铅离子-苯甲羟肟酸配合物捕收剂(Pb-BHA)的单晶结构分析  

Single crystal structure analysis of lead ion-benzohydroxamic acid complex collector(Pb-BHA)

作　　者：卫召 孙伟[2] 韩海生[2] 刘叠 桂夏辉[1] 邢耀文[1] WEI Zhao;SUN Wei;HAN Haisheng;LIU Die;GUI Xiahui;XING Yaowen(Chinese National Engineering Research Center of Coal Preparation and Purification,China University of Mining and Technology,Xuzhou 221116,China;School of Minerals Processing and Bioengineering,Central South University,Changsha 410083,China;College of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China)

机构地区：[1]中国矿业大学国家煤加工与洁净化工程技术研究中心,徐州221116 [2]中南大学资源加工与生物工程学院,长沙410083 [3]中南大学化学化工学院,长沙410083

出　　处：《中国有色金属学报》2024年第1期302-313,共12页The Chinese Journal of Nonferrous Metals

基　　金：国家自然科学基金资助项目(52122406)。

摘　　要：铅离子-苯甲羟肟酸配合物捕收剂(Pb-BHA)在钨矿、锡石和钛铁矿等氧化矿浮选中展现出良好的浮选性能和应用前景,但其精确分子结构尚不清楚,阻碍了配合物浮选作用机理的深入认识和金属基捕收剂分子设计的开展。本文培养了铅离子与BHA摩尔比分别为1∶1和2∶1的两种Pb-BHA配合物单晶(配合物1和配合物2),并采用X射线结构分析方法对其结构进行解析,包括配合物晶体结构、分子结构、空间堆积结构、分子间相互作用等。结果表明:配合物1的分子式为Pb_(6)L_(8)(NO_(3))_(4)(HL=BHA),配合物2的分子式为[Pb_(6)L_(8)(NO_(3))_(3)]NO_(3),铅离子与配体氧原子配位形成非平面“O,O”五元环螯合物构型,铅离子配位数为五配位、六配位和七配位。配合物分子通过Pb—O键与临近配合物相键接形成具有单体重复结构的三维扩展堆积聚合物。配合物中弱相互作用以O…H、H…H、Pb…O为主,π-π相互作用在分子间相互作用中占据主导,其次是N—H…O氢键作用。Pb-BHA配合物单晶结构的综合分析为研究配合物的液相结构及矿物表面吸附结构、浮选行为调控方法、浮选作用机理以及新型金属基捕收剂分子设计等提供了重要研究基础。Lead ion-benzohydroxamic acid complex collector(Pb-BHA)shows good flotation performance and application prospect in the flotation of tungsten,cassiterite,ilmenite and other oxide ores,but its precise molecular structure is still unclear,which hindering the in-depth understanding of the flotation mechanism of the complex and the development of the molecular design of metal-group collector.In this paper,two single crystals of Pb-BHA complex(complex-1 and complex-2)with the molar ratio of lead ion to BHA of 1∶1 and 2∶1,respectively,were cultured,and their structures were analyzed by X-ray structure analysis,including the crystal structure,molecular structure,spatial packing structure and molecular interaction of the complex.The results show that the molecular formula of complex 1 is Pb_(6)L_(8)(NO_(3))4(HL=BHA),the molecular formula of complex-2 is[Pb_(6)L_(8)(NO_(3))_(3)]NO_(3),and the coordination of lead ions with the oxygen atoms of ligand forms a non-planar“O,O”five-member ring chelate configuration,and the coordination number of lead ions are five,six and seven.Complex molecules are bonded to adjacent complexes by Pb—O bond to form three-dimensional extended stacked polymers with monomer repeating structure.The O…H,H···H,Pb…O are the main weak interactions in the complex.Theπ-πinteraction dominates the intermolecular interaction,followed by N—H…O hydrogen bonding.The comprehensive analysis of the single crystal structure of Pb-BHA complex provides an important research basis for the study of the liquid phase structure of the complex,the adsorption structure of complex on mineral surface,the regulation method of complex's flotation behavior,the flotation mechanism and the molecular design of new metal-group collector.

关 键 词：配合物 捕收剂 单晶 X射线结构分析 分子间相互作用 

分 类 号：TD952[矿业工程—选矿]