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doping engineering of lithium-aluminum layered double hydroxides for high-efficiency lithium extraction from salt lake brines

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Nano Research 2024年第3期17卷 1646-1654页

作者： Lingjie Zhang Tingting Zhang Yunliang Zhao Guangfeng Dong Shuaike Lv Songliang Ma Shaoxian Song Mildred Quintana School of Chemical and Environmental engineering Wuhan Polytechnic UniversityWuhan 430023China School of Resources and Environmental engineering Wuhan University of TechnologyWuhan 430070China Facultad de Ciencias Universidad Autonoma de San Luis PotosiAv.Parque Chapultepec 1570San Luis Potosi 78210Mexico Wuhan Clayene Technology Co. Ltd.Wuhan 430223China State Development Investment Xinjiang Lop Nur Potash Corporation Hami 839000China

Lithium-aluminum layered double hydroxides(LiAl-LDH)have been be successfully applied in commercial-scale for lithium extraction from salt lake brine,however,further advancement of their applications is hampered by suboptimal Li^(+)adsorption performance and ambiguous extraction process.Herein,a doping engineering strategy was developed to fabricate novel Zn^(2+)-doped LiAl-LDH(LiZnAl-LDH)with remarkable higher Li^(+)adsorption capacity(13.4 mg/g)and selectivity(separation factors of 213,834,171 for Li^(+)/K^(+),Li^(+)/Na^(+),Li^(+)/Mg^(2+),respectively),as well as lossless reusability in Luobupo brine compared to the pristine LiAl-LDH.Further,combining experiments and simulation calculations,it was revealed that the specific surface area,hydrophilic,and surface attraction for Li^(+)of LiZnAl-LDH were significantly improved,reducing the adsorption energy(Ead)and Gibbs free energy(ΔG),thus facilitating the transfer of Li^(+)from brine into interface followed by insertion into voids.Importantly,the intrinsic oxygen vacancies derived from Zn-doping depressed the diffusion energy barrier of Li^(+),which accelerated the diffusion process of Li^(+)in the internal bulk of LiZnAl-LDH.This work provides a general strategy to overcome the existing limitations of Li^(+)recovery and deepens the understanding of Li^(+)extraction on LiAl-LDH.

关键词： lithium extraction salt lake brines doping engineering lithium-aluminum layered double hydroxides density functional theory

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Defects and doping engineering towards high performance lead-free or lead-less perovskite solar cells

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Journal of Energy Chemistry 2022年第5期31卷 420-438页

作者： Wenying Cao Zhaosheng Hu Zhenhua Lin Xing Guo Jie Su Jingjing Chang Yue Hao State Key Discipline Laboratory of Wide Band Gap Semiconductor Technology School of MicroelectronicsXidian UniversityXi’an 710071ShaanxiChina Advanced Interdisciplinary Research Center for Flexible Electronics Xidian UniversityXi’an 710071ShaanxiChina

Up to now, perovskite solar cells(PSCs) have reached a certified 25.5% efficiency. As a promising photo-electric material, the metal halide perovskite possesses many outstanding properties such as tunable bandgap, long diffusion length, high absorption coefficient and carrier mobility. In spite of these remarkable properties, defects are inevitable during the solution processing. Therefore, many efforts have been made to reduce defects in perovskite films and thus improve the performance of devices. Among them,substitution or doping engineering is one of the most studied methods. Meanwhile, due to the poor stability of the organic-inorganic hybrid perovskite and the toxicity of Pb-based perovskite materials, all inorganic perovskite and lead-less or lead-free perovskite have emerged as promising materials. Here,we focus on the defect engineering especially substitutions on different sites in an ABX_(3) structure. The particular attention is devoted towards lead-less or lead-free perovskites, and we discuss several common elements or groups used to partially replace Pb^(2+). It is noted that proper elemental doping at different sites is an important guarantee for obtaining high-performance lead-less or lead-free PSCs.

关键词： Perovskite Defects doping engineering Lead-free Lead-less Solar cells

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Two-dimensional perovskite SrNbO_(2) N with Zr doping for accelerating photoelectrochemical water splitting

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Journal of Materials Science & Technology 2023年第11期142卷 176-184页

作者： Thanh Tam Thi Tran Van-Huy Trinh Jeongsuk Seo Department of Chemistry College of Natural SciencesChonnam National University77 Yongbong-roBuk-guGwangju 61186South Korea

The superior ability of perovskite-type SrNbO_(2) N to absorb intensive visible light makes it a potential semiconductor to produce hydrogen and oxygen by photoelectrochemical(PEC)water splitting under sunlight.The surface morphologies,such as shape and structure,of the oxynitride strongly affect its photoactivity,although the mechanism has been hardly studied.Herein,we report a two-dimensional(2D)porous SrNbO_(2) N plate with Zr doping,nitrided from layered perovskite Sr_(5)Nb_(4)O_(15) and also its largely enhanced PEC water splitting activity.Zr^(4+)was doped in Sr_(5)Nb_(4)O_(15) during flux-assisted calcination using KCl,producing 2D-type truncated-octahedral Sr_(5)Nb_(4)O_(15):Zr plates approximately 50 nm in thickness.The nitridation completely transformed Sr_(5)Nb_(4)O_(15):Zr to 2D single-crystalline SrNbO_(2) N:Zr with a large surface area,which was subsequently used to fabricate a thin and uniform photoanode by the spin coating method.As a result,the Co(OH)_(x)/SrNbO_(2) N:Zr/FTO photoanode capable of absorbing visible light of up to 680 nm exhibited an activity of 2.0 mA cm^(-2) at 1.23 V vs the reversible hydrogen electrode for water splitting under AM 1.5G simulated sunlight.This improvement in photoactivity mainly originated from the 2D surface morphology of SrNbO_(2) N:Zr,which is clearly distinguishable from 3D-type oxynitrides.According to electrochemical analyses,the 2D structure of SrNbO_(2) N:Zr boosted the separation and accelerated the transfer of charges photogenerated during the water splitting,thus driving the reaction further.Therefore,the result empirically demonstrates that controlling the surface morphology of SrNbO_(2) N is an effective strategy to suppress the recombination of charges and minimize their diffusion pathway,eventually enhancing the PEC activity.

关键词： Solar water splitting Water oxidation BaNbO_(2)N doping engineering Flux-assisted calcination Spin coating

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