CN105597828B - 一种氧化石墨烯/卟啉复合物光催化剂的制备方法 - Google Patents
一种氧化石墨烯/卟啉复合物光催化剂的制备方法 Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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Abstract
本发明属于光催化技术领域，具体为一种氧化石墨烯/卟啉复合物光催化剂的制备方法。本发明方法的具体步骤如下：(1)将氧化石墨烯于水中分散，得到氧化石墨烯分散液；再向其中加入可溶性金属盐，之后离心分离，取下层沉淀，干燥、研磨，得到粉末状的金属离子掺杂的氧化石墨烯；(2)将金属离子掺杂的氧化石墨烯分散在水中，加入溶有卟啉化合物的四氢呋喃溶液，离心，取下层沉淀，干燥即得氧化石墨烯/卟啉复合材料。本发明反应条件温和，操作简单，成本低廉；其将金属离子作为卟啉/氧化石墨烯的界面连接剂，促进光生电子在氧化石墨烯和卟啉间的快速传递，进而抑制复合材料快速的电子‑空穴复合，从而提高催化剂的催化性能。
Description
技术领域
本发明涉及光催化技术领域，具体的说，涉及一种氧化石墨烯/卟啉复合物光催化剂的制备方法。
背景技术
由于化石燃料的短缺和环境污染问题已经出现在人们的面前，开发一种新能源是现如今人们关注的重点问题。通过光催化利用太阳能生产清洁的氢气是其中一个重要方式。然而，由于对光的弱吸收能力，电子-空穴的快速复合和低稳定性的束缚，目前研究材料的光转换效率仍然很低。
氧化石墨烯(GO)具有优异的结构特性，如大的比表面积，高的电子和热导率。此外，丰富的含氧官能团，如环氧，羟基和羧基，使得GO更容易被进一步改性。CN201310473878公开了光催化剂氧化石墨烯掺杂二氧化钛纳米纤维及其制备方法，将二氧化钛凝胶纤维按照5℃/min的速度进行升温至600℃，维持炉温3h，然后随炉冷却至室温20～25℃制得二氧化钛纳米纤维，然后将所述二氧化钛纳米纤维均匀分散在乙醇中，并向其中加入氧化石墨烯，继续分散至少2h，即可制得氧化石墨烯掺杂二氧化钛纳米纤维。该催化剂具有较好的光催化性能，适合应用在有机物的光解，污水处理等多方面，但是对于电子-空穴的快速复合没有提出更好的解决办法。中国专利(公开号：104028309 A)公开了一种卟啉敏化的二氧化钛纳米线/还原氧化石墨烯复合材料，首先制备二氧化钛纳米线和还原氧化石墨烯，然后用电泳沉积法将还原氧化石墨烯沉积在二氧化钛纳米线上，最后用卟啉敏化二氧化钛/还原氧化石墨烯复合材料，得到复合型光催化剂。该复合型光催化剂主要利用染料敏化的原理，对亚甲基蓝等有机污染物有较好的催化降解作用，但是对光生电子-空穴对的快速复合也没有提出更好的解决办法。CN201410621933涉及一种银/氧化石墨烯/氮化碳复合光催化材料及其制备方法。利用银的高电导性可以加速光生电子对的分离，延长活性组分的寿命，提高了复合光催化材料的催化活性，但是所用的银价格较贵，限制了产品的推广应用。
卟啉具有特殊的大环共轭结构，其特殊的结构和热稳定性在催化领域已被广泛关注。
发明内容
为了克服现有技术的不足，本发明的目的在于提供一种新型的氧化石墨烯/卟啉复合物光催化剂的制备方法。以金属离子作为界面连接剂，卟啉作为光的捕获体，氧化石墨烯作为电子传递的受体，通过配位作用和静电作用，制备了一种新型的氧化石墨烯/卟啉复合物光催化剂。其方法工艺简单，反应条件温和、成本低廉，所得催化剂催化活性高。
为了提高光生电子的转移效率，抑制光生电子-空穴的快速复合，本发明通过加入金属离子改变氧化石墨烯和卟啉之间的界面连接模式，进而提高氧化石墨烯和卟啉之间电子转移效率和复合光催化剂的制氢活性。
本发明提供了一种氧化石墨烯/卟啉复合物光催化剂的制备方法，具体步骤如下：
(1)将氧化石墨烯(GO)于水中分散，得到氧化石墨烯分散液；再向其中加入可溶性金属盐，之后离心分离，取下层沉淀，干燥后研磨，得到粉末状的金属离子掺杂的氧化石墨烯(GO-M)；
(2)将金属离子掺杂的氧化石墨烯(GO-M)分散在水中，加入溶有卟啉化合物的四氢呋喃溶液，离心，取下层沉淀，干燥即得氧化石墨烯/卟啉(GO-M-P)复合材料。
本发明中，可溶性金属盐选自可溶性的钾盐、钙盐、锌盐、铜盐、钴盐或者铬盐中的一种或几种。本发明中的可溶是指金属离子对应的金属盐溶于水，如对钾盐来说，可以是KCl、K2SO4，KNO3，K2CO3等，对于钙盐来说，可以是CaCl2，Ca(NO3)2等，而CaCO3因为不溶于水，所以不适合。
本发明中，氧化石墨烯与可溶性金属盐的质量比为8:1～20:1，其中优选的质量比为9：1～15：1。
本发明中，氧化石墨烯分散液中，氧化石墨烯的质量比浓度在6％-10％之间。
本发明中，氧化石墨烯与卟啉化合物的质量比为90：10～98：2，其中优选的质量比为93：7～97：3。
本发明中，卟啉化合物选自(5,15-二苯基)-10,20-二(4-吡啶基)卟啉，(5,15-二苯基)-10,20-二(4-羟基苯基)卟啉或(5,15-二苯基)-10,20-二(4-羧基苯基)卟啉中的一种或几种。
本发明中，在含有卟啉化合物的四氢化喃溶液中，卟啉化合物的质量百分比浓度在3％-8％之间。
本发明的有益效果在于：本发明反应条件温和，操作简单，成本低廉；其将金属离子作为界面连接剂，促进光生电子在GO和卟啉间的快速传递，进而抑制复合材料快速的电子-空穴复合，从而提高催化剂的催化性能。
具体实施方式
下面结合具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例1
取8g氧化石墨烯加入到100g去离子水中，得到氧化石墨烯水分散液。然后加入1g六水氯化铬搅拌1h后离心。将离心得到的下层沉淀放入真空烘箱中45℃干燥6h后取出并研磨成粉末状。将掺杂铬离子的氧化石墨烯分散在100g去离子水中，加入5g含4％(wt％)(5,15-二苯基)-10,20-二(4-吡啶基)卟啉的四氢呋喃溶液，搅拌2h后，离心并在45℃真空烘箱中干燥即得氧化石墨烯/卟啉复合物(GO-Cr-P)光催化剂。
实施例2
取20g氧化石墨烯加入到200g去离子水中，得到氧化石墨烯分散液。然后加入1g醋酸钴搅拌2h后离心。将离心得到的下层沉淀放入真空烘箱中45℃干燥6h后取出并研磨成粉末状。将掺杂钴离子的氧化石墨烯分散在250g去离子水中，加入50g含4％(wt％)(5,15-二苯基)-10,20-二(4-吡啶基)卟啉的四氢呋喃溶液，搅拌2h后，离心并在45℃真空烘箱中干燥即得氧化石墨烯/卟啉复合物(GO-Co-P)光催化剂。
实施例3
取10g氧化石墨烯加入100g去离子水中，得到氧化石墨烯分散液。然后加入0.3g氯化钾和0.4g醋酸锌搅拌2h后离心。将离心得到的下层沉淀放入真空烘箱中45℃干燥6h后取出并研磨成粉末状。将掺杂钾离子和锌离子的氧化石墨烯分散在150g去离子水中，加入15g含4％(wt％)(5,15-二苯基)-10,20-二(4-羧基苯基)卟啉的四氢呋喃溶液，搅拌2h后，离心并在45℃真空烘箱中干燥即得氧化石墨烯/卟啉复合物(GO-K-Zn-P)光催化剂。
实施例4
取8g氧化石墨烯加入到100g去离子水中，得到氧化石墨烯水分散液。然后加入1g六水氯化铬搅拌1h后离心。将离心得到的下层沉淀放入真空烘箱中45℃干燥6h后取出并研磨成粉末状。将掺杂铬离子的氧化石墨烯分散在100g去离子水中，加入5g含4％(wt％)(5,15-二苯基)-10,20-二(4-羟基苯基)卟啉的四氢呋喃溶液，搅拌2h后，离心并在45℃真空烘箱中干燥即得氧化石墨烯/卟啉复合物(GO-Cr-P)光催化剂。
比较例1
取8g氧化石墨烯加入100g去离子水中，加入5g含4％(wt％)(5,15-二苯基)-10,20-二(4-吡啶基)卟啉的四氢呋喃溶液，搅拌2h后，离心并在45℃真空烘箱中干燥即得氧化石墨烯/卟啉复合物(GO-P)光催化剂。
界面电阻测试
以实施例4得到的GO-Cr-P复合材料、比较例1得到的GO-P材料，以及以实施例4的工艺条件制备的其他复合材料(区别仅在于，制备过程中将六水氯化铬分别用其他不同可溶性盐代替)作为样品，将涂有样品的FTO导电玻璃作为工作电极，铂丝作为对电极，Ag/AgCl电极作为参比电极，含有0.1mol L-1 KCl的0.01mol L-1 K3Fe(CN)6/K4Fe(CN)6(1:1)的水溶液为电解质。在室温条件下利用电化学工作站测试。界面电阻测试结果如表1所示。
表1各种复合物的界面电阻
| 复合物 | GO-P | GO-Co-P | GO-Cr-P | GO-Cu-P | GO-Ca-P | GO-Zn-P | GO-Zn-K-P |
| 电阻(Ω) | 112 | 54 | 56 | 64 | 69 | 73 | 65 |
光催化性能测试
分别将10mg的样品与6mL三乙醇胺和54mL去离子水放在光解水反应器皿中，300W氙灯作为光源，使用氮气(99.99％)作为载气，抽真空，使用在线气相色谱仪分析。性能测试结果如表2所示。
表2氧化石墨烯/卟啉复合物光催化制氢性能
结果表明：金属离子的引入由于减小了卟啉和氧化石墨烯之间的界面电阻，提高了卟啉光电子的转移效率，从而明显提高卟啉/氧化石墨烯复合催化剂的光催化性能。由于不同金属离子，相同类型的卟啉或相同金属离子，不同类型的卟啉之间的配位键强度不同，因此导致金属在作为界面桥连剂时对卟啉光生电子的转移也存在差别。在我们所研究的卟啉分子中(5,15-二苯基)-10,20-二(4-吡啶基)卟啉的活性较高，钴离子作为界面桥连剂界面电子电阻最小。
Claims (8)
1.一种氧化石墨烯/卟啉复合物光催化剂的制备方法，其特征在于，具体步骤如下：
(1)将氧化石墨烯于水中分散，得到氧化石墨烯分散液；再向其中加入可溶性金属盐，之后离心分离，取下层沉淀，干燥、研磨，得到粉末状的金属离子掺杂的氧化石墨烯；所述可溶性金属盐选自可溶性的钾盐、钙盐、锌盐、铜盐、钴盐或者铬盐中的一种或几种；
(2)将金属离子掺杂的氧化石墨烯分散在水中，加入溶有卟啉化合物的四氢呋喃溶液，离心，取下层沉淀，干燥即得金属离子桥连的氧化石墨烯/卟啉复合材料。
2.根据权利要求1所述的制备方法，其特征在于，氧化石墨烯与可溶性金属盐的质量比为8:1～20:1。
3.根据权利要求2所述的制备方法，其特征在于，氧化石墨烯与可溶性金属盐的质量比为9:1～15:1。
4.根据权利要求1所述的制备方法，其特征在于，氧化石墨烯分散液中，氧化石墨烯的质量比浓度在6％-10％之间。
5.根据权利要求1所述的制备方法，其特征在于，氧化石墨烯与卟啉化合物的质量比为90：10～98：2。
6.根据权利要求1所述的制备方法，其特征在于，氧化石墨烯与卟啉化合物的质量比为93：7～97：3。
7.根据权利要求5或6所述的制备方法，其特征在于，所述卟啉化合物选自(5,15-二苯基)-10,20-二(4-吡啶基)卟啉，(5,15-二苯基)-10,20-二(4-羟基苯基)卟啉或(5,15-二苯基)-10,20-二(4-羧基苯基)卟啉中的一种或几种。
8.根据权利要求1所述的制备方法，其特征在于，在含有卟啉化合物的四氢化喃溶液中，卟啉化合物的质量百分比浓度在3％-8％之间。
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| CN102498239A (zh) * | 2009-08-04 | 2012-06-13 | 金泰克斯公司 | 用于电化学传感器中的阴极材料和相关的装置、以及其制造方法 |
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| CN101773855A (zh) * | 2010-01-19 | 2010-07-14 | 华南理工大学 | 大环化合物修饰石墨烯的氧还原催化剂及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| "负载于多壁碳纳米管上卟啉锡的可见光催化活性";严亚，等;《无机化学学报》;20101031;第26卷(第10期);第1.1-1.4节 * |
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