CN107694589B - 一种用于光电催化产氢的薄膜复合材料的制备方法 - Google Patents
一种用于光电催化产氢的薄膜复合材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于光电催化产氢的薄膜复合材料的制备方法，首先通过热蒸气液聚法制备g‑C3N4薄膜；然后采用水浴法将Sb2S3纳米球负载到g‑C3N4薄膜上；最后通过光电化学沉积法将Co‑Pi纳米颗粒沉积到g‑C3N4/Sb2S3上最终得到g‑C3N4/Sb2S3/Co‑Pi薄膜复合材料。本发明提升了g‑C3N4的可见光吸收，促进了光生电子‑空穴对的分离；制备方法简单易操作，整体成本低廉。
Description
技术领域
本发明属于材料制备技术领域，具体为一种用于光电催化产氢的g-C3N4/Sb2S3/Co-Pi薄膜复合材料的制备方法。
背景技术
氢能作为理想高效的绿色能源，具有高能量密度、易储存等优点，可以作为解决能源危机和保持社会可持续发展的关键推动力。自20世纪70年代起，日本学者Fujishima和Honda报道了将TiO2半导体用作光电化学分解水的光阳极材料后，由于其优异的稳定性，可用性，无毒性和低价格，TiO2已经成为传统的光电阳极材料用于光电化学分解水产生氢气。然而，由于其较宽的带隙3.2eV，使其仅吸收占太阳光百分之四的紫外光，导致太阳光利用率低。因此，吸收可见光的新型光电极材料引起人们的广泛研究兴趣，特别是价格低廉的非金属光电极材料。
类石墨碳氮化物g-C3N4作为非金属有机光催化剂，禁带宽度约为2.7eV，由于其可见光反应、无毒、低成本、高化学热力学稳定性等优点，使得人们对其的研究兴趣日益增加。其优异的化学热力学稳定性归因于g-C3N4结构中的三均三嗪单元。架状结构的g-C3N4薄膜具有较大的比表面积，提供了较多的反应位点，且架状结构促进了光的反射捕获。此外架状结构的g-C3N4薄膜应用于光电化学分解水产氢时，将不会像粉末或块体那样分散在水中不易回收循环利用。较宽的可见光吸收范围和较好的光生电子-空穴对分离是衡量半导体光电催化性能好的关键性因素。而Sb2S3等硫化物半导体禁带宽度普遍较窄以至于可以大幅度提高可见光响应范围，Co-Pi等共催化剂在分离光生电子-空穴对方面显示出了优异的性能。因此将Sb2S3和Co-Pi共同负载在g-C3N4薄膜表面，以达到g-C3N4基薄膜复合材料较佳的光电催化性能。
发明内容
本发明的目的在于提出一种用于光电催化产氢的g-C3N4/Sb2S3/Co-Pi薄膜复合材料的制备方法，能够提升g-C3N4的光电催化性能。
本发明技术方案为：一种用于光电催化产氢的薄膜复合材料的制备方法，包括如下步骤：
步骤一：通过热蒸气液聚法制备g-C3N4薄膜
将尿素或者硫脲放入坩埚或者方舟中，转移到马弗炉中处理，即可得到附在FTO导电玻璃上的架状结构的g-C3N4薄膜。
步骤二：采用水浴法将Sb2S3纳米球负载到g-C3N4薄膜上
将所述步骤一中制备的样品置于生长溶液中水浴反应，取出后经过去离子水清洗，烘干得到g-C3N4/Sb2S3薄膜。
步骤三：通过光电化学沉积法将Co-Pi纳米颗粒沉积到g-C3N4/Sb2S3薄膜上，最终得到g-C3N4/Sb2S3/Co-Pi薄膜复合材料。
进一步的，所述步骤一具体为：将5-10g的尿素或者硫脲研磨成细粉末，然后取1.5-8g细粉末装满到坩埚或者方舟中，将FTO导电玻璃以导电面朝下的方式盖压在坩埚或者方舟上，转移到马弗炉中处理，即可得到附在FTO导电玻璃上的架状结构的g-C3N4薄膜。
进一步的，所述马弗炉中处理的工艺参数为：以2℃/min的升温速率加热200℃后保温1h然后继续以2℃/min升温到500℃后保温2h，冷却至室温；
或者以2℃/min的升温速率加热500℃后保温2h，冷却至室温。
进一步的，所述步骤二的制备工艺参数为：将所述步骤一中制备的样品置于60-70℃的生长溶液中水浴反应0.5-1.5h取出后经过去离子水清洗，80℃烘干得到g-C3N4/Sb2S3薄膜。
进一步的，所述生长溶液的制备工艺参数为：将0.64-0.96gSbCl3溶解在1体积的丙酮中，然后加入29体积的去离子水，得到SbCl3溶液；将6.2-9.3gNa2S2O3·5H2O溶解在25mL的去离子水中，得到Na2S2O3·5H2O溶液；将Na2S2O3·5H2O溶液加入到SbCl3溶液中，磁力搅拌至变成橘红色即为生长溶液。
进一步的，所述Na2S2O3·5H2O溶液与所述SbCl3溶液的体积比为1：3。
进一步的，所述步骤三的制备工艺参数为：将所述步骤二制得的g-C3N4/Sb2S3薄膜作为工作电极，Ag/AgCl作为参比电极，Pt片作为对电极，电解液为Co-Pi生长溶液，光源为100mW·cm-2的氙灯，应用电压为0.35-0.45V，沉积时间为60～600s；沉积薄膜后经过去离子水清洗，80℃烘干，最终得到g-C3N4/Sb2S3/Co-Pi薄膜。
进一步的，所述Co-Pi生长溶液的制备工艺参数为：Co(NO3)2溶液与磷酸钾溶液以浓度比1：200的比例混合即为Co-Pi生长溶液。
进一步的，所述磷酸钾溶液的制备工艺参数为：K2HPO4和KH2PO4溶液以体积比为8：5混合，即为磷酸钾溶液，此时磷酸钾溶液的pH为7。
与现有技术相比，本发明的有益效果为：
(1)本发明能够有效加强可见光吸收，促进光生电子-空穴对的分离。
(2)本发明的制备方法简单易操作，整体成本低廉。
(3)本发明所制得的g-C3N4/Sb2S3/Co-Pi薄膜复合材料可见光吸收优异，光电催化性能较高。
附图说明
图1为实施例中所得的g-C3N4/Sb2S3/Co-Pi薄膜复合材料的扫描电镜图像。
具体实施方式
下面的实施例可以使本专业技术人员更全面的理解本发明，但不以任何方式限制本发明。
实施例1
一种用于光电催化产氢的薄膜复合材料的制备方法，包括如下步骤：
步骤一：将10g硫脲研磨成粉末，取7g的粉末填装到60×90mm的方舟中，将FTO导电玻璃以导电面朝下的方式完全盖亚在方舟上，转移到马弗炉中，以2℃/min的升温速率加热200℃后保温1h，然后继续以2℃/min升温到500℃后保温2h，冷却至室温，即可得到附在FTO导电玻璃上的架状结构的g-C3N4薄膜。
步骤二：将0.64gSbCl3溶解到2.5ml的丙酮中后加入72.5ml的去离子水，将6.2g的Na2S2O3·5H2O加入到25ml的去离子水中，将Na2S2O3·5H2O溶液倒入到SbCl3溶液中，磁力搅拌至溶液变成橘红色，即为生长溶液，然后将步骤一制得的样品置于70℃的生长溶液中水浴1h，取出后经过去离子水清洗，80℃烘干得到g-C3N4/Sb2S3薄膜。
步骤三：称取2.8g的K2HPO4和1.1g的KH2PO4加到100ml的去离子水中，pH为7，然后加入0.03g Co(NO3)2磁力搅拌充分溶解后作为Co-Pi生长溶液备用。
g-C3N4/Sb2S3薄膜作为工作电极，Ag/AgCl作为参比电极，Pt片作为对电极，电解液为Co-Pi生长溶液，在100mW·cm-2的氙灯照射下，应用0.4V的电压沉积200s，最后取出后经过去离子水清洗，80℃烘干得到g-C3N4/Sb2S3/Co-Pi薄膜。
实施例2
一种用于光电催化产氢的薄膜复合材料的制备方法，包括如下步骤：
步骤一：将5g硫脲研磨成粉末，取1.5g的粉末填装到5ml坩埚中，将FTO导电玻璃以导电面朝下的方式完全盖亚在方舟上，转移到马弗炉中，以2℃/min的升温速率加热500℃后保温2h，冷却至室温，即可得到附在FTO导电玻璃上的架状结构的g-C3N4薄膜。
步骤二：将0.96g SbCl3溶解到2.5ml的丙酮中后加入72.5ml的去离子水，将9.3g的Na2S2O3·5H2O加入到25ml的去离子水中，将Na2S2O3·5H2O溶液倒入到SbCl3溶液中，磁力搅拌至溶液变成橘红色，即为生长溶液，然后将步骤一制得的样品置于65℃的生长溶液中水浴45min，取出后经过去离子水清洗，80℃烘干得到g-C3N4/Sb2S3薄膜。
步骤三：称取2.8g的K2HPO4和1.1g的KH2PO4加到100ml的去离子水中，pH为7，然后加入0.06g Co(NO3)2磁力搅拌充分溶解后作为Co-Pi生长溶液备用。
g-C3N4/Sb2S3薄膜作为工作电极，Ag/AgCl作为参比电极，Pt片作为对电极，电解液为Co-Pi生长溶液，在100mW·cm-2的氙灯照射下，应用0.45V的电压沉积600s，最后取出后经过去离子水清洗，80℃烘干得到g-C3N4/Sb2S3/Co-Pi薄膜。
实施例3
一种用于光电催化产氢的薄膜复合材料的制备方法，包括如下步骤：
步骤一：将10g尿素研磨成粉末，取8g的粉末填装到到25ml坩埚中，将FTO导电玻璃以导电面朝下的方式完全盖亚在方舟上，转移到马弗炉中，以2℃/min的升温速率加热500℃后保温2h，冷却至室温，即可得到附在FTO导电玻璃上的架状结构的g-C3N4薄膜。
步骤二：将0.96gSbCl3溶解到1.5ml的丙酮中后加入72.5ml的去离子水，将9.3g的Na2S2O3·5H2O加入到25ml的去离子水中，将Na2S2O3·5H2O溶液倒入到SbCl3溶液中，磁力搅拌至溶液变成橘红色，即为生长溶液，然后将步骤一制得的样品置于60℃的生长溶液中水浴1.5h，取出后经过去离子水清洗，80℃烘干得到g-C3N4/Sb2S3薄膜。
步骤三：称取1.4g的K2HPO4和0.55g的KH2PO4加到50ml的去离子水中，pH为7，然后加入0.06g Co(NO3)2磁力搅拌充分溶解后作为Co-Pi生长溶液备用。
g-C3N4/Sb2S3薄膜作为工作电极，Ag/AgCl作为参比电极，Pt片作为对电极，电解液为Co-Pi生长溶液，在100mW·cm-2的氙灯照射下，应用0.35V的电压沉积60s，最后取出后经过去离子水清洗，80℃烘干得到g-C3N4/Sb2S3/Co-Pi薄膜。
本发明的作用机理是：半导体材料作为光电阳极被光照射后，吸收获得不小于其禁带宽度的光子能量，使得半导体价带上的电子被激发成为光生电子跃迁至半导体的导带位置，价带位置上留下光生空穴，从而在半导体内产生光生电子-空穴对。光生电子具有强还原性，通过外部导线到达对电极表面与水反应产生氢气。
如图1所示，本发明所获得的g-C3N4/Sb2S3/Co-Pi薄膜复合材料，因架状结构具有较大的比表面积，Sb2S3和Co-Pi分布情况良好。本发明所制得的g-C3N4/Sb2S3/Co-Pi薄膜复合材料可见光吸收优异，光电催化性能较高。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。
Claims (2)
1.一种用于光电催化产氢的薄膜复合材料的制备方法，其特征在于，包括如下步骤：
步骤一：通过热蒸气液聚法制备g-C3N4薄膜，将5-10g的尿素或者硫脲研磨成细粉末，然后取1.5-8g细粉末装满到坩埚或者方舟中，将FTO导电玻璃以导电面朝下的方式盖压在坩埚或者方舟上，转移到马弗炉中处理，以2℃/min的升温速率加热到200℃后保温1h然后继续以2℃/min升温到500℃后保温2h，冷却至室温；或者以2℃/min的升温速率加热500℃后保温2h，冷却至室温，即可得到附在FTO导电玻璃上的架状结构的g-C3N4薄膜；
步骤二：采用水浴法将Sb2S3纳米球负载到g-C3N4薄膜上，将步骤一中制备的样品置于60-70℃的生长溶液中水浴反应0.5-1.5h，所述生长溶液的制备工艺参数为：将0.64-0.96gSbCl3溶解在1体积的丙酮中，然后加入29体积的去离子水，得到SbCl3溶液；将6.2-9.3gNa2S2O3·5H2O溶解在25mL的去离子水中，得到Na2S2O3·5H2O溶液；将Na2S2O3·5H2O溶液加入到SbCl3溶液中，磁力搅拌至变成橘红色即为生长溶液，其中Na2S2O3·5H2O溶液与SbCl3溶液的体积比为1:3，样品取出后经过去离子水清洗，80℃烘干得到g-C3N4/Sb2S3薄膜；
步骤三：通过光电化学沉积法将Co-Pi纳米颗粒沉积到g-C3N4/Sb2S3薄膜上，将制得的g-C3N4/Sb2S3薄膜作为工作电极，Ag/AgCl作为参比电极，Pt片作为对电极，电解液为Co-Pi生长溶液，其制备工艺参数为：Co(NO3)2溶液与磷酸钾溶液以浓度比1:200的比例混合，光源为100mW cm-2的氙灯，应用电压为0.35-0.45V，沉积时间为60～600s；沉积薄膜后经过去离子水清洗，80℃烘干，最终得到g-C3N4/Sb2S3/Co-Pi薄膜复合材料。
2.如权利要求1所述的一种用于光电催化产氢的薄膜复合材料的制备方法，其特征在于，所述磷酸钾溶液的制备工艺参数为：K2HPO4和KH2PO4溶液以体积比为8：5混合，即为磷酸钾溶液，此时磷酸钾溶液的pH为7。
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