Coordination configurations of cupric tartrate in electronic industry wastewater  

电子工业废水中酒石酸铜的配位构型

作　　者：Ming-jun HAN Jian-yong HE Wei SUN Sai LI Heng YU Tong YUE Xin WEI Chen-yang ZHANG 韩明君;何建勇;孙伟;李赛;余恒;岳彤;魏鑫;张晨阳(中南大学矿物加工与生物工程学院战略含钙矿产资源清洁高效利用湖南省重点实验室,长沙410083;苏州东方环境工程有限公司,苏州215110;湖南省有色金属研究院复杂铜铅锌伴生金属资源综合利用湖南省重点实验室,长沙410100;昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室,昆明650093)

机构地区：[1]Key Laboratory of Hunan Province for Clean and Efficient Utilization of Strategic Calcium-containing Mineral Resources,School of Minerals Processing and Bioengineering,Central South University,Changsha 410083,China [2]Suzhou Dongfang Environmental Engineering Co.,Ltd.,Suzhou 215110,China [3]Key Laboratory of Hunan Province for Comprehensive Utilization of Complex Copper−Lead Zinc Associated Metal Resources,Hunan Research Institute for Nonferrous Metals,Changsha 410100,China [4]State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization,Kunming University of Science and Technology,Kunming 650093,China

出　　处：《Transactions of Nonferrous Metals Society of China》2022年第11期3753-3766,共14页中国有色金属学报（英文版）

基　　金：the National Key Research and Development Program of China(No.2019YFC0408303);the Natural Science Foundation of Hunan Province,China(No.2021JJ20069);the Changsha Science and Technology Project,China(Nos.kq2106016,kq2009005);Higher Education Discipline Innovation Project(111 Project),China(No.B14034);the Fundamental Research Funds for the Central Universities of Central South University,China(No.2021zzts0887).

摘　　要：The coordination structure of cupric tartrate(Cu−TA)complex was investigated by ultraviolet−visible(UV-Vis)and liquid chromatography/mass spectrometer(LC-MS)firstly;furthermore,effective coordination configurations and electronic properties of Cu−TA in aqueous solution were systematically revealed by density functional theory(DFT)calculations.Consistently,Job plots show the possible existence of[Cu(TA)]and[Cu(TA)_(2)]^(2-)at 230 and 255 nm based on UV-Vis results.LC-MS results confirm the existence of the single and high coordination complexes[Cu_(2)(TA)_(2)]^(+),[Cu(TA)_(2)]^(+)and[Cu_(2)(TA)_(3)(H_(2)O)_(2)(OH)_(2)]^(2+).DFT calculation results show that carboxylic oxygen and hydroxyl oxygen of tartaric acid(TA)are preferred sites for Cu(Ⅱ)coordination.[Cu(TA)](1H,3H sites O of TA coordinated with Cu(Ⅱ)),[Cu(TA)_(2)]^(2-)(two 1^(C),2^(H) sites O of TA coordinated with Cu(Ⅱ)),and[Cu(TA)_(3)]^(4-)(three 2H,3H sites O of TA coordinated with Cu(Ⅱ))should be dominant coordination configurations of Cu−TA.The corresponding Gibbs reaction energies are-170.1,-136.2,and-90.2 kJ/mol,respectively.采用紫外可见光谱(UV-Vis)和液相色谱/质谱(LC-MS)分析酒石酸铜(Cu−TA)配合物的配位结构,并通过密度泛函理论(DFT)计算系统地揭示酒石酸铜在水溶液中的有效配位构型和电子特性。UV−Vis在230和255 nm处的Job图一致显示可能存在[Cu(TA)]和[Cu(TA)_(2)]^(2-)。LC−MS结果证实单配位和高配位配合物[Cu_(2)(TA)_(2)]^(+)、[Cu(TA)_(2)]^(+)和[Cu_(2)(TA)_(3)(H_(2)O)_(2)(OH)_(2)]^(2+)的存在。DFT计算结果表明,酒石酸(TA)的羧基氧和羟基氧是Cu(Ⅱ)的优选配位位点。[Cu(TA)](酒石酸分子1号碳的羟基氧和3号碳的羟基氧与Cu(II)配位)、[Cu(TA)_(2)]^(2-)(2个酒石酸分子1号碳的羧基氧和2号碳的羟基氧与Cu(Ⅱ)配位)以及[Cu(TA)_(3)]^(4-)(3个酒石酸分子2号碳的羟基氧和3号碳的羟基氧与Cu(Ⅱ)配位)是酒石酸铜的主要配位构型。三者的吉布斯自由能分别为-170.1、-136.2和-90.2 kJ/mol。

关 键 词：electronic industry wastewater copper tartaric acid cupric tartrate complex coordination configuration density functional theory 

分 类 号：X76[环境科学与工程—环境工程] O641.4[理学—物理化学]