CN114984988B - Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型催化剂的制备及其应用 - Google Patents
Zn0.5Cd0.5S/CuInS2/Bi2Se3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Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型催化剂的制备及其应用,属于催化材料领域。以原位沉积法制得“2D‑2D”结构Zn0.5Cd0.5S/CuInS2p‑n异质结构,接着超声法将类金属Bi2Se3纳米片助催化剂与其复合在一起形成“2D‑2D‑2D”结构Zn0.5Cd0.5S/CuInS2/Bi2Se3三元复合型光催化剂。本发明中,n‑型半导体Zn0.5Cd0.5S和p‑型半导体CuInS2形成内建电场;Bi2Se3纳米片助催化剂作为电子捕获中心提供更多反应活性位点;“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;上述复合型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Zn0.5Cd0.5S/CuInS2/Bi2Se3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。氢能制取与应用已成为当前研究的一个热点,传统制氢工艺如电解水、煤炭转化等能耗大,且伴随大量的二氧化碳释放。与传统制氢工艺相比,光催化重整生物质制氢减少了二氧化碳的排放,用可持续的生物质染料替代了化石燃料,制氢潜力巨大。在众多的生物质中,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。
到目前为止,研究者们开发和设计了很多氧化物、硫化物、氮化物、碳化物等许多高活性制氢光催化剂。ZnxCd1-xS固溶体,作为金属硫化物在电催化水分解、氧化还原反应、染料敏化太阳能电池和超级电容器等诸多领域都表现出卓越化性能。ZnxCd1-xS除了具有带隙窄、平带电势高优点外,还可通过界面处与其它金属键合的中间硫原子进行有效的电荷转移。尽管ZnxCd1-xS具有适宜禁带宽度和较高的导带位置,然而光催化反应过程中电子和空穴对的快速复合,严重影响了ZnxCd1-xS光催化活性。
然而,目前光催化重整纤维素制氢催化剂方面还存在很多缺陷,如光催化剂稳定性差,可见光吸收能力弱及光反应过程中光生电荷的快速复合仍是光催化重整纤维素制氢过程中的限制因素。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
为提高ZnxCd1-xS光催化剂的活性,多种改性策略如杂原子掺杂,构建异质结构,助催化剂负载等被用来增强ZnxCd1-xS的产氢活性。而本发明以2D结构Bi2Se3为助催化剂,成功将其与n-型结构Zn0.5Cd0.5S纳米片和p-型结构CuInS2纳米片复合在一起形成“2D-2D-2D”结构Zn0.5Cd0.5S/CuInS2/Bi2Se3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,n-型半导体Zn0.5Cd0.5S和p-型半导体CuInS2形成内建电场,加速了光生电子和空穴的定向迁移和分离;此外,Bi2Se3纳米片助催化剂作为电子捕获中心不仅可以提供更多反应活性位点,还可进一步提高电荷分离效率;再者,“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,本发明中所制备的“2D-2D-2D”结构Zn0.5Cd0.5S/CuInS2/Bi2Se3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Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型光催化剂,催化剂中Zn0.5Cd0.5S、CuInS2与Bi2Se3质量比为1:0.01-0.15:0.01-0.1;XRD中在25.8°、27.2°、28.2°、36.2°、44.9°、48.2°、53.1°存在衍射峰;XPS中在1021.41eV、1044.42eV、932.14eV、951.99eV、444.79eV、452.38eV、444.78eV、404.85eV、411.62eV、225.80eV、53.54eV、54.09eV、159.78eV、163.33eV、166.89eV、156.25eV和617.78eV存在结合能。上述数据允许存在上下0.1偏差。
进一步地,上述符合型光催化剂中,以2D结构的Bi2Se3为助催化剂,将其与n-型半导体Zn0.5Cd0.5S和p-型半导体CuInS2复合在一起制得。
XRD数据分析图1中可以明显观察到纯Zn0.5Cd0.5S在25.8°、27.2°、28.2°、36.2°、44.9°、48.2°、53.1°存在七个衍射峰,分别对应(100)晶面、(002)晶面、(101)晶面、(102)晶面、(110)晶面、(103)晶面和(200)晶面,Zn0.5Cd0.5SXRD光谱和标准卡片JCPDS no.89-2943相一致,说明Zn0.5Cd0.5S样品成功合成。纯CuInS2可以从图中很明显观察到在27.7°、46.1°、54.9°存在三个衍射峰,分别对应(112)晶面、(204)晶面(116)晶面,与之前报道文献是相吻合。纯Bi2Se3从图1中很明显观察到在18.7°、25.0°、27.8°、29.4°、35.4°、38.2°、40.3°、42.9°、43.7°、47.7°、50.9°、53.4°、57.5°、60.9°、66.6°、71.5°、75.0°、78.0°存在十八个衍射峰,分别对应(006)晶面、(101)晶面、(104)晶面、(105)晶面、(018)晶面、(0012)晶面、(1010)晶面、(0111)晶面、(110)晶面、(0015)晶面、(021)晶面、(205)晶面、(1016)晶面、(0210)晶面、(1115)晶面、(0120)晶面、(128)晶面和(2110)晶面,与之前报道文献是相吻合。Zn0.5Cd0.5S/CuInS2/Bi2Se3样品中存在Zn0.5Cd0.5S衍射峰,但衍射图谱中未观察到CuInS2和Bi2Se3衍射峰,这可能是由于CuInS2和Bi2Se3含量较低或CuInS2和Bi2Se3衍射峰太弱导致。
XPS分析Zn0.5Cd0.5S/CuInS2/Bi2Se3样品元素组成,从图2中可以看出Zn 2p3/2和Zn2p1/2结合能为1021.41eV和1044.42eV,Cd 3d5/2和Cd 3d3/2结合能为404.85eV和411.62eV,图谱中S 2s结合能为225.8eV。说明样品中包含Zn元素、Cd元素和S元素。图谱中Cu 2p3/2和Cu 2p1/2结合能为932.14eV和951.99eV,In 3d5/2和In 3d3/2结合能为444.79eV和452.38eV。说明样品中包含Cu元素和In元素。图谱中Se 3d5/2和Se 3d3/2结合能为53.54eV和54.09eV,Bi4d5结合能为444.78eV。XPS图谱观察到三体系复合材料中包含Zn、Cd、S、Cu、In、Bi和Se元素,进一步证明成功的制备出Zn0.5Cd0.5S/CuInS2/Bi2Se3复合材料。
Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型光催化剂经过了XRD和XPS表征,XRD显示存在Zn0.5Cd0.5S衍射峰,同时未发现其它杂质峰,说明所制备样品纯度很高;同时由于CuInS2和Bi2Se3负载量较小,CuInS2和Bi2Se3衍射峰并未检测出。XPS表明所制备Zn0.5Cd0.5S/CuInS2/Bi2Se3样品中包含Zn、Cd、S、Cu、In、Bi和Se元素,进一步证实了所制备样品中有Zn0.5Cd0.5S、CuInS2和Bi2Se3存在。
本发明所述“2D-2D-2D”结构Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型催化剂制备方法,包括如下步骤:
1)将氯化锌、氯化镉和硫化钠溶解在乙二醇溶液中,在氮气氛围下,将溶液在180-240℃进行水热反应,得到2D结构Zn0.5Cd0.5S纳米片。
2)将氯化铜、氯化铟、硫代乙酰胺和Zn0.5Cd0.5S纳米片分散于去离子水中,经剧烈搅拌后将所得混合溶液在180-220℃进行水热反应,得到“2D-2D”结构的Zn0.5Cd0.5S/CuInS2复合物。
3)将聚乙烯吡咯烷酮溶解在乙二醇中,然后加入硝酸铋和二氧化硒,经剧烈搅拌后将所得混合溶液在180-240℃进行水热反应,得到2D结构的Bi2Se3纳米片。
4)将Zn0.5Cd0.5S/CuInS2复合物和Bi2Se3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Zn0.5Cd0.5S/CuInS2/Bi2Se3三元复合型光催化剂。
进一步地,在上述技术方案中,第一步所述氯化锌、氯化镉和硫化钠摩尔比为1:1:2。
进一步地,在上述技术方案中,第二步所述氯化铜、氯化铟、硫代乙酰胺的摩尔比为1:1:10-100;Zn0.5Cd0.5S/CuInS2复合物中,Zn0.5Cd0.5S与CuInS2质量比为1:0.01-0.15。
进一步地,在上述技术方案中,第三步所述硝酸铋与二氧化硒摩尔比为1:1.5。
进一步地,在上述技术方案中,第四步所述Zn0.5Cd0.5S/CuInS2/Bi2Se3三元复合物中,Zn0.5Cd0.5S、CuInS2与Bi2Se3质量比为1:0.01-0.15:0.01-0.1。
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Zn0.5Cd0.5S/CuInS2/Bi2Se3三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:光源300W氙灯;催化剂量0.05g;去离子水量100mL;纤维素0.5-2g。
从图3中可知,纯Zn0.5Cd0.5S光催化重整纤维素的产氢速率为164μmol g-1h-1,而Zn0.5Cd0.5S/CuInS2/Bi2Se3光催化重整纤维素的产氢速率3012μmol g-1h-1,表现出明显增强光催化重整纤维素制氢性能。
本发明有益效果:
本发明“2D-2D-2D”结构Zn0.5Cd0.5S/CuInS2/Bi2Se3三元复合型光催化剂。
1、n-型半导体Zn0.5Cd0.5S和p-型半导体CuInS2形成内建电场,加速了光生电子和空穴的定向迁移和分离;
2、Bi2Se3纳米片助催化剂作为电子捕获中心不仅可以提供更多反应活性位点,还可进一步提高电荷分离效率;
3、“2D-2D-2D”结构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Zn0.5Cd0.5S/CuInS2/Bi2Se3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Zn0.5Cd0.5S、CuInS2、Bi2Se3及Zn0.5Cd0.5S/CuInS2/Bi2Se3XRD图谱;
图2为实施例1所制备Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型光催化剂XPS图谱(a-h);
图3为实施例1所制备Zn0.5Cd0.5S、Zn0.5Cd0.5S/CuInS2、Zn0.5Cd0.5S/CuInS2/Bi2Se3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)Zn0.5Cd0.5S纳米片制备:依次称取2mmol ZnCl2、2mmolCdCl2和4mmol Na2S·9H2O溶解于40mL乙二醇溶液,然后向溶液中加入20mL浓度为0.5mol/LNaOH水溶液,在氮气氛围下,将溶液在180℃进行水热回流反应4h,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12h得到2D结构Zn0.5Cd0.5S纳米片。
2)Zn0.5Cd0.5S/CuInS2复合物制备:称取0.012mmol CuCl、0.012mmol InCl3、0.5mmol硫代乙酰胺溶和0.1g步骤1)所制得Zn0.5Cd0.5S纳米片分散于40mL去离子水中,经剧烈搅拌1h,将所得混合溶液转移到水热反应器中在180℃水热反应12h,待反应结束并冷却至室温后进行抽滤,先后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12h,得到“2D-2D”结构Zn0.5Cd0.5S/CuInS2复合物。
3)Bi2Se3纳米片制备:在搅拌状态下,将0.8g聚乙烯基吡咯烷酮溶解到溶解在40mL乙二醇中,然后加入2mmol Bi(NO3)3·5H2O和3mmol SeO2,经剧烈搅拌1h后将所得混合溶液转移到水热反应器中在180℃水热反应12h,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12h,得到2D结构Bi2Se3纳米片。
4)Zn0.5Cd0.5S/CuInS2/Bi2Se3复合样品制备:称取步骤(2)所得0.1g Zn0.5Cd0.5S/CuInS2复合物和步骤3)所得0.3mg Bi2Se3纳米片混合分散于50mL水溶液中超声2h,随后将溶液继续搅拌10h,将得到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Zn0.5Cd0.5S/CuInS2/Bi2Se3三元复合型光催化剂。
从图1中可以明显看出制备Zn0.5Cd0.5S/CuInS2/Bi2Se3样品中存在Zn0.5Cd0.5S和CuInS2的衍射峰,同时未发现其它物质衍射峰,说明所制备Zn0.5Cd0.5S和CuInS2样品纯度比较高。但衍射图谱中未观察到Bi2Se3衍射峰,这可能是由于Bi2Se3含量较低或者Bi2Se3纳米片衍射峰太弱导致。Bi2Se3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Zn0.5Cd0.5S/CuInS2/Bi2Se3样品中包含Zn、Cd、S、Cu、In、Bi和Se元素,进一步证实了所制备样品中有Zn0.5Cd0.5S、CuInS2和Bi2Se3存在。
从图3中可以看出所制备三元体系Zn0.5Cd0.5S/CuInS2/Bi2Se3样品光催化重整纤维素制氢性能明显高于Zn0.5Cd0.5S、Zn0.5Cd0.5S/CuInS2和Zn0.5Cd0.5S/CuInS2/Bi2Se3样品,说明p-n异质结构构建、助催化剂Bi2Se3引入及特殊“2D-2D-2D”结构构建有效增强了Zn0.5Cd0.5S样品的光催化重整纤维素产氢性能。
实施例2
1)Zn0.5Cd0.5S纳米片制备:依次称取2mmol ZnCl2、2mmol CdCl2和4mmol Na2S·9H2O溶解于40mL乙二醇溶液,然后向溶液中加入20mL浓度为0.5mol/LNaOH水溶液,在氮气氛围下,将溶液在240℃进行水热回流反应4h,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12h,得到2D结构Zn0.5Cd0.5S纳米片。
2)Zn0.5Cd0.5S/CuInS2复合物的制备:称取0.05mmol CuCl、0.05mmol InCl3、5mmol硫代乙酰胺溶和0.1g步骤1)所制得Zn0.5Cd0.5S纳米片分散于40mL去离子水中,经剧烈搅拌1h,将所得混合溶液转移到水热反应器中在240℃水热反应12h,待反应结束并冷却至室温后进行抽滤,先后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12h,得到“2D-2D”结构Zn0.5Cd0.5S/CuInS2复合物。
3)Bi2Se3纳米片制备:在搅拌状态下,将0.8g聚乙烯基吡咯烷酮溶解到溶解在40mL乙二醇中,然后加入2mmol Bi(NO3)3·5H2O和3mmol SeO2,经剧烈搅拌1h,将所得混合溶液转移到水热反应器中在180℃水热反应12h,待反应结束并冷却至室温后进行抽滤,先后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12h,得到2D结构Bi2Se3纳米片。
4)Zn0.5Cd0.5S/CuInS2/Bi2Se3复合样品制备:称取步骤(2)所得0.1g Zn0.5Cd0.5S/CuInS2复合物和步骤3)所得0.3mg Bi2Se3纳米片混合分散于50mL水溶液中超声2h,随后将溶液继续搅拌10h,将得到的产物经过去离子水和无水乙醇抽滤洗涤,真空干燥后得到“2D-2D-2D”结构Zn0.5Cd0.5S/CuInS2/Bi2Se3三元复合型光催化剂。
实施例3
1)Zn0.5Cd0.5S纳米片制备:依次称取2mmol ZnCl2、2mmol CdCl2和4mmol Na2S·9H2O溶解于40mL乙二醇溶液,然后向溶液中加入20mL浓度为0.5mol/LNaOH水溶液,在氮气氛围下,将溶液在220℃进行水热回流反应4h,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12h得到2D结构的Zn0.5Cd0.5S纳米片。
2)Zn0.5Cd0.5S/CuInS2复合物制备:称取0.004mmol CuCl、0.004mmol InCl3、0.04mmol硫代乙酰胺溶和0.1g步骤1)所制得Zn0.5Cd0.5S纳米片分散于40mL去离子水中,经剧烈搅拌1h,将所得混合溶液转移到水热反应器中在220℃水热反应12h,待反应结束并冷却至室温后进行抽滤,先后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12h,得到“2D-2D”结构Zn0.5Cd0.5S/CuInS2复合物。
3)Bi2Se3纳米片制备:在搅拌状态下,将0.8g聚乙烯基吡咯烷酮溶解到溶解在40mL乙二醇中,然后加入2mmol Bi(NO3)3·5H2O和3mmol SeO2,经剧烈搅拌1h,将所得混合溶液转移到水热反应器中在240℃水热反应12h,待反应结束并冷却至室温后进行抽滤,先后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12h,得到2D结构Bi2Se3纳米片。
4)Zn0.5Cd0.5S/CuInS2/Bi2Se3复合样品制备:称取步骤(2)所得0.1g Zn0.5Cd0.5S/CuInS2复合物和步骤3)所得1.0mg Bi2Se3纳米片混合分散于50mL水溶液中超声2h,随后将溶液继续搅拌10h,将得到的产物经过去离子水和无水乙醇抽滤洗涤,真空干燥后得到“2D-2D-2D”结构Zn0.5Cd0.5S/CuInS2/Bi2Se3三元复合型光催化剂。
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Zn0.5Cd0.5S光催化重整纤维素产氢速率为164μmol g-1h-1,而采用实施例1中得到Zn0.5Cd0.5S/CuInS2/Bi2Se3复合催化剂的光催化重整纤维素产氢速率高达3012μmol 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“2D-2D-2D”结构Zn0.5Cd0.5S/CuInS2/Bi2Se3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 (6)
1.一种Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型光催化剂的制备方法,其特征在于,包括如下步骤:
1)将氯化锌、氯化镉和硫化钠溶解在乙二醇溶液中,在氮气氛围下,将溶液在180-240℃进行水热反应,得到2D结构Zn0.5Cd0.5S纳米片;
2)将氯化铜、氯化铟、硫代乙酰胺和Zn0.5Cd0.5S纳米片分散于去离子水中,经剧烈搅拌后将所得混合溶液在180-240℃进行水热反应,得到“2D-2D”结构Zn0.5Cd0.5S/CuInS2复合物;
3)将聚乙烯吡咯烷酮溶解在乙二醇中,然后加入硝酸铋和二氧化硒,经剧烈搅拌后将所得混合溶液在180-240℃进行水热反应,得到2D结构Bi2Se3纳米片;
4)将Zn0.5Cd0.5S/CuInS2复合物和Bi2Se3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Zn0.5Cd0.5S/CuInS2/Bi2Se3三元复合型光催化剂;其中:催化剂中Zn0.5Cd0.5S、CuInS2与Bi2Se3质量比为1: 0.01-0.15: 0.01-0.1;XRD中在25.8°、27.2°、28.2°、36.2°、44.9°、48.2°、53.1°存在衍射峰;XPS中在1021.41 eV、1044.42 eV、932.14eV、951.99 eV、444.79 eV、452.38 eV、444.78 eV、404.85 eV、411.62 eV、225.80 eV、53.54 eV、54.09eV、159.78 eV、163.33 eV、166.89 eV、156.25 eV和617.78 eV存在结合能。
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)所述氯化锌、氯化镉与硫化钠摩尔比为1: 1: 2。
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2)所述氯化铜、氯化铟与硫代乙酰胺摩尔比为1: 1: 10-100。
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3)所述硝酸铋与二氧化硒摩尔比为1: 1.5。
5.采用权利要求1所述制备方法得到的Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型光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。
6.根据权利要求5所述Zn0.5Cd0.5S/CuInS2/Bi2Se3复合型光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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