黄腐酸络合铜离子光谱学特征及机理构建  

The Spectroscopic Characteristics of Fulvic Acid Complexed With Copper Ion and the Construction of the Mechanism of Action

作　　者：徐恒山 巩冠群[1,2] 张英杰[1,2] 袁飞 张永霞 XU Heng-shan;GONG Guan-qun;ZHANG Ying-jie;YUAN Fei;ZHANG Yong-xia(Key Laboratory of Coal Processing and Efficient and Clean Utilization,Ministry of Education,Xuzhou 221116,China;School of Chemical Engineering,China University of Mining and Technology,Xuzhou 221116,China)

机构地区：[1]煤炭加工与高效洁净利用教育部重点实验室,江苏徐州221116 [2]中国矿业大学化工学院,江苏徐州221116

出　　处：《光谱学与光谱分析》2022年第4期1010-1016,共7页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21776299,21576281);中国矿业大学研究生教育教学改革与研究实践项目(2019YJSJG043,YJSJG-2018-01)资助。

摘　　要：二价金属离子Cu^(2+)在很多工矿企业周围水源及土壤中存量超标,造成生态环境恶化,传统的药剂及生物处理容易产生二次污染。黄腐酸由性质相似分子团簇构成,具有水溶性好、络合作用强及化学活性高的特点,对环境中Cu^(2+)分布、迁移和生物利用度可以实现高效控制与环保处理,是近年科学研究热点。现代多光谱表征分析有助于揭示黄腐酸与金属离子作用过程构效关系变化、环境效应及重金属离子迁移行为规律,对黄腐酸与Cu^(2+)络合过程特点及作用机理研究具有重要科学价值。综述了近年来黄腐酸与Cu^(2+)络合作用相关基础理论研究,通过红外光谱、三维荧光光谱及差分光谱等方法对黄腐酸与Cu^(2+)络合前后表征对比分析和学科交叉协同研究,探讨了pH、离子浓度以及黄腐酸组分构成差异等对络合过程的影响,揭示了黄腐酸与Cu^(2+)络合作用位点的结构特性及作用规律,羧基与酚羟基等含氧酸性官能团是Cu^(2+)与黄腐酸络合的主要位点,羧基型位点络合Cu^(2+)作用显著,酚羟基型位点有助于增加Cu^(2+)络合物稳定性,含氮官能团也在络合过程中发挥重要作用。在此基础上,进一步指出pH值的变化将改变黄腐酸活性位点对Cu^(2+)的亲和力,原因主要与活性位点上Cu^(2+)与H^(+)之间的离子交换以及黄腐酸的静电吸引力有关;不同结构特征的黄腐酸对Cu^(2+)络合效果主要体现在具有不同数量的酚羟基、羧基以及含氮官能团活性位点;溶液中共存Fe^(3+),Mg^(2+)和Al^(3+)等离子会与Cu^(2+)在黄腐酸的活性结合位点上产生显著络合竞争;同时溶液环境中K^(+)和Na^(+)等非强吸附作用离子浓度增加,使得溶液中大量正电荷离子就近进入黄腐酸的电子层而增强电荷屏蔽效应,进而也抑制Cu^(2+)与黄腐酸络合。总结并展望了黄腐酸相关学科技术理论在现代农业、生态修复及环境治理等领域科学�The divalent metal ion Cu^(2+) exceeds the standard in water sources and soils around many industrial and mining enterprises,causing deterioration of the ecological environment,and traditional chemical and biological treatments are prone to secondary pollution.Fulvic acid is composed of molecular clusters with similar properties.It has the characteristics of good water solubility,strong complexation and high chemical activity.It can efficiently control the distribution,migration and bioavailability of Cu^(2+) in the environment and is a hot spot in scientific research in recent years.Modern multispectral characterization analysis is helpful to reveal the changes in the structure-activity relationship between fulvic acid and metal ions,environmental effects and the migration behavior of heavy metal ions.It has important scientific value for studying the characteristics and mechanism of the complexation process of fulvic acid and Cu^(2+).This article reviews the basic theoretical research on the complexation of fulvic acid with Cu^(2+) in recent years.This paper further analyzes the characterization of fulvic acid and Cu^(2+) before and after complexation through infrared spectroscopy,fluorescence spectroscopy,differential spectroscopy,and interdisciplinary collaborative research.The effects of pH,ion concentration and the difference in composition of fulvic acid on the complexation process were discussed.The complex sites’ structural characteristics and action rules between fulvic acid and Cu^(2+) are revealed.Oxygen-containing acidic functional groups,such as carboxyl and phenolic hydroxyl,are the main complex sites between the complexation process of Cu^(2+) and fulvic acid.The carboxyl site has a significant ability to complex Cu^(2+).The phenolic hydroxyl site is helpful to increase the stability of the Cu^(2+) and fulvic acid complex,and the nitrogen-containing functional group also plays an important role in the complex process.On this basis,this article further points out that the change of pH value will

关 键 词：黄腐酸 铜离子 离子络合 活性位点 谱图表征 作用机理 

分 类 号：O656.4[理学—分析化学]