti3C2/CuCo2S4样品中包含Zn、In、S、Ti、C、Cu和Co元素,进一步证实了所制备样品中有ZnIn2S4、Ti3C2和CuCo2S4存在。
从图3中可看出所制备三元体系ZnIn2S4/Ti3C2/CuCo2S4样品光催化重整纤维素制氢性能明显高于ZnIn2S4、ZnIn2S4/Ti3C2和ZnIn2S4/CuCo2S4样品,说明Ti3C2和CuCo2S4引入,有效增强了ZnIn2S4样品光催化重整纤维素产氢性能。
实施例2
1)ZnIn2S4/Ti3C2制备:依次称取0.4mmol Zn(CH3COO)2、0.8mmol InCl3、1.6mmolCH3CSNH2和0.0017g柔性Ti3C2纳米片分散于24ml含乙醇55vol%的水溶液中,室温条件下搅拌30分钟,将溶液转移至100mL聚四氟乙烯高压反应釜中,将反应釜在烘箱中180℃保持1小时,待反应结束并冷却至室温后进行抽滤,先后用去离子水和无水乙醇各清洗三遍,收集的固体样品转移至真空干燥箱中于60℃干燥12小时,得到ZnIn2S4/Ti3C2样品。制备过程中不加Ti3C2纳米片,采用上述同样步骤可制得纯ZnIn2S4样品。
2)CuCo2S4纳米片制备:称取2mmol Co(NO3)2·6H2O、1mmol Cu(NO3)2·3H2O置于30mL水中,室温条件下搅拌10分钟以保证溶解完全,再称取4mmol硫脲加入上述溶液并剧烈搅拌15分钟,随后在搅拌下缓慢加入2ml乙二胺,之后将该溶液转移至50mL聚四氟乙烯高压反应釜中,将反应釜置于烘箱中200℃保持12小时,待反应结束并冷却至室温后进行抽滤,先后用去离子水和无水乙醇各清洗三遍,收集的固体样品转移至真空干燥箱中于60℃干燥12小时,得到CuCo2S4样品。
3)ZnIn2S4/Ti3C2/CuCo2S4复合样品的制备:称取步骤2)所得0.0011g CuCo2S4纳米片和步骤1)所得0.1g ZnIn2S4/Ti3C2纳米片混合分散于50mL水溶液中超声30min,接着在80℃水浴锅中进行循环回流4小时;待反应结束冷却至室温,将得到的产物经过去离子水和无水乙醇抽滤洗涤,真空干燥,得到“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4三元复合型光催化剂。
实施例3
1)ZnIn2S4/Ti3C2制备:依次称取0.4mmol Zn(CH3COO)2、0.8mmol InCl3、1.6mmolCH3CSNH2和0.017g柔性Ti3C2纳米片分散于24mL含乙醇65vol%水溶液中,室温条件下搅拌30分钟后将溶液转移至100mL聚四氟乙烯高压反应釜中,将反应釜在烘箱中200℃保持1小时,待反应结束并冷却至室温后进行抽滤,先后用去离子水和无水乙醇各清洗三遍,收集的固体样品转移至真空干燥箱中于60℃干燥12小时,得到ZnIn2S4/Ti3C2样品。制备过程中不加Ti3C2纳米片,采用上述同样的步骤可制得纯ZnIn2S4样品。
2)CuCo2S4纳米片制备:称取2mmol Co(NO3)2·6H2O、1mmol Cu(NO3)2·3H2O置于30mL水中,室温条件下搅拌10分钟以保证溶解完全,再称取4mmol硫脲加入上述溶液并剧烈搅拌15分钟,随后在搅拌下缓慢加入2ml乙二胺,之后将该溶液转移至50ml聚四氟乙烯高压反应釜中,将反应釜置于烘箱中240℃保持12小时,待反应结束并冷却至室温后进行抽滤,先后用去离子水和无水乙醇各清洗三遍,收集的固体样品转移至真空干燥箱中于60℃干燥12小时,得到CuCo2S4样品。
3)ZnIn2S4/Ti3C2/CuCo2S4复合样品制备:称取步骤2)所得0.0165g CuCo2S4纳米片和步骤1)所得0.1g ZnIn2S4/Ti3C2纳米片混合分散于50mL水溶液中超声30min,接着在90℃水浴锅中进行循环回流4小时;待反应结束冷却至室温,将得到的产物经过去离子水和无水乙醇抽滤洗涤,真空干燥,得到“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4三元复合型光催化剂。
实施例4光催化重整纤维素产氢实验:
操作条件:光源300W氙灯;催化剂0.05g;去离子水100mL;纤维素1g。从图3中可知,纯ZnIn2S4光催化重整纤维素的产氢速率为132μmol g-1h-1,而采用实施例1中得到ZnIn2S4/Ti3C2/CuCo2S4复合催化剂光催化重整纤维素产氢速率高达2856μmol g-1h-1,表现出明显增强的光催化制氢性能。
结合图1、图2和图3结果可证明已经成功制得具有增强光催化重整纤维素产氢性能的“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4复合型光催化剂。
实施例5
采用实施例2-3制备得到复合光催化剂得到类似的产氢效果。
以上实施例描述了本发明的基本原理、主要特征及优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (8)
1.一种ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂的制备方法,其特征在于,包括如下步骤:
1)将醋酸锌、氯化铟、硫代乙酰胺和柔性Ti3C2纳米片分散于乙醇和水混合溶液中,随后将溶液在160-200℃进行水热反应,得到“2D-2D”结构ZnIn2S4/Ti3C2复合物;
2)将硝酸钴和硝酸铜分散于去离子水中,经搅拌溶解后加入硫脲和乙二胺,然后将所得混合溶液在180-240℃进行水热反应,得到2D结构CuCo2S4纳米片;
3)将ZnIn2S4/Ti3C2复合物和CuCo2S4纳米片分散于水溶液中超声,随后在60- 90℃循环回流,得到“2D-2D-2D”结构ZnIn2S4/Ti3C2/CuCo2S4三元复合型光催化剂。
2.根据权利要求1所述复合型光催化剂的制备方法,其特征在于:步骤1)所述醋酸锌、氯化铟与硫代乙酰胺摩尔比为1: 2: 4。
3.根据权利要求1所述复合型光催化剂的制备方法,其特征在于:步骤1)所述乙醇和水体积比1: 0.5-1。
4.根据权利要求1所述复合型光催化剂的制备方法,其特征在于:步骤1)所述ZnIn2S4/Ti3C2复合物中,ZnIn2S4与Ti3C2质量比为1: 0.01-0.1。
5.根据权利要求1所述复合型光催化剂的制备方法,其特征在于:步骤2)所述硝酸钴、硝酸铜与硫脲摩尔比为1: 0.5: 2。
6.根据权利要求1所述复合型光催化剂的制备方法,其特征在于:步骤3)ZnIn2S4/Ti3C2/CuCo2S4复合物中,ZnIn2S4、Ti3C2与CuCo2S4的质量比为1: 0.01-0.1: 0.01- 0.15。
7.ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂在光催化重整纤维素制氢的应用,其特征在于:纤维素与催化剂产生的空穴首先发生氧化反应生成糖类和小分子中间产物,然后中间产物与光生电子发生还原反应生成氢气;所述ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂,催化剂中ZnIn2S4、Ti3C2与CuCo2S4质量比为1: 0.01-0.1: 0.01-0.15;XRD中在21.7°、27.8°、31.4°、39.9°、47.5°、52.4°、54.9°、56.0°存在衍射峰;XPS中在1021.97 eV、1045.07 eV、445.18eV、452.74 eV、161.97 eV、163.14 eV、932.45 eV、952.50 eV、779.30 eV、795.20 eV、459.16 eV、462.50 eV、464.60 eV、282.12 eV、284.93 eV、286.67 eV和288.62 eV存在结合能。
8.根据权利要求7所述ZnIn2S4/Ti3C2/CuCo2S4复合型催化剂在光催化重整纤维素制氢的应用,其特征在于:操作条件为,光源 300W氙灯;催化剂0.05 g;去离子水100 mL;纤维素0.5-2 g。
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