WATER RESEARCH
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2025
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IF 12.4
Shijun Miao,Pengcheng Yin,Shu Zhang,Zijie Zhang,Dawei Li,Feihu Li
Capacitive deionization (CDI) is a highly efficient approach for sustainable water desalination and ion-selective separation from complex brines. Layered metatitanic acid (H₂TiO₃, HTO) is a promising platform for electrochemical separation of monovalent ions due to its unique structural properties, but it faces lower conductivity when applied solely to CDI. Coupling HTO with carbon offers a valid strategy to address its charge transfer limitation and thereby enhance the CDI performance. Herein, we report a yolk-shell structured HTO/carbon electrode (denoted as ys-HTO@C) based on a stepwise nanoscale architectonic strategy that demonstrates superior charge transfer and storage properties and, therefore, better CDI performance relative to its core-shell structured and bulk counterparts (denoted as cs-HTO@C and HTO, respectively). Electrochemical desalination reveals that ys-HTO@C electrode has a Na⁺ adsorption capacity of 53.1 mg g -1 in 500 mg L -1 of NaCl solution at 1.2 V, a charge efficiency of 0.68, and moderate cycling stability (70.5% of capacity retention over 40 cycles) due to its unique void space inside. Structural analyses indicate that capacity fading during cycling is primarily attributed to carbon oxidation and HTO degradation over time. Additionally, lithium extractions in synthetic and actual brines show that the HTO/carbon electrodes exhibit preferential capture of Li⁺ over Na⁺, Ca²⁺, Mg²⁺, and Pb²⁺ ions, with a separation factor of Li⁺/Na⁺ up to 60.7 for the ys-HTO@C electrodes in natural brine from East Taijinaier Salt Lake. It was observed that Li⁺ selectivity is concentration-dependent and likely driven by both the HTO’s intrinsic Li⁺ preference and the ion’s properties. The findings underscore the potential of the yolk-shell construction strategy for preparing novel and highly efficient electrodes for electrochemical desalination and selective Li⁺ extraction from complex brines.
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高影响因子
APPLIED SURFACE SCIENCE
·
2026
·
IF 6.6
Qipeng Zhang,Jiayi Xu,Chaoyue Li,Zhihao Lu,Siqu Zou,Yu Miao,Jiale Li,Chenglong Shi,Lei Zhang,Yong Wang,Yaru Qin
Porous PVA@SA/HTO hydrogel beads were fabricated via a dual-crosslinking strategy. • A high Li + capacity of 23.36 mg·g −1 was achieved with rapid adsorption kinetics. • Robust stability was maintained over 20 cycles with negligible Ti loss (<0.1%). • Continuous lithium separation was successfully validated in fixed-bed column tests. Lithium-ion sieves (LISs) are promising adsorbents for lithium recovery, but powdered LISs often suffer from difficult solid–liquid separation, poor recoverability, and limited continuous-flow applicability. Herein, spherical PVA@SA/H 2 TiO 3 (PVA@SA/HTO) composite hydrogel bead adsorbents were fabricated through crosslinking-assisted shaping and freeze-drying. The optimized PVA@SA/HTO-4 exhibited a three-dimensional porous network with a specific surface area of 24.97 m 2 ·g −1 , nearly twice that of pristine HTO powder (12.52 m 2 ·g −1 ). Under optimized batch conditions, PVA@SA/HTO-4 achieved an equilibrium Li + adsorption capacity of 23.36 mg·g −1 , retained 86.7% of its capacity after 20 adsorption–desorption cycles, and showed Ti dissolution loss below 0.1% in each cycle. In Xitaijinair Salt Lake brine, PVA@SA/HTO-4 showed preferential Li + adsorption, with separation factors of 582.90, 326.66, 324.23, and 86.59 over Na + , K + , Mg 2+ , and Ca 2+ , respectively. Kinetic, isotherm, FTIR, and XPS analyses indicated that Li + adsorption mainly proceeded through H + /Li + ion exchange at HTO exchange sites. Fixed-bed breakthrough and closed-loop recirculation experiments further demonstrated the continuous-flow operability of PVA@SA/HTO-4 under the tested LiCl solution conditions. This work offers a promising shaped hydrogel strategy for recoverable, cycling-stable, and dynamically applicable HTO-based lithium-ion sieves Download: Download high-res image (217KB) Download: Download full-size image
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2025
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IF 5.4
Liyang Zhou,Aixue Bi,Xu Yang,Feng Xue,Shengui Ju
Titanium-based lithium-ion sieves (LISs) have attracted considerable attention because of their superior adsorption capacity and cycling stability in lithium ion extraction. In this paper, an S-doped H 2 TiO 3 -ferrite ion sieve was successfully synthesized through co-precipitation scheme. The recycling problem of lithium ion sieve powder was effectively solved by utilizing its magnetic separation property. LTSO-Ferrite was prepared in one step using a high-temperature solid-phase method, with an optimal molar ratio of FeCl 2 : TiS 2 : TiO 2 = 0.2: 0.2: 1. The adsorption capacity of S-doped H 2 TiO 3 -Ferrite (HTSO-Ferrite) reached 43.02 mg/g, and the magnetization value was 4.81 emu/g. The adsorption energy and structure of Li + on LTSO-Ferrite were determined using density functional theory (DFT) to assess the feasibility of lithium absorption. The adsorption behavior of LTSO-Ferrite toward Li + followed the Langmuir isotherm and pseudo-second-order kinetic models, indicating that the adsorption was endothermic and spontaneous. LTSO-Ferrite exhibited good selectivity for heteroatoms in simulated brine. Magnetic recovery rate remained at 98 % with an adsorption capacity of 36.16 mg/g after five cycles, which is 84 % of its maximum adsorption capacity. LTSO-Ferrite exhibited magnetic separation properties, offering a promising approach for developing lithium adsorbents for extraction from unsalted lake brine.
研究领域:
材料科学
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环境科学
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高影响因子
Gels
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2026
·Vol. 12
·期 10
·873
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IF 6.4
Xueqiao Wang,Jing Wang,Wenxuan Wang,Ruimeng Liu,Yimin Shi,Daxin Liang
Efficient seawater lithium harvesting requires adsorbents combining high selectivity with scalable, low-energy fabrication. Although H2TiO3lithium-ion sieves (HTO-LIS) exhibit exceptional Li+selectivity, their deployment is hindered by strict alkaline requirements and reliance on energy-intensive shaping processes such as freeze-drying. Herein, we report a cellulose nanofibril (CNF) composite aerogel addressing both challenges simultaneously. Ammonium phytate (AP), a bio-derived polyphosphate, serves a dual function: as a green crosslinker for CNF and as an in situ alkalinity generator, creating a localized alkaline microenvironment around immobilized HTO nanoparticles that enables efficient topotactic H+/Li+exchange at seawater-relevant pH 8 without requiring strongly alkaline bulk conditions. Crucially, the AP-crosslinked CNF skeleton withstands capillary forces during ambient-pressure drying, preserving a hierarchical macroporous network without freeze-drying. The resulting AP-CNF@HTO monolith achieves a Li+capacity of 19.08 mg g−1at pH 8, a 128.9% enhancement over pristine HTO, with excellent selectivity against competing ions in real seawater and 88.3% capacity retention after ten cycles. This work demonstrates that rational bio-based crosslinker selection can concurrently solve the alkaline microenvironment and ambient-drying challenges of HTO-LIS composites, offering an ambient-pressure-drying route with reduced reliance on energy-intensive freeze-drying for seawater lithium enrichment.
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高影响因子
Surfaces and Interfaces
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2024
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IF 5.7
Rui You,Zhiyang He,Feng Xue,Shengui Ju
The lithium-ion sieve primarily exists in powder form, which poses challenges such as poor fluidity and permeability, as well as difficulties in recovery. The H₂TiO₃ (HTO) particles were introduced into polyacrylamide (PAM) via in situ polymerization to prepare a tough and porous nanocomposite hydrogel (HTO@PAM). This method effectively addresses the recovery difficulties associated with powdered lithium-ion sieves and, due to the hydrophilic groups in polyacrylamide, enhances the desorption of Li + and improves the adsorption performance. The results show that HTO@PAM-4 is the optimal ratio, with an adsorption performance of 32.8 mg/g. Tensile strength tests using a universal testing machine indicated that HTO@PAM-4 has a tensile strength of 0.19 MPa, demonstrating excellent mechanical properties. Infrared spectroscopy detected the presence of hydrophilic groups (-CONH 2 ) in HTO@PAM, and surface tension measurements showed a water contact angle of 8.9 °, indicating good hydrophilicity. The recyclability of HTO@PAM-4 was investigated, and after six cycles, the adsorption capacity was 25.4 mg/g, which is 77 % of the maximum adsorption performance, demonstrating recyclability. The results indicate that HTO@PAM exhibits excellent mechanical properties, adsorption performance, and recyclability, making it a material with promising practical applications.
研究领域:
材料科学
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环境工程
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CHEMICAL ENGINEERING JOURNAL
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2021
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IF 13.273
Kaiyu Zhao,Bojia Tong,Xiaoping Yu,Yafei Guo,Yingchun Xie,Tianlong Deng
The recovery of lithium has received widespread attention. Adsorption is one of the most promising methods, but the synthesis of adsorbents with high adsorption performance and stability is still a huge challenge. Herein, a novel porous fiber using H 2 TiO 3 (HTO) as the core material was developed for lithium recovery from geothermal water. HTO was successfully coated and uniformly distributed in the polysulfone (PSF) fiber by a commercialized spinning apparatus combined with the wet spinning technology. When the percentage of HTO in PSF/HTO was 50%, the material showed high adsorption performance, even close to that of powdery HTO. The stability and adsorption capacity of PSF/HTO were further improved using hyperfine H 2 TiO 3 synthesized by a modified solid-state method. Compared with other composite adsorbents reported at present, the maximum adsorption capacity and adsorption rate were obtained, and even the adsorption capacity for 25.78 mg·L − 1 Li + in geothermal water reached 22.66 mg·g −1 after only 60 min with a recovery rate of 88.68%. The distribution coefficient of Li + was 2 ∼ 3 orders of magnitude higher than other coexisting ions, and the average dissolution loss rate of Ti did not exceed 0.6% during cyclic tests. Because of the excellent adsorption properties of PSF/HTO, especially the feasibility of large-scale preparation using commercialized spinning apparatus, the material developed in this work can be used as a potential adsorbent for lithium recovery from geothermal water or other liquid lithium resources.
研究领域:
材料科学
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环境工程
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化学工程
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2026
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IF 8.8
Dandan Zhao,Yuchun Ren,Chen Fu,Yiqing Liu,Dongmei Wang,Zhengjun Gong,How Yong Ng
The rapid expansion of the shale gas industry has led to the production of large volumes of wastewater containing valuable lithium resources. Although various lithium-ion sieve (LIS) materials have been developed for selective lithium recovery from shale gas wastewater (SGW), their adsorption capacity and selectivity are severely limited under natural near-neutral conditions. Here, a polydopamine (PDA)-modified Ni–H 2 TiO 3 (HTO)/MXene/polysulfone (PSF) composite membrane was developed for sustainable and selective lithium recovery from real SGW at its natural pH of 7.92. Surface polymerization of dopamine modulated the zeta potential of the membrane, effectively enhancing its Li + adsorption performance. The PDA/Ni-HTO/MXene/PSF membrane achieved a high adsorption capacity of 38.31 mg g −1 within 2 h, while maintaining excellent cycling stability and fouling resistance. Mechanistic analyses revealed that the synergistic effects between PDA and MXene enhanced the electronic capture ability of Ti–O and C–O coordination sites and activated interfacial π-electronic structures and charge redistribution, thereby promoting Li + adsorption and transport. The integrated membrane-based approach couples lithium recovery with wastewater treatment, offering a pathway for simultaneous resource recovery with reduced chemical input and secondary salinity loading.
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高影响因子
Particuology
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2026
·
IF 4.3
Ye Wang,Yuxin Xie,Xiaojing Guo,Xi Yan,Yan Chen,Ping Hu,Peng Cheng,Wanzhong Lang
The solid-state synthesis of H 2 TiO 3 (HTO) lithium ion-sieves is highly sensitive to the particle size of the TiO 2 precursor, which governs both structural properties and ultimate adsorption performance. This study reveals a striking morphological convergence during the synthesis of Li 2 TiO 3 (LTO) intermediates: despite employing TiO 2 precursors spanning 15-40 nm, the resulting LTO particles consistently exhibited a narrow size range of 28-32 nm, indicating a distinctive size-regulation mechanism in the solid-state reaction. In contrast, precursors ≥60 nm led to fragmented structures with reduced crystallinity. Leveraging this finding, we identified 40 nm as a critical precursor size for crafting optimal HTO adsorbents. The 40 nm-derived HTO (40-HTO) delivered a superior equilibrium Li + adsorption capacity of 58.02 mg g -1 , a pseudo-second-order rate constant 2.3-fold higher than that of its 150 nm-derived counterpart, and exceptional cyclic stability (<0.15% Ti dissolution over 10 cycles). Importantly, in a simulated concentrated brine with a high Mg 2+ /Li + mass ratio of 20, 40-HTO maintained a high Li + uptake of 36.5 mg g -1 and exhibited exceptional selectivity, with a separation factor as high as 780. This work underscores precursor size engineering, targeting a critical size threshold, as a vital strategy for developing high-efficiency lithium ion-sieves.
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高影响因子
Materials Science and Engineering B-Advanced Functional Solid-State Materials
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2026
·
IF 5.7
Zhiyang He,Zhengqi Zhu,Yanfeng Chen,Feng Xue,Shengui Ju
Silane coupling agent (KH570) was grafted onto Li 2 TiO 3 @GO via its -OH group. • The 12-crown-4 functional group serves as a side arm for the Li + imprinting agent. • H 2 TiO 3 @GO-CR was engineered and exhibited a bifunction Li + capture effect. To enhance lithium-ion adsorption performance, we designed a novel ion-sieve (denoted as H 2 TiO 3 @GO-CR) that synergistically combines the ion-imprinting effect with the intrinsic lithium capture capability of H 2 TiO 3 . This ion-imprinted monomer containing 12-crown-4-ether groups was fabricated through a two-step reaction involving ring-opening and self-condensation. The abundant -OH functional groups on graphene oxide (GO) served as a bridge to graft this monomer onto H 2 TiO 3 . The successful incorporation of the crown ether into the composite was proved by the FT-IR band at 553 cm −1 , and the Raman shift at 154.2 cm −1 . Owing to its unique dual-adsorption structure and functional groups, H 2 TiO 3 @GO-CR exhibited an excellent adsorption capacity of 39.87 mg·g −1 , with XPS analysis verifying an elevated surface hydroxyl (OH) content of 65.68%. In selectivity tests using simulated salt lake brine, the separation factors ( α Li Me) of H 2 TiO 3 @GO-CR for Li + against competing ions (Na + , K + , Ca 2+ , Mg 2+ ) all exceeded 80, demonstrating exceptional selectivity toward Li + . The α Li Mg = 295.0 shows high selectivity in salt lake brine, which is further substantiated by density functional theory (DFT) calculations of adsorption energies. This work brings a novel strategy for developing bifunctional lithium ion-sieves. Download: Download high-res image (265KB) Download: Download full-size image
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高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2022
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IF 6.371
Yue Yin,Xian Luo,Benjun Xu
Li 4 Ti 5 O 12 (LTO) is the most promising anode material for lithium-ion batteries owing to its excellent cycle stability and safety. However, the electrochemical performance of LTO at high rates is limited by its low conductivity. Generally, LTO preparation requires organic titanium sources, which are expensive. In this study, inexpensive H 2 TiO 3 was used as the titanium source, LiOH‧H 2 O served as the lithium source, and NH 3 ‧H 2 O was added to control the pH of the solution. Simple one-step liquid-phase deposition and calcination were performed for obtaining in situ self-assembled LTO submicron spheres with stable morphology and excellent electrochemical performance. According to electrochemical performance tests, the sample calcined with 4 mL of 25% NH 3 ‧H 2 O at 700 °C (LTO-4–700) exhibited the best performance. Its discharge capacity remained at 176.4 mAh g −1 over 100 cycles at 87.5 mA g −1 and retained at 136.7 mAh g −1 over 500 cycles at 875 mA g −1 , and its specific capacity was 105.6 mAh g −1 over 1000 cycles, even at a current of 1750 mA g −1 with a retention rate of 96.7%. Furthermore, LTO-4–700 exhibited excellent rate performance at 3500 mA g −1 compared to other samples. Cyclic voltammetry and electrochemical impedance spectroscopy confirmed that submicron spherical LTO-4–700 had a high Li + migration rate and low electrochemical impedance.
研究领域:
材料科学
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电化学
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能源存储
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高影响因子
危险品化学品经营许可证（带存储）