Binda Lu, Xinyang Wang, Yufang Zhang, Qiankun Wang, Feng Jiang*, Wanran Lin, Lingfei Liu, Peiyuan Ye, Wang Lu, Zhouguang Lu and Zhenghe Xu*,
{"title":"超越离子交换：揭开锂离子在H2TiO3上吸附的复杂性。","authors":"Binda Lu, Xinyang Wang, Yufang Zhang, Qiankun Wang, Feng Jiang*, Wanran Lin, Lingfei Liu, Peiyuan Ye, Wang Lu, Zhouguang Lu and Zhenghe Xu*, ","doi":"10.1021/acsami.5c06231","DOIUrl":null,"url":null,"abstract":"<p >Layered titanium acid (H<sub>2</sub>TiO<sub>3</sub> or HTO) has been extensively utilized as a lithium-ion sieve in studies on lithium extraction from salt lake brines. However, the actual lithium uptake by layered HTO, commonly known through an ion exchange mechanism, is much lower than the theoretical value. The hypothesis is that there is a clear need to further elucidate the mechanism of lithium-ion adsorption for the purpose of guiding the design of a lithium ion sieve (LIS). In this study, lithium adsorption on layered HTO as a function of pH was investigated to gain deeper insight into its underlying adsorption mechanism. Lithium adsorption was found to increase significantly with pH, in particular, at pH 14. To comprehend this strong pH dependency, thermogravimetric analysis-differential scanning calorimetry (TG-DSC) techniques were used to analyze the state of HTO layers before and after lithium adsorption. Surprisingly, HTO surfaces at pH 14 exhibited fewer hydration layers and a higher abundance of hydroxyl groups compared with values at lower pH values. Characterization of HTO before and after lithium adsorption using X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed an anatase type of TiO<sub>2</sub> in HTO at pH 14. Fourier transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (SSNMR) measurements showed a significant alteration in the configuration of hydroxyl groups within HTO layers after Li<sup>+</sup> adsorption at pH 14, distinguishing it from the behavior observed at other pH values. These findings demonstrate that lithium adsorption occurs predominantly through LiOH molecules, which displace interlayer water molecules. The results from density functional theory (DFT) calculations align well with our experimental findings. This research provides a more profound understanding of lithium adsorption in multilayer LIS materials and a scientific basis for the design of innovative multilayer structures for the extraction of lithium from salt lake brines.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"17 27","pages":"39628–39641"},"PeriodicalIF":8.2000,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Beyond Ion Exchange: Unraveling the Complexity of Lithium-Ion Adsorption on H2TiO3\",\"authors\":\"Binda Lu, Xinyang Wang, Yufang Zhang, Qiankun Wang, Feng Jiang*, Wanran Lin, Lingfei Liu, Peiyuan Ye, Wang Lu, Zhouguang Lu and Zhenghe Xu*, \",\"doi\":\"10.1021/acsami.5c06231\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Layered titanium acid (H<sub>2</sub>TiO<sub>3</sub> or HTO) has been extensively utilized as a lithium-ion sieve in studies on lithium extraction from salt lake brines. However, the actual lithium uptake by layered HTO, commonly known through an ion exchange mechanism, is much lower than the theoretical value. The hypothesis is that there is a clear need to further elucidate the mechanism of lithium-ion adsorption for the purpose of guiding the design of a lithium ion sieve (LIS). In this study, lithium adsorption on layered HTO as a function of pH was investigated to gain deeper insight into its underlying adsorption mechanism. Lithium adsorption was found to increase significantly with pH, in particular, at pH 14. To comprehend this strong pH dependency, thermogravimetric analysis-differential scanning calorimetry (TG-DSC) techniques were used to analyze the state of HTO layers before and after lithium adsorption. Surprisingly, HTO surfaces at pH 14 exhibited fewer hydration layers and a higher abundance of hydroxyl groups compared with values at lower pH values. Characterization of HTO before and after lithium adsorption using X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed an anatase type of TiO<sub>2</sub> in HTO at pH 14. Fourier transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (SSNMR) measurements showed a significant alteration in the configuration of hydroxyl groups within HTO layers after Li<sup>+</sup> adsorption at pH 14, distinguishing it from the behavior observed at other pH values. These findings demonstrate that lithium adsorption occurs predominantly through LiOH molecules, which displace interlayer water molecules. The results from density functional theory (DFT) calculations align well with our experimental findings. 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Beyond Ion Exchange: Unraveling the Complexity of Lithium-Ion Adsorption on H2TiO3
Layered titanium acid (H2TiO3 or HTO) has been extensively utilized as a lithium-ion sieve in studies on lithium extraction from salt lake brines. However, the actual lithium uptake by layered HTO, commonly known through an ion exchange mechanism, is much lower than the theoretical value. The hypothesis is that there is a clear need to further elucidate the mechanism of lithium-ion adsorption for the purpose of guiding the design of a lithium ion sieve (LIS). In this study, lithium adsorption on layered HTO as a function of pH was investigated to gain deeper insight into its underlying adsorption mechanism. Lithium adsorption was found to increase significantly with pH, in particular, at pH 14. To comprehend this strong pH dependency, thermogravimetric analysis-differential scanning calorimetry (TG-DSC) techniques were used to analyze the state of HTO layers before and after lithium adsorption. Surprisingly, HTO surfaces at pH 14 exhibited fewer hydration layers and a higher abundance of hydroxyl groups compared with values at lower pH values. Characterization of HTO before and after lithium adsorption using X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed an anatase type of TiO2 in HTO at pH 14. Fourier transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (SSNMR) measurements showed a significant alteration in the configuration of hydroxyl groups within HTO layers after Li+ adsorption at pH 14, distinguishing it from the behavior observed at other pH values. These findings demonstrate that lithium adsorption occurs predominantly through LiOH molecules, which displace interlayer water molecules. The results from density functional theory (DFT) calculations align well with our experimental findings. This research provides a more profound understanding of lithium adsorption in multilayer LIS materials and a scientific basis for the design of innovative multilayer structures for the extraction of lithium from salt lake brines.
期刊介绍：
ACS Applied Materials & Interfaces is a leading interdisciplinary journal that brings together chemists, engineers, physicists, and biologists to explore the development and utilization of newly-discovered materials and interfacial processes for specific applications. Our journal has experienced remarkable growth since its establishment in 2009, both in terms of the number of articles published and the impact of the research showcased. We are proud to foster a truly global community, with the majority of published articles originating from outside the United States, reflecting the rapid growth of applied research worldwide.
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