Synchronistic synthesis and immobilization of phthalocyanine on graphene oxide and its photocatalytic performance

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

Abstract

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

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

CLC Number:

TQ426

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.

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.

Figures/Tables 12

References 23

1	BHUVANESWARI K , PALANISAMY G , PAZHANIVEL T , et al . Photocatalytic performance on visible light induced ZnS QDs-MgAl layered double hydroxides hybrids for methylene blue dye degradation[J]. Chemistry Select, 2018, 3(47): 13419-13426.
2	HU M Q , LOU H , YAN X L , et al . In-situ fabrication of ZIF-8 decorated layered double oxides for adsorption and photocatalytic degradation of methylene blue[J]. Microporous and Mesoporous Materials, 2018, 271: 68-72.
3	MAHMOODI N M , ABDI J . Nanoporous metal-organic framework (MOF-199): synthesis, characterization and photocatalytic degradation of basic blue 41[J]. Microchemical Journal, 2019, 144: 436-442.
4	NIE Y C , YU F , WANG L C , et al . Photocatalytic degradation of organic pollutants coupled with simultaneous photocatalytic H₂evolution over graphene quantum dots/Mn-N-TiO₂/g-C₃N₄ composite catalysts: performance and mechanism[J]. Applied Catalysis B: Environmental, 2018, 227: 312-321.
5	AGOCS T Z , PUSKAS I , VARGA E , et al . Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants[J]. Beilstein Journal of Organic Chemistry, 2016, 12: 2873-2882.
6	LOEB S K , ALVAREZ P J J , BRAME J A , et al . The technology horizon for photocatalytic water treatment: sunrise or sunset?[J]. Environmental Science & Technology, 2018, 53(6): 2937-2947.
7	BOTTARI G , DE LA TORRE G , TORRES T , et al . Phthalocyanine-nanocarbon ensembles: from discrete molecular and supramolecular systems to hybrid nanomaterials[J]. Accounts of Chemical Research, 2015, 48(4): 900-910.
8	ZHANG W J , SONG N Z , ZHENG H J , et al . Cobalt phthalocyanine tetracarboxylic acid functionalized polymer monolith for selective enrichment of glycopeptides and glycans[J]. Proteomics, 2018, 18(20): 1-24.
9	MADHURI K P , JOHN N S . Supercapacitor application of nickel phthalocyanine nanofibres and its composite with reduced graphene oxide[J]. Applied Surface Science, 2017, 449: 528-536.
10	ZHANG X H , PENG T Y , YU L Y , et al . Visible/near-infrared-light-induced H₂productionover g-C₃N₄Co-sensitized by organic dye and zinc phthalocyanine derivative[J]. ACS Catalysis, 2015, 5(2): 504-510.
11	ZHANG X , WU Z S , ZHANG X , et al . Highly selective and active CO₂ reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures[J]. Nature Communications, 2017, 8: 14675-14683.
12	LIM J Y, MUBARAK N M , ABDULLAH E C , et al . Recent tends in the synthesis of graphene and graphene oxide based nanomaterials for removal of heavy metals:a review[J]. Journal of Industrial and Engineering Chemistry, 2018, 66: 29-44.
13	ZHANG F L , LI S , ZHANG Q , et al . Adsorption of different types of surfactants on graphene oxide[J]. Journal of Molecular Liquids, 2019, 276: 338-346.
14	USMAN M S , HUSSEIN M Z , KURA A U , et al . Graphene oxide as a nanocarrier for a theranostics delivery system of protocatechuic acid and gadolinium/gold nanoparticles[J]. Molecules, 2018, 23(2): 500-516.
15	SIRIVIRIYANUN A , TSAI Y J , VOON S H , et al . Cyclodextrin- and dendrimer-conjugated graphene oxide as a nanocarrier for the delivery of selected chemotherapeutic and photosensitizing agents[J]. Materials Science & Engineering C, 2018, 89: 307-315.
16	VADIVEL S , VANITHA M , MUTHUKRISHNARAJ A , et al . Graphene oxide-BiOBr composite material as highly efficient photocatalyst for degradation of methylene blue and rhodamine-B dyes[J]. Journal of Water Process Engineering, 2014, 1: 17-26.
17	DANG L F , LIU Y F , ZHANG R R , et al . Immobilization of β-(N,N-dimethylaminoethoxy) phthalocyanine zinc on silica surface and its photocatalytic activity[J]. Journal of Functional Polymers, 2019, 32(4): 493-500.
18	HU L , ZHANG H J , GAO A Q , et al . Functional modification of cellulose fabrics with phthalocyanine derivatives and the UV light-induced antibacterial performance[J]. Carbohydrate Polymers, 2018, 201: 382-386.
19	MANI V , DEVASENATHIPATHY R , CHEN S M , et al . Immobilization of glucose oxidase on graphene and cobalt phthalocyanine composite and its application for the determination of glucose[J]. Enzyme and Microbial Technology, 2014, 66: 60-66.
20	DOU T W , ZANG L L , ZHANG Y H , et al . Hybrid g-C₃N₄ nanosheet/carbon paper membranes for the photocatalytic degradation of methylene blue[J]. Materials letters, 2019, 244: 151-154.
21	PARK J A , YANG B , LEE J, et al . Ultrasonic spray pyrolysis synthesis of reduced graphene oxide/anatase TiO₂ composite and its application in the photocatalytic degradation of methylene blue in water[J]. Chemosphere, 2018, 191: 738-746.
22	LU L L , SHAN R , SHI Y Y , et al . A novel TiO₂/biochar composite catalysts for photocatalytic degradation of methyl orange[J]. Chemosphere, 2019, 222: 391-398.
23	ALY H M, MOUSTAFA M E , NASSAR M Y , et al . Synthesis and characterization of novel Cu(Ⅱ) complexes with 3-substituted-4-amino-5-mercapto-1,2,4-triazole Schiff bases: a new route to CuO nanoparticles[J]. Journal of Molecular Structure, 2015, 1086: 223-231.

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