黄腐酸络合铜离子光谱学特征及机理构建

doi:10.3964/j.issn.1000-0593(2022)04-1010-07

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摘要：二价金属离子Cu²⁺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Cu²⁺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Cu²⁺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Cu²⁺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Cu²⁺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Cu²⁺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Cu²⁺与黄腐酸络合的主要位点，羧基型位点络合Cu²⁺作用显著，酚羟基型位点有助于增加Cu²⁺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Cu²⁺的亲和力，原因主要与活性位点上Cu²⁺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Cu²⁺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Fe³⁺，Mg²⁺和Al³⁺等离子会与Cu²⁺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Cu²⁺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应用共存的问题及挑战。

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

Abstract：The divalent metal ion Cu²⁺ 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 Cu²⁺ 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 Cu²⁺. This article reviews the basic theoretical research on the complexation of fulvic acid with Cu²⁺ in recent years. This paper further analyzes the characterization of fulvic acid and Cu²⁺ 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 Cu²⁺ are revealed. Oxygen-containing acidic functional groups, such as carboxyl and phenolic hydroxyl, are the main complex sites between the complexation process of Cu²⁺ and fulvic acid. The carboxyl site has a significant ability to complex Cu²⁺. The phenolic hydroxyl site is helpful to increase the stability of the Cu²⁺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 change the affinity of the active site of fulvic acid to Cu²⁺, the reason is mainly related to the ion exchange between Cu²⁺ and H⁺ on the active site and the electrostatic attraction of fulvic acid. The difference in FA components affects the complexation of FA and Cu²⁺, which is mainly reflected in the different numbers of phenolic hydroxyl, carboxyl and nitrogen-containing functional groups in different FA. The coexistence of Fe³⁺, Mg²⁺ and Al³⁺ the solution will have significant competition with Cu²⁺ at the active binding site of fulvic acid. At the same time, the concentration of non-strong adsorption ions such as K⁺ and Na⁺ in the solution environment increases, so that a large number of positively charged ions in the solution enter the electronic layer of fulvic acid nearby to enhance the charge shielding effect, inhibiting the complexation of Cu²⁺ and FA. Finally, this paper summarizes and looks forward to the problems and challenges of coexistence of scientific application of fulvic acid-related disciplines and technical theories in modern agriculture, ecological restoration and environmental governance.

Key words：Fulvic acid; Copper ion; Ion complexation; Active site; Spectral characterization; Mechanism of action

收稿日期: 2021-03-26 修订日期: 2021-06-21

中图分类号:

O656.4

基金资助: 国家自然科学基金项目（21776299，21576281）和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

通讯作者: 巩冠群 E-mail: ggqzyj@126.com

作者简介: 徐恒山，1997年生，中国矿业大学化工学院硕士研究生 e-mail: 18821671546@163.com

引用本文:

徐恒山，巩冠群，张英杰，袁飞，张永霞. 黄腐酸络合铜离子光谱学特征及机理构建[J]. 光谱学与光谱分析, 2022, 42(04): 1010-1016.
XU Heng-shan, GONG Guan-qun, ZHANG Ying-jie, YUAN Fei, ZHANG Yong-xia. The Spectroscopic Characteristics of Fulvic Acid Complexed With Copper Ion and the Construction of the Mechanism of Action. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(04): 1010-1016.

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