氧化石墨烯表面同步合成与固载酞菁及其光催化性能

doi:10.16085/j.issn.1000-6613.2019-0600

摘要/Abstract

摘要：

首先在氧化石墨烯（GO）上键合邻苯二腈前体，然后通过“同步合成与固载”的方法在含邻苯二腈的GO表面键合醛基钴酞菁（CoAlPc），制得GO负载化的钴酞菁复合催化剂CoAlPc/GO。通过红外光谱仪（FTIR）、透射电镜（TEM）、紫外-可见光分光光度计（UV-vis）等对其结构、形貌进行表征。以有机污染物亚甲基蓝（MB）为目标降解物，研究所制CoAlPc/GO复合催化剂在可见光下的光催化性能。重点考察了pH和CoAlPc/GO投加量对亚甲基蓝降解率的影响及其循环稳定性。结果表明，通过共价键合的方法能够成功在GO表面固载醛基钴酞菁（CoAlPc），得到负载化酞菁光催化剂CoAlPc/GO。所制备的CoAlPc/GO电荷转移阻抗较CoAlPc大大减小，从而表现出良好的光催化活性。可见光照射60min，在一定量H₂O₂存在下，较低的CoAlPc/GO用量（0.003g）便能有效催化MB降解，其降解率高达99.9%。MB在 $· O 2 -$ 、·OH和空穴的共同作用下氧化降解。此外，CoAlPc/GO还表现出了很好的重复使用性，循环使用7次仍具有较好的光催化活性。

关键词: 酞菁, 氧化石墨烯, 同步合成与固载, 催化剂, 降解

Abstract:

Graphene oxide(GO) supported cobalt phthalocyanine composite catalyst CoAlPc/GO was prepared by synchronistic synthesis and immobilization of aldehyde cobalt phthalocyanine (CoAlPc) on the GO surface, which was initially bonded with phthalonitrile. The structure and morphology of the composite catalyst were characterized by FTIR, TEM and UV-vis spectroscopy. Finally, the photocatalytic activity of CoAlPc/GO was investigated under visible light by using methylene blue (MB) as the target degradant. The effects of dosage and pH of CoAlPc/GO on the degradation rate of MB and reusability were investigated. The results showed that CoAlPc was successfully supported on the GO surface by synchronous synthesis and immobilization, yielding a heterogeneous photocatalyst CoAlPc/GO. CoAlPc/GO showed a smaller charge transfer impedance than CoAlPc, thus exhibited good photocatalytic activity. In the presence of a certain amount of H₂O₂, and visible light irradiation of 60min, MB could be effectively degraded by only small amount of CoAlPc/GO (0.003g), and the degradation rate was as high as 99.9%. MB was degraded by the synergistic effects from ·O₂ ^-、·OH and the holes. Moreover, CoAlPc/GO also possessed good reusability, and its photocatalytic activity was still good after reused for 7 times.

Key words: phthalocyanine, graphene oxide, synchronistic synthesis and immobilization, catalyst, degradation

中图分类号:

TQ426

刘叶峰,左鹏,陈南,王飞,焦纬洲,王蕊欣. 氧化石墨烯表面同步合成与固载酞菁及其光催化性能[J]. 化工进展, 2020, 39(1): 190-198.

Yefeng LIU,Peng ZUO,Nan CHEN,fei WANG,Weizhou JIAO,Ruixin WANG. Synchronistic synthesis and immobilization of phthalocyanine on graphene oxide and its photocatalytic performance[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 190-198.

图/表 12

图1 在GO表面同步合成与固载CoAlPc的化学反应过程

图2 NH2-GO、AlPPN/GO和CoAlPc/GO的红外光谱图

图3 GO、AlPPN/GO和CoAlPc/GO在THF中的紫外可见光谱图

图4 GO和CoAlPc/GO的热失重曲线图

图5 GO、CoAlPc/GO的HR-TEM和CoAlPc/GO的EDS谱图

图6 CoAlPc和CoAlPc/GO的交流阻抗图

图7 CoAlPc/GO对亚甲基蓝溶液光催化降解活性的影响

图8 CoAlPc/GO光催化降解MB的反应机理示意图

图9 CoAlPc/GO用量对光催化降解MB的影响

图10 不同pH的CoAlPc/GO用量对MB的光催化降解曲线图和zeta电位图

图11 CoAlPc/GO和CoAlPc/GO-H2O2对MB的光催化降解曲线

图12 CoAlPc/GO催化剂光催化降解MB的重复使用性

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