Fe3O4/g-C3N4复合催化剂增强芬顿/光-芬顿和类过氧化酶反应的活性及稳定性

引用本文: Shafaq Sahar, Akif Zeb, 刘亚男, Naseeb Ullah, 徐安武. Fe₃O₄/g-C₃N₄复合催化剂增强芬顿/光-芬顿和类过氧化酶反应的活性及稳定性[J]. 催化学报, 2017, 38(12): 2110-2119. doi: 10.1016/S1872-2067(17)62957-7 shu

Citation: Shafaq Sahar, Akif Zeb, Yanan Liu, Naseeb Ullah, Anwu Xu. Enhanced Fenton, photo‐Fenton and peroxidase-like activity and stability over Fe₃O₄/g-C₃N₄ nanocomposites[J]. Chinese Journal of Catalysis, 2017, 38(12): 2110-2119. doi: 10.1016/S1872-2067(17)62957-7 shu

Fe₃O₄/g-C₃N₄复合催化剂增强芬顿/光-芬顿和类过氧化酶反应的活性及稳定性

a 中国科学技术大学合肥微尺度物质科学国家实验室, 安徽合肥 230026, 中国;
b 国家科技大学土木与环境工程学院(SCEE), 环境科学与工程研究所(IESE), 伊斯兰堡H-12区, 巴基斯坦
基金项目:
国家自然科学基金（51572253；21771171）；中国科学院合肥科学中心（2015SRG-HSC048）；自然科学基金与荷兰科学研究组织的合作计划（51561135011）；中国科学院奖学金计划.

摘要: 石墨相的氮化碳（g-C₃N₄）已被广泛用于光催化、水分解、光子检测器、电池、以及光电阴极.与其他光催化材料相比，g-C₃N₄具有价格低廉，易制备，无毒无污染等优点.此外，C₃N₄具有适宜的带隙（2.7 eV），能有效地吸收可见光.有关C₃N₄的光催化研究很多，但是其降解效率受限于电子空穴对的快速复合.因此，为了提高C₃N₄光催化反应效率，需要对其进行改性.磁铁矿（Fe₃O₄）广泛用于光催化和芬顿/光-芬顿反应.Fe₃O₄晶体具有反式尖晶石结构，其中Fe²⁺和Fe³⁺同时存在.研究表明，磁铁矿在酸性条件下催化效果显著，然而，它的比表面积小，随着反应时间的推移，铁离子会溶出，不利于有机物降解反应.因此，近来许多研究着重于磁铁矿复合物的制备，以提高磁铁矿的稳定性及催化性能.
本文通过惰性氛围高温焙烧三聚氰胺制备了g-C₃N₄，再通过氯化铁和乙酸钠在乙醇中于180℃溶剂热反应，制备Fe₃O₄纳米粒子，最后通过静电自组装过程制备出Fe₃O₄/g-C₃N₄纳米复合材料.利用X射线衍射（XRD），扫描电子显微镜（SEM）及X射线光电子光谱（XPS）等手段验证其组成和结构.XRD结果表明，Fe₃O₄/g-C₃N₄复合材料中可以清晰看到Fe₃O₄和g-C₃N₄的衍射峰，说明这两种材料的晶相得以保持.SEM和TEM结果表明，Fe₃O₄纳米颗粒很好地附着在g-C₃N₄薄片上.XPS结果表明，氮化碳中存在典型的三种N峰；此外还存在铁的两种价态.光-芬顿活性测试中，相同条件下，Fe₃O₄/g-C₃N₄在60 min内将罗丹明B（RhB）几乎降解完全，而单组份的Fe₃O₄或g-C₃N₄对RhB的降解小于50%.可见，复合后的Fe₃O₄/g-C₃N₄光催化性能得到很大提升.单g-C₃N₄本身由于快速的电子空穴复合以及对双氧水的弱亲和力，因而对RhB降解效果差.单独的Fe₃O₄由于在中性或者碱性条件下反而会抑制光催化芬顿活性.对于制备的Fe₃O₄/g-C₃N₄复合材料，具有以下优点：（1）电子在Fe³⁺和g-C₃N₄的LUMO轨道上的转移降低了电子-空穴对的复合；（2）Fe₃O₄均匀分布在g-C₃N₄上，对于H₂O₂的吸附提供了有利的高比表面积；（3）Fe₃O₄和g-C₃N₄之间的界面相互作用使得Fe₃O₄的稳定性提高.通过降解RhB的动力学研究，得到反应速率为0.02 min^-1，属准一级反应.分析检测结果表明，光-芬顿反应后，RhB分子被彻底矿化降解，没有中间产物生成，最终降解为CO₂和水.
同时，通过对辣根过氧化物酶（HRP）模拟催化进行测试，以3，3'，5，5'-四甲基联苯胺盐酸盐（TMB）作为基质，同时添加双氧水和Fe₃O₄/g-C₃N₄，在pH值为4.5条件下，TMB可以被有效氧化.实验表明，Fe₃O₄/g-C₃N₄添加量为25 mg/ml时，对TMB氧化性能最佳.复合催化剂还用于多巴胺的催化氧化反应.结果表明，多巴胺的氧化反应速率常数为1.21 min^-1，属一级动力学反应.
总之，复合材料提高了RhB的光催化降解活性和稳定性；对TMB和HRP亲和性好，表现出高的类过氧化酶反应活性；有效的多巴胺氧化反应表明其有望用于生物基氧化反应中.实验结果表明，本文发展的Fe₃O₄/g-C₃N₄复合材料为其他类型复合材料的制备与应用提供了新的思路.

关键词:

English

Enhanced Fenton, photo‐Fenton and peroxidase-like activity and stability over Fe₃O₄/g-C₃N₄ nanocomposites

a Division of Nanomaterials and Chemistry, Hefei National Laboratory for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, Anhui, China;
b Institute of Environmental Sciences and Engineering(IESE), School of Civil and Environmental Engineering(SCEE), National University of Sciences and Technology(NUST), Sector H-12, Islamabad, Pakistan
Received Date: 10 October 2017
Revised Date: 30 October 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (51572253, 21771171), Scientific Research Grant of Hefei Science Center of CAS (2015SRG-HSC048), cooperation between NSFC and Netherlands Organization for Scientific Research (51561135011), and CAS-TWAS Scholarship Program.

Abstract: We prepared the Fe₃O₄/g-C₃N₄ nanoparticles (NPs) through a simple electrostatic self-assembly method with a 3:97 weight ratio to investigate their Fenton, photo-Fenton and oxidative functionalities besides photocatalytic functionality. We observed an improvement of the Fenton and photo-Fenton activities of the Fe₃O₄/g-C₃N₄ nanocomposites. This improvement was attributed to efficient charge transfer between Fe₃O₄ and g-C₃N₄ at the heterojunctions, inhibition of electron-hole recombination, a high surface area, and stabilization of Fe₃O₄ against leaching by the hydrophobic g-C₃N₄. The obtained NPs showed a higher degradation potential for rhodamine B (RhB) dye than those of Fe₃O₄ and g-C₃N₄. As compared to photocatalysis, the efficiency of RhB degradation in the Fenton and photo-Fenton reactions was increased by 20% and 90%, respectively. Additionally, the horseradish peroxidase (HRP) activity of the prepared nanomaterials was studied with 3,3,5,5-tetramethylbenzidinedihydrochloride (TMB) as a substrate. Dopamine oxidation was also examined. Results indicate that Fe₃O₄/g-C₃N₄ nanocomposites offers more efficient degradation of RhB dye in a photo-Fenton system compared with regular photocatalytic degradation, which requires a long time. Our study also confirmed that Fe₃O₄/g-C₃N₄ nanocomposites can be used as a potential material for mimicking HRP owing to its high affinity for TMB. These findings suggest good potential for applications in biosensing and as a catalyst in oxidation reactions.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

Fe₃O₄/g-C₃N₄复合催化剂增强芬顿/光-芬顿和类过氧化酶反应的活性及稳定性

English

Enhanced Fenton, photo‐Fenton and peroxidase-like activity and stability over Fe₃O₄/g-C₃N₄ nanocomposites

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