Laccase-like activity of Mn<sub>3</sub>O<sub>4</sub> nanoparticles and its application in degrading acridine orange

化学工业与工程

Chemcial Industry and Engineering

2025, Vol. 42

Issue (1) :59-68 DOI: 10.13353/j.issn.1004.9533.20220809

Current Issue | Next Issue | Archive | Adv Search

<< | >>

Laccase-like activity of Mn₃O₄ nanoparticles and its application in degrading acridine orange

HAN Qian, GE Zhiqiang

School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Abstract	Reference	Related Articles

Download: PDF (4635KB) HTML () Export: BibTeX or EndNote (RIS) Supporting Info

Abstract Natural laccase suffers from several inherent drawbacks, such as complex purification process, poor stability and high cost, significantly constraining their practical applications. The construction of inorganic nanozymes with laccase activity is a promising strategy to overcome these limitations. In this study, Mn₃O₄ nanoparticles were prepared using a chemical precipitation method. The laccase-like activity was evaluated using 2,4-dichlorophenol as the substrate. Additionally, the removal performance of the nanoparticles towards AO in aqueous solution was investigated. This study shows that Mn₃O₄ nanoparticles have redox activity similar to laccase, and enzyme kinetics experiments demonstrate that Mn₃O₄ nanozyme has higher catalytic efficiency than natural laccase at the same concentration. Furthermore, Mn₃O₄ nanozyme have a wider temperature (25—75 ℃) and pH (6—7) tolerance range, and the storage stability at room temperature is significantly higher than that of natural laccase. In the presence of the redox mediator HBT, Mn₃O₄ nanoparticles can swiftly and effectively remove AO from aqueous solution, with a removal efficiency of 70% in just 5 min. Therefore, Mn₃O₄, as a laccases-like nanozyme, has excellent developing potential in treatment of dye wastewater due to high catalytic activity, superior storage stability, simplicity of preparation and low cost.

	Service

	Email this article
	Add to my bookshelf
	Add to citation manager
	Email Alert
	RSS
	Articles by authors
	HAN Qian
	GE Zhiqiang

Keywords： Mn₃O₄ nanoparticles laccase nanozyme acridine orange degradation

Received 2022-09-01;

About author:

Cite this article:

HAN Qian, GE Zhiqiang.Laccase-like activity of Mn₃O₄ nanoparticles and its application in degrading acridine orange[J] Chemcial Industry and Engineering, 2025,V42(1): 59-68

[1] 赖超凤, 李爽, 彭丽丽, 等. 漆酶及其在有机合成中应用的研究进展[J]. 化工进展, 2010, 29(7): 1300-1308 LAI Chaofeng, LI Shuang, PENG Lili, et al. Progress of applications of laccase in organic synthesis[J]. Chemical Industry and Engineering Progress, 2010, 29(7): 1300-1308(in Chinese)
[2] 徐鑫, 张国庆, 胡渤洋, 等. 真菌漆酶及其介体系统: 来源、机理与应用[J]. 生物技术进展, 2020, 10(1): 30-39 XU Xin, ZHANG Guoqing, HU Boyang, et al. Fungal laccases and their mediator systems: Sources, mechanisms and applications[J]. Current Biotechnology, 2020, 10(1): 30-39(in Chinese)
[3] CAÑAS A I, CAMARERO S. Laccases and their natural mediators: Biotechnological tools for sustainable eco-friendly processes[J]. Biotechnology Advances, 2010, 28(6): 694-705
[4] 龚睿, 孙凯, 谢道月. 真菌漆酶在绿色化学中的研究进展[J]. 生物技术通报, 2018, 34(4): 24-34 GONG Rui, SUN Kai, XIE Daoyue. Applications of fungal laccase in green chemistry[J]. Biotechnology Bulletin, 2018, 34(4): 24-34(in Chinese)
[5] WEI M, LEE J, XIA F, et al. Chemical design of nanozymes for biomedical applications[J]. Acta Biomaterialia, 2021, 126: 15-30
[6] WU J, WANG X, WANG Q, et al. Nanomaterials with enzyme-like characteristics (nanozymes): Next-generation artificial enzymes (II)[J]. Chemical Society Reviews, 2019, 48(4): 1004-1076
[7] LIANG H, LIN F, ZHANG Z, et al. Multicopper laccase mimicking nanozymes with nucleotides as ligands[J]. ACS Applied Materials & Interfaces, 2017, 9(2): 1352-1360
[8] WANG Y, HE C, LI W, et al. Catalytic performance of oligonucleotide-templated Pt nanozyme evaluated by laccase substrates[J]. Catalysis Letters, 2017, 147(8): 2144-2152
[9] XU H, YAN N, QU Z, et al. Gaseous heterogeneous catalytic reactions over Mn-based oxides for environmental applications: A critical review[J]. Environmental Science & Technology, 2017, 51(16): 8879-8892
[10] DURÁN F G, BARBERO B P, CADÚS L E, et al. Manganese and iron oxides as combustion catalysts of volatile organic compounds[J]. Applied Catalysis B: Environmental, 2009, 92(1/2): 194-201
[11] MARTIN S T. Precipitation and dissolution of iron and manganese oxides[J]. Environmental Catalysis, 2005, 1: 61-82
[12] ZHANG H, WEBER E J. Identifying indicators of reactivity for chemical reductants in sediments[J]. Environmental Science & Technology, 2013, 47(13): 6959-6968
[13] KIM S C, SHIM W G. Catalytic combustion of VOCs over a series of manganese oxide catalysts[J]. Applied Catalysis B: Environmental, 2010, 98(3/4): 180-185
[14] LI X, ZHOU L, GAO J, et al. Synthesis of Mn₃O₄ nanoparticles and their catalytic applications in hydrocarbon oxidation[J]. Powder Technology, 2009, 190(3): 324-326
[15] SINGH M, KAUR M, SANGHA M K, et al. Comparative evaluation of manganese oxide and its graphene oxide nanocomposite as polyphenol oxidase mimics[J]. Materials Today Communications, 2021, 27: 102237
[16] WANG X, LIU J, QU R, et al. The laccase-like reactivity of manganese oxide nanomaterials for pollutant conversion: Rate analysis and cyclic voltammetry[J]. Scientific Reports, 2017, 7: 7756
[17] 崔国星, 朱建伟, 张启卫. 硫酸锰氧化法制备Mn₃O₄的研究[J]. 矿冶工程, 2008, 28(4): 72-76 CUI Guoxing, ZHU Jianwei, ZHANG Qiwei. Study of preparation of manganic manganous oxide from manganese sulfate by oxidation[J]. Mining and Metallurgical Engineering, 2008, 28(4): 72-76(in Chinese)
[18] GE Z, WU B, SUN T, et al. Laccase-like nanozymes fabricated by copper and tannic acid for removing malachite green from aqueous solution[J]. Colloid and Polymer Science, 2021, 299(10): 1533-1542
[19] 钟平方, 彭惠民, 彭方毅, 等. 漆酶催化酚类、苯胺类化合物的动力学分析及其测定废水中邻苯二酚的应用研究[J]. 环境科学, 2010, 31(11): 2673-2677 ZHONG Pingfang, PENG Huimin, PENG Fangyi, et al. Kinetic analysis of laccase catalyze phenolic and aniline compounds and detecting catechol in wastewater[J]. Environmental Science, 2010, 31(11): 2673-2677(in Chinese)
[20] 卢蓉, 夏黎明. 漆酶氧化还原介质系统的作用机理及其应用[J]. 纤维素科学与技术, 2004, 12(1): 37-44 LU Rong, XIA Liming. Advances in research and application of laccase mediator system[J]. Journal of Cellulose Science and Technology, 2004, 12(1): 37-44(in Chinese)
[21] ANDREU G, VIDAL T. Laccase from Pycnoporus cinnabarinus and phenolic compounds: Can the efficiency of an enzyme mediator for delignifying kenaf pulp be predicted?[J]. Bioresource Technology, 2013, 131: 536-540
[22] LI Y, QU J, GAO F, et al. In situ fabrication of Mn₃O₄ decorated graphene oxide as a synergistic catalyst for degradation of methylene blue[J]. Applied Catalysis B: Environmental, 2015, 162: 268-274
[23] REMUCAL C K, GINDER-VOGEL M. A critical review of the reactivity of manganese oxides with organic contaminants[J]. Environmental Science Processes & Impacts, 2014, 16(6): 1247-1266
[24] XIE T, DYRSSEN D. Simultaneous determination of partition coefficients and acidity constants of chlorinated phenols and gualacols by gas chromatography[J]. Analytica Chimica Acta, 1984, 160: 21-30
[25] LIN K, LIU W, GANT J. Oxidative removal of bisphenol A by manganese dioxide: Efficacy, products, and pathways[J]. Environmental Science & Technology, 2009, 43(10): 3860-3864
[26] 孔晓燕, 林坤德. 漆酶催化转化溴酚类化合物的动力学研究[J]. 浙江工业大学学报, 2014, 42(3): 344-348 KONG Xiaoyan, LIN Kunde. Transformation kinetics of bromophenols by laccase[J]. Journal of Zhejiang University of Technology, 2014, 42(3): 344-348(in Chinese)
[27] 胡平平, 付时雨. 漆酶催化活性中心结构及其特性研究进展[J]. 林产化学与工业, 2001, 21(3): 69-75 HU Pingping, FU Shiyu. Advances in the studies on structure of catalytic active site and characteristics of laccase[J]. Chemistry & Industry of Forest Products, 2001, 21(3): 69-75(in Chinese)
[28] CANTARELLA G, GALLI C, GENTILI P. Free radical versus electron-transfer routes of oxidation of hydrocarbons by laccase/mediator systems[J]. Journal of Molecular Catalysis B: Enzymatic, 2003, 22(3/4): 135-144
[29] 谢道月, 刘琦, 汪珺, 等. MnO₂纳米酶催化ABTS的显色反应及其在Fe²⁺和Pb²⁺检测中的应用[J]. 环境化学, 2019, 38(12): 2843-2850 XIE Daoyue, LIU Qi, WANG Jun, et al. Chromogenic reaction of ABTS catalyzed by MnO₂ nanozyae and its application in the visual detection of Fe²⁺ and Pb²⁺[J]. Environmental Chemistry, 2019, 38(12): 2843-2850(in Chinese)
[30] DADIGALA R, BANDI R, ALLE M, et al. Effective fabrication of cellulose nanofibrils supported Pd nanoparticles as a novel nanozyme with peroxidase and oxidase-like activities for efficient dye degradation[J]. Journal of Hazardous Materials, 2022, 436: 129165