Rong Huang , Jian Liu , Shanshan Ru , Ping Wang , Jiamei Hao , Hulin Gao
{"title":"载锂蒙脱土的构效关系:八面体锂锁定机制","authors":"Rong Huang , Jian Liu , Shanshan Ru , Ping Wang , Jiamei Hao , Hulin Gao","doi":"10.1016/j.partic.2025.06.001","DOIUrl":null,"url":null,"abstract":"<div><div>The structural complexity of lithium-bearing clay minerals and limitations of conventional characterization methods impede efficient lithium extraction from montmorillonite-type ores. This study employs density functional theory to elucidate structure-activity relationships governing lithium occurrence in montmorillonite, with particular emphasis on octahedral locking mechanisms and interfacial reaction barriers. Systematic calculations reveal four potential lithium occurrence sites: Al-O octahedra, Si-O tetrahedral lattices, interlayer sites and Li substituted H site. Lithium demonstrates optimal stability within Mg-Al-O octahedral lattices, exhibiting the lowest interaction energy (−672.982 kJ/mol) and substantial Mulliken charge transfer (2.35 e), confirming this configuration as the primary hosting environment. Density of states analysis uncovers critical electronic structure features: the 1s orbital of lithium remains energetically isolated from the Fermi level, explaining its chemical inertness and resistance to direct leaching. Conversely, the reactive 2p orbital of oxygen near the Fermi level facilitate surface interactions with flotation reagents. These electronic signatures imply the feasibility of flotation recovery alongside hydrometallurgical approaches. The octahedral locking mechanism originates from Li-induced dynamic symmetry reconstruction. This process achieves energy minimization through bond-angle regularization, while the notable contraction of Al-O/Mg-O bonds enhances electrostatic coupling. These synergistic effects ultimately establish a structural-charge dual-locking mechanism. This study delivers atomic-level insights into lithium occurrence mechanisms, addressing critical gaps in clay-type lithium mineralogy and revealing structure-activity relationships that guide sustainable lithium recovery via interface regulation.</div></div>","PeriodicalId":401,"journal":{"name":"Particuology","volume":"104 ","pages":"Pages 42-51"},"PeriodicalIF":4.1000,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Structure-activity relationships in lithium-hosting montmorillonite: Octahedral lithium locking mechanisms\",\"authors\":\"Rong Huang , Jian Liu , Shanshan Ru , Ping Wang , Jiamei Hao , Hulin Gao\",\"doi\":\"10.1016/j.partic.2025.06.001\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The structural complexity of lithium-bearing clay minerals and limitations of conventional characterization methods impede efficient lithium extraction from montmorillonite-type ores. This study employs density functional theory to elucidate structure-activity relationships governing lithium occurrence in montmorillonite, with particular emphasis on octahedral locking mechanisms and interfacial reaction barriers. Systematic calculations reveal four potential lithium occurrence sites: Al-O octahedra, Si-O tetrahedral lattices, interlayer sites and Li substituted H site. Lithium demonstrates optimal stability within Mg-Al-O octahedral lattices, exhibiting the lowest interaction energy (−672.982 kJ/mol) and substantial Mulliken charge transfer (2.35 e), confirming this configuration as the primary hosting environment. Density of states analysis uncovers critical electronic structure features: the 1s orbital of lithium remains energetically isolated from the Fermi level, explaining its chemical inertness and resistance to direct leaching. Conversely, the reactive 2p orbital of oxygen near the Fermi level facilitate surface interactions with flotation reagents. These electronic signatures imply the feasibility of flotation recovery alongside hydrometallurgical approaches. The octahedral locking mechanism originates from Li-induced dynamic symmetry reconstruction. This process achieves energy minimization through bond-angle regularization, while the notable contraction of Al-O/Mg-O bonds enhances electrostatic coupling. These synergistic effects ultimately establish a structural-charge dual-locking mechanism. This study delivers atomic-level insights into lithium occurrence mechanisms, addressing critical gaps in clay-type lithium mineralogy and revealing structure-activity relationships that guide sustainable lithium recovery via interface regulation.</div></div>\",\"PeriodicalId\":401,\"journal\":{\"name\":\"Particuology\",\"volume\":\"104 \",\"pages\":\"Pages 42-51\"},\"PeriodicalIF\":4.1000,\"publicationDate\":\"2025-06-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Particuology\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1674200125001592\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Particuology","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1674200125001592","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
Structure-activity relationships in lithium-hosting montmorillonite: Octahedral lithium locking mechanisms
The structural complexity of lithium-bearing clay minerals and limitations of conventional characterization methods impede efficient lithium extraction from montmorillonite-type ores. This study employs density functional theory to elucidate structure-activity relationships governing lithium occurrence in montmorillonite, with particular emphasis on octahedral locking mechanisms and interfacial reaction barriers. Systematic calculations reveal four potential lithium occurrence sites: Al-O octahedra, Si-O tetrahedral lattices, interlayer sites and Li substituted H site. Lithium demonstrates optimal stability within Mg-Al-O octahedral lattices, exhibiting the lowest interaction energy (−672.982 kJ/mol) and substantial Mulliken charge transfer (2.35 e), confirming this configuration as the primary hosting environment. Density of states analysis uncovers critical electronic structure features: the 1s orbital of lithium remains energetically isolated from the Fermi level, explaining its chemical inertness and resistance to direct leaching. Conversely, the reactive 2p orbital of oxygen near the Fermi level facilitate surface interactions with flotation reagents. These electronic signatures imply the feasibility of flotation recovery alongside hydrometallurgical approaches. The octahedral locking mechanism originates from Li-induced dynamic symmetry reconstruction. This process achieves energy minimization through bond-angle regularization, while the notable contraction of Al-O/Mg-O bonds enhances electrostatic coupling. These synergistic effects ultimately establish a structural-charge dual-locking mechanism. This study delivers atomic-level insights into lithium occurrence mechanisms, addressing critical gaps in clay-type lithium mineralogy and revealing structure-activity relationships that guide sustainable lithium recovery via interface regulation.
期刊介绍:
The word ‘particuology’ was coined to parallel the discipline for the science and technology of particles.
Particuology is an interdisciplinary journal that publishes frontier research articles and critical reviews on the discovery, formulation and engineering of particulate materials, processes and systems. It especially welcomes contributions utilising advanced theoretical, modelling and measurement methods to enable the discovery and creation of new particulate materials, and the manufacturing of functional particulate-based products, such as sensors.
Papers are handled by Thematic Editors who oversee contributions from specific subject fields. These fields are classified into: Particle Synthesis and Modification; Particle Characterization and Measurement; Granular Systems and Bulk Solids Technology; Fluidization and Particle-Fluid Systems; Aerosols; and Applications of Particle Technology.
Key topics concerning the creation and processing of particulates include:
-Modelling and simulation of particle formation, collective behaviour of particles and systems for particle production over a broad spectrum of length scales
-Mining of experimental data for particle synthesis and surface properties to facilitate the creation of new materials and processes
-Particle design and preparation including controlled response and sensing functionalities in formation, delivery systems and biological systems, etc.
-Experimental and computational methods for visualization and analysis of particulate system.
These topics are broadly relevant to the production of materials, pharmaceuticals and food, and to the conversion of energy resources to fuels and protection of the environment.