CN109174143A - 一种钙钛矿基复合纳米光催化材料及制备方法与用途 - Google Patents
一种钙钛矿基复合纳米光催化材料及制备方法与用途 Download PDFInfo
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Abstract
本发明涉及一种钙钛矿基复合纳米光催化材料及制备方法与用途，属于材料制备和光催化的技术领域。本发明制备出具有还原性和催化性的二维铌酸钙钾纳米片，将其与非贵金属助催化剂磷化钴通过机械搅拌法制备廉价易得、结构稳定且催化活性高的磷化钴/铌酸钙钾复合光催化产氢材料。本技术方案在室温下进行物理机械搅拌复合，高效且节能。非贵金属助催化剂CoP纳米颗粒均匀分散于K+Ca2Nb3O10 ‑纳米片表面，颗粒尺寸约为2‑3nm，可提供较多活性位点，促进光生电子和空穴的分离，使复合光催化材料具有提高的产氢活性。
Description
技术领域
本发明涉及一种钙钛矿基复合纳米光催化材料及制备方法与用途，属于材料制备和光催化的技术领域。
技术背景
近年来，光催化技术因具有运行成本低、反应条件温和以及二次污染小等诸多特点，受到研究者的广泛关注。光催化分解水产氢技术可以将低密度的太阳能转化为清洁且高密度的氢能，因此它在解决能源危机与环境污染问题中有着重要的应用价值。
在众多二维半导体材料中，从Dion-Jacobson相(M[An-1BnO3n+1])层状钙钛矿结构铌酸盐剥离出的二维铌酸钙钾多元金属氧化物纳米片(K+Ca2Nb3O10 -)具有良好的稳定性能，尤其是该纳米片光催化材料的导带由高能级的Nb 4d轨道组成，产生的光生电子具有很强的还原能力能够催化水分解产氢。但是，单纯的二维K+Ca2Nb3O10 -光催化材料缺乏足够的活性位点，导致其表面大量光生电子与空穴重组而猝灭，从而降低光催化效率。为了解决这个问题，单纯的K+Ca2Nb3O10 -常被用来与助催化剂复合，得到的助催化剂/K+Ca2Nb3O10 -复合光催化剂能有效的促进光生电子和空穴的分离，最终提高光催化产氢效率。
在众多的助催化材料中，过渡金属磷化物因具有类贵金属特性、良好的电子电导率和化学稳定性受到研究者的广泛关注。其基本构筑单元是各向同性的晶体结构，易暴露出更多的活性位点，具有较高的光生电子与空穴的分离效率，因此可作为一种良好的非贵金属助催化剂。同时，相比于贵金属助催化剂，过渡金属磷化物成本低廉，原料来源广泛，更适合于商业化应用。
迄今为止，尚未发现有人采用机械搅拌法制备非贵金属助催化剂磷化钴/铌酸钙钾复合纳米光催化材料(CoP/K+Ca2Nb3O10 -)，所用的K+Ca2Nb3O10 -具有稳定的理化性质、原材料廉价易得、无毒且以其为载体制备CoP/K+Ca2Nb3O10 -复合纳米光催化材料的反应工艺简单，所得产品光催化活性好，稳定性高，生产过程绿色环保，有望大规模工业化生产。
发明内容
本发明目的是提供一种新的在室温条件下，以简单易行的机械搅拌法合成非贵金属助催化剂CoP/K+Ca2Nb3O10 -复合纳米光催化材料的方法。
本发明通过以下技术方案实现：
步骤(1)制备铌酸钙钾纳米片(K+Ca2Nb3O10 -)：称取干燥的K2CO3、CaCO3和Nb2O5于研钵中，经研磨混合后置于半封闭的坩埚中，随后将坩埚转移至自动程序控温的升温管式炉中在1000-1200℃煅烧8-10h。待自然冷却至室温后，取出，用研钵研磨至粉末状后，加入到5mol·L-1的HNO3溶液中搅拌2-3d，进行质子化处理。将质子化得到的白色沉淀用去离子水和无水乙醇清洗去除HNO3，再经离心、干燥得到白色固体HCa2Nb3O10。称取HCa2Nb3O10和质量分数为10％的四丁基氢氧化铵溶液加入到去离子水中搅拌7d后，经离心得上层胶质物质。最后将胶质物质逐滴加入到2mol·L-1的KCl溶液中得到白色沉淀，将上述沉淀用去离子水和无水乙醇清洗，离心，真空干燥得到K+Ca2Nb3O10 -纳米片。
步骤(2)制备非贵金属助催化剂磷化钴纳米颗粒(CoP)：量取0.05mol·L-1的Co(NO3)2·6H2O溶液于烧杯中搅拌，以2秒/滴的速度滴加0.25mol·L-1的NaOH溶液于烧杯中得到混合溶液，并将混合溶液搅拌2h，最后将得到的Co(OH)2沉淀经离心、去离子水洗涤、无水乙醇洗涤后，置于60℃真空烘箱中，干燥12h。取出干燥的Co(OH)2与NaH2PO2·H2O研磨，混匀后置于坩埚中，随后将坩埚转移至自动程序控温的升温管式炉中在氮气保护下250-300℃煅烧0.5-1h，待自然冷却至室温后，取出，所得黑色粉末为CoP纳米颗粒。
步骤(3)制备磷化钴/铌酸钙钾复合纳米光催化材料(CoP/K+Ca2Nb3O10 -)：称取K+Ca2Nb3O10 -纳米片分散于去离子水中，经超声、搅拌处理得到均一稳定的悬浊液；在搅拌的情况下加入CoP纳米颗粒，加入完毕后继续机械搅拌12h，最后将所得混合液体置于60℃真空烘箱中，干燥12h，得到CoP/K+Ca2Nb3O10 -复合纳米光催化材料。
所述铌酸钙钾纳米片合成过程中，K+、Ca2+和Nb5+的摩尔比为1.1:2:3。HCa2Nb3O10和四丁基氢氧化铵溶液的比例为1g：5ml。
所述非贵金属助催化剂磷化钴/铌酸钙钾复合纳米光催化材料中，磷化钴占磷化钴/铌酸钙钾复合纳米光催化材料质量的0.7-4％，优选1％。
所述超声分散所用超声机的功率为250W，超声处理时间为0.5-1h。
所述机械搅拌处理使用磁力搅拌器，搅拌处理时间为0.5h-7d。
利用X射线衍射仪(XRD)、透射电子显微镜(TEM)以及高分辨透射电子显微镜(HRTEM)对产物进行形貌结构分析，并通过Labsolar 6A全玻璃自动在线微量气体分析系统及气相色谱仪检测光催化分解水产氢效率。
与现有技术相比，本发明的有益效果是：本技术方案制备出具有还原性和催化性的二维K+Ca2Nb3O10 -纳米片，将其与非贵金属助催化剂CoP通过机械搅拌法制备廉价易得、结构稳定且催化活性高的光催化产氢材料，采用资源丰富、低成本、无毒且无污染的原材料，有利于环保，且制备工艺简单可与现有技术制备的光催化材料相比，本技术方案在室温下进行物理机械搅拌复合，高效且节能。非贵金属助催化剂CoP纳米颗粒均匀分散于K+Ca2Nb3O10 -纳米片表面，颗粒尺寸为2-3nm，可提供较多活性位点，促进光生电子和空穴的分离，使复合光催化材料具有提高的产氢活性。
附图说明
图1为K+Ca2Nb3O10 -、CoP以及CoP/K+Ca2Nb3O10 -复合纳米光催化剂的XRD衍射谱图。由图可以看出，CoP、K+Ca2Nb3O10 -单体和CoP/K+Ca2Nb3O10 -复合纳米光催化材料已成功制备且复合样品结晶度高、无杂质。
图2a和b为1％CoP/K+Ca2Nb3O10 -样品的不同尺度的透射电子显微镜照片。a中插图为K+Ca2Nb3O10 -单体样品的高分辨透射电子显微镜照片；b中插图为CoP单体样品的高分辨透射电子显微镜照片。由图可以看出，CoP/K+Ca2Nb3O10 -复合纳米光催化材料已成功制备且其中的CoP和K+Ca2Nb3O10 -具有清晰可见的晶格条纹。
图3为不同质量比的光催化材料催化分解水产氢效率图，所制备的1％CoP/K+Ca2Nb3O10 -复合纳米光催化材料具有最优异的光催化活性，样品在催化反应5h后产氢效率达452umol·g-1。
具体实施方式
实施例1K+Ca2Nb3O10 -纳米片的制备
K+Ca2Nb3O10 -纳米片的制备采用高温固相反应法：称取0.3406g K2CO3、0.8968gCaCO3和1.7865g Nb2O5于研钵中，经研磨混合后置于半封闭的坩埚中，然后将坩埚转移至自动程序控温的升温管式炉中1200℃煅烧10h。待自然冷却至室温后取出，用研钵研磨至粉末状后，取4g加入到200ml 5mol·L-1的HNO3溶液中搅拌3d，进行质子化处理。将质子化得到的白色沉淀分别用去离子水和无水乙醇清洗3次除去HNO3，再经6000rad/min离心，60℃烘干12h得到白色固体HCa2Nb3O10。取0.1g HCa2Nb3O10和0.5ml质量分数10％的四丁基氢氧化铵溶液分散于100ml去离子水搅拌7d，经1500rad/min离心得上层胶质物体。最后将胶质物体以3秒/滴的速度逐滴加入到100ml 2mol·L-1的KCl溶液中得到白色沉淀，将上述沉淀分别用去离子水和无水乙醇清洗3次，经6000rad/min离心，最后置于60℃真空干燥箱中干燥24h得到K+Ca2Nb3O10 -纳米片。
实施例2非贵金属助催化剂CoP纳米颗粒的制备
CoP助催化剂的制备采用共沉淀法和低温磷化法：量取50ml 0.05mol·L-1的Co(NO3)2·6H2O溶液于烧杯中搅拌，以2秒/滴的速度滴加20ml 0.25mol·L-1的NaOH溶液于烧杯中得到混合溶液，并将混合溶液搅拌2h，最后将得到的Co(OH)2沉淀经离心、去离子水洗涤3次、无水乙醇洗涤3次后，置于60℃真空烘箱中，干燥12h。取出0.05g干燥的Co(OH)2与0.25g NaH2PO2·H2O研磨，混匀后置于坩埚中，随后将坩埚转移至自动程序控温的升温管式炉中在氮气保护下300℃煅烧1h，升温速率为2℃/min，待反应结束自然冷却至室温后，取出，所得黑色粉末为CoP纳米颗粒。
实施例3 0.7％CoP/K+Ca2Nb3O10 -复合纳米光催化材料的制备
CoP/K+Ca2Nb3O10 -复合纳米光催化材料的制备采用机械搅拌法：称取0.0993g K+Ca2Nb3O10 -分散于60ml去离子水中，经超声处理1h和搅拌处理1h得到均一稳定的悬浊液。在搅拌的情况下，加入0.0007g CoP纳米颗粒于上述悬浊液搅拌12h，充分混合。将上述所得混合液体置于60℃真空烘箱中，干燥12h，取出，研磨成粉末得到0.7％CoP/K+Ca2Nb3O10 -复合纳米光催化材料。
实施例4 1％CoP/K+Ca2Nb3O10 -复合纳米光催化材料的制备
CoP/K+Ca2Nb3O10 -复合纳米光催化材料的制备采用机械搅拌法：称取0.0990g K+Ca2Nb3O10 -分散于60ml去离子水中，经超声处理1h和搅拌处理1h得到均一稳定的悬浊液。在搅拌的情况下，加入0.0010g CoP纳米颗粒于上述悬浊液搅拌12h，充分混合。将上述所得混合液体置于60℃真空烘箱中，干燥12h，取出，研磨成粉末得到1％CoP/K+Ca2Nb3O10 -复合纳米光催化材料。
实施例5 2％CoP/K+Ca2Nb3O10 -复合纳米光催化材料的制备
CoP/K+Ca2Nb3O10 -复合纳米光催化材料的制备采用机械搅拌法：称取0.0980g K+Ca2Nb3O10 -分散于60ml去离子水中，经超声处理1h和搅拌处理1h得到均一稳定的悬浊液。在搅拌的情况下，加入0.0020g CoP纳米颗粒于上述悬浊液搅拌12h，充分混合。将上述所得混合液体置于60℃真空烘箱中，干燥12h，取出，研磨成粉末得到2％CoP/K+Ca2Nb3O10 -复合纳米光催化材料。
实施例6 4％CoP/K+Ca2Nb3O10 -复合纳米光催化材料的制备
CoP/K+Ca2Nb3O10 -复合纳米光催化材料的制备采用机械搅拌法：称取0.0960g K+Ca2Nb3O10 -分散于60ml去离子水中，经超声处理1h和搅拌处理1h得到均一稳定的悬浊液。在搅拌的情况下，加入0.0040g CoP纳米颗粒于上述悬浊液搅拌12h，充分混合。将上述所得混合液体置于60℃真空烘箱中，干燥12h，取出，研磨成粉末得到4％CoP/K+Ca2Nb3O10 -复合纳米光催化材料。
实施例7 CoP/K+Ca2Nb3O10 -复合纳米材料光催化活性实验
(1)以甲醇为牺牲剂：配制100ml 20vol％的甲醇/水溶液置于光催化反应瓶中。
(2)称取0.050g CoP/K+Ca2Nb3O10 -复合纳米光催化材料，加入到步骤(1)所配好的反应液中，持续搅拌，开启冷却水，光催化反应瓶抽真空后，进行光催化产氢实验。
(3)通过气相色谱仪每1h检测一次体系内气体成分。
(4)由图3可见所制备的CoP/K+Ca2Nb3O10 -复合纳米光催化材料具有优异的光催化产氢活性，尤其是1％CoP/K+Ca2Nb3O10 -样品在催化反应5h后产氢效率达452umol·g-1。
Claims (6)
1.一种钙钛矿基复合纳米光催化材料的制备方法，所述钙钛矿基复合纳米光催化材料为CoP/K+Ca2Nb3O10 -复合纳米光催化材料，非贵金属助催化剂CoP纳米颗粒均匀分散于K+Ca2Nb3O10 -纳米片表面，颗粒尺寸为2-3nm，其特征在于：采用机械搅拌法制备CoP/K+Ca2Nb3O10 -复合纳米光催化材料，具体步骤如下：称取K+Ca2Nb3O10 -纳米片分散于去离子水中，经超声、搅拌处理得到均一稳定的悬浊液；在搅拌的情况下加入CoP纳米颗粒，加入完毕后继续机械搅拌12h，最后将所得混合液体置于60℃真空烘箱中，干燥12h，得到CoP/K+Ca2Nb3O10 -复合纳米光催化材料。
2.如权利要求1所述的一种钙钛矿基复合纳米光催化材料的制备方法，其特征在于：所述CoP/K+Ca2Nb3O10 -复合纳米光催化材料中，CoP占CoP/K+Ca2Nb3O10 -复合纳米光催化材料质量的0.7％-4％。
3.如权利要求2所述的一种钙钛矿基复合纳米光催化材料的制备方法，其特征在于：所述CoP/K+Ca2Nb3O10 -复合纳米光催化材料中，CoP占CoP/K+Ca2Nb3O10 -复合纳米光催化材料质量的1％。
4.如权利要求1所述的一种钙钛矿基复合纳米光催化材料的制备方法，其特征在于：所述超声分散所用超声机的功率为250W，超声处理时间为0.5-1h。
5.如权利要求1所述的一种钙钛矿基复合纳米光催化材料的制备方法，其特征在于：所述机械搅拌处理使用磁力搅拌器，搅拌处理时间为0.5h-7d。
6.如权利要求1-5任一所述制备方法制备的钙钛矿基复合纳米光催化材料的用途，其特征在于，用于光催化分解水产氢的用途。
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