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Materials Today Chemistry · 2026 · IF 7.4

Ti4+ doping regulates cationic potential to construct a P2/O3 biphasic structure for synergistic optimization of cathode materials for sodium-ion batteries

Jun Cong,Shaohua Luo,Shengxue Yan

Prime Novelty Statement • Ti 4+ doping successfully induces the transformation of the material from a single P2 phase to a more stable P2/O3 biphasic coexistence structure. • The stabilization mechanism of Ti 4+ doping is elucidated from a thermodynamic perspective using the total cationic potential and high-entropy design theories. • The optimized material achieves a ∼41% reduction in volume strain, significantly boosting structural reversibility and cycling stability. Layered oxides are ideal cathode materials for sodium-ion batteries (SIBs), but their practical application is limited by sluggish ionic kinetics and detrimental phase transitions under high potential. To address this issue, this study proposes a bulk doping modification strategy to optimize the Na 1.1 Ni 2/9 Fe 1/3 Mn 1/3 Cu 1/18 Mg 1/18 O 2 (NaNFMCM) cathode material via Ti 4+ doping. The results demonstrate that an appropriate amount of Ti 4+ doping (x = 0.1) can effectively regulate the total cation potential ( Φ cation ), driving the material to form a stable P2/O3 biphasic coexistence structure with uniform layered flake-like morphology and homogeneous elemental distribution. This structure thermodynamically suppresses irreversible phase transitions, enhances interfacial kinetics by reducing charge transfer resistance, and significantly reduces the lattice volume strain during Na + deintercalation/intercalation (with Δ V max decreasing from 11.48% to 6.79%). Benefiting from the enhanced crystal structural stability, the modified material exhibits a reversible capacity of 147.3 mAh/g at 0.1C. After cycling at various rates, it still delivers 139.6 mAh/g when the rate is returned to 0.1C, corresponding to a capacity retention of 94.8% relative to its initial 0.1C capacity. Combined with density functional theory calculations, this work elucidates the intrinsic mechanism by which doping modulates the crystal structure and optimizes electronic conduction and ion diffusion kinetics at the electronic level. From the perspectives of thermodynamics and structural evolution, this study reveals the stabilization mechanism of Ti 4+ doping, providing a clear design principle for the development of high-performance and high-stability layered oxide cathode materials for SIBs. The Na 1.1 Ti 0.1 (Ni 2/9 Fe 1/3 Mn 1/3 Cu 1/18 Mg 1/18 ) 0.9 O 2 exhibits excellent electrochemical performance: it delivers a reversible capacity of 147.3 mAh/g at 0.1C and maintains a capacity retention rate of 94.8% after 40 cycles. Download: Download high-res image (227KB) Download: Download full-size image

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Frontiers in Bioengineering and Biotechnology · 2020 · IF 3.644

An Integral Recognition and Signaling for Electrochemical Assay of Protein Kinase Activity and Inhibitor by Reduced Graphene Oxide-Polydopamine-Silver Nanoparticle-Ti4+ Nanocomposite

Wang Jialong,Liu Xueqian,Wang Chao,Liu Dengren,Li Fang,Wang Li,Liu Shufeng

A novel electrochemical biosensing method for protein kinase (PKA) activity was demonstrated by using a reduced graphene oxide-polydopamine-silver nanoparticle-Ti4+ (rGO-PDA-AgNPs-Ti4+) nanocomposite. The obtained nanocomposite possessed an integral capability for phosphopeptide recognition and signal readout. The polydopamine modified reduced graphene oxide (rGO-PDA) was firstly prepared based on a self-polymerization method of dopamine. The silver ions were adsorbed onto polydopamine (PDA) layer and directly reduced into silver nanoparticles (AgNPs), which was used for electrochemical signal reporting. Then, the Ti4+ cations were attached onto the PDA layer for phosphopeptide recognition according to the strong coordination ability of PDA with Ti4+ and phosphate group. The prepared rGO-PDA-AgNPs-Ti4+ nanocomposites were characterized with different methods. The developed rGO-PDA-AgNPs-Ti4+ nanocomposites were then employed for electrochemical analysis of PKA-catalyzed kemptide phosphorylation. The sensitive detection toward PKA activity was realized with an experimental detection limit of about 0.01 U/mL. It may be also extended for the inhibitor evaluation. Thus, it provided a facile and sensitive means for electrochemical analysis of PKA activity and inhibitor screening.

研究领域: 生物化学 · 分析化学 · 纳米材料科学
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CHINESE JOURNAL OF ANALYTICAL CHEMISTRY · 2021 · IF 1.134

A complementary bimetal synergized with polyethyleneimine functionalized affinity chromatography nanosphere for enrichment of global phosphopeptides

Jiang-Long DU,Meng-Yao FU,Ying-Hua YAN,Chuan-Fan DING

A novel metal-organic framework (MOF) synergized with Polyethyleneimine (PEI) functionalized hydrophilic magnetic nanosphere with two kinds of biological friendly metal ions (Fe 3 O 4 @PDA@MIL(Ti)-PEI-Nb) was fabricated and synthesized to enrich global phosphopeptides in complex biological samples. Based on the preference of Ti 4+ towards mono-phosphopeptides and the preference of Nb 5+ towards multi-phosphopeptides as well as the strong cationic charge density environment created by the high protonation of branched-PEI in acidic solution, the material performed prominently in the phosphopeptides enrichment, both in the standard protein for simulation and the three typical practical biological samples. The obtained material exhibits extremely high sensitivity (0.1 fmol), good selectivity (molar ratio of β-casein: BSA=1:5000), and excellent enrichment ability such as capturing 34 phosphopeptides from saliva. The combination of the comprehensive enrichment performance and biocompatibility presents a broad application prospect in phosphorylated proteomics.

研究领域: 分析化学 · 生物化学 · 材料科学 · 蛋白质组学
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Journal of Energy Chemistry · 2021 · IF 9.676

Insights into the enhanced structure stability and electrochemical performance of Ti4+/F− co-doped P2-Na0.67Ni0.33Mn0.67O2 cathodes for sodium ion batteries at high voltage

Pengfei Zhou,Jing Zhang,Zhennan Che,Zuhao Quan,Ju Duan,Xiaozhong Wu,Junying Weng,Jinping Zhao,Jin Zhou

P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 is considered as a promising cathode material for sodium-ion battery (SIBs) because of its high capacity and discharge potential. However, its practical use is limited by Na + /vacancy ordering and P2-O2 phase transition. Herein, a Ti 4+ /F − co-doping strategy is developed to address these issues. The optimal P2-Na 0.67 Ni 0.33 Mn 0.37 Ti 0.3 O 1.9 F 0.1 exhibits much enhanced sodium storage performance in the high voltage range of 2.0–4.4 V, including a cycling stability of 77.2% over 300 cycles at a rate of 2 C and a high-rate capability of 87.7 mAh g −1 at 6 C. Moreover, the P2-Na 0.67 Ni 0.33 Mn 0.37 Ti 0.3 O 1.9 F 0.1 delivers reversible capacities of 82.7 and 128.1 mAh g −1 at −10 and 50 °C at a rate of 2 C, respectively. The capacity retentions over 200 cycles at −10 °C is 94.2%, implying more opportunity for practical application. In-situ X-ray diffraction analysis reveals that both P2-O2 phase transitions and Na + /vacancy ordering is suppressed by Ti 4+ /F − co-doping, which resulting in fast Na + diffusion and stable phase structure. The hard carbon//P2-Na 0.67 Ni 0.33 Mn 0.37 Ti 0.3 O 1.9 F 0.1 full cell exhibits a high energy density of 310.2 Wh kg −1 and remarkable cyclability with 82.1% retention after 300 cycles at 1 C in the voltage range of 1.5–4.2 V. These results demonstrate that the co-doping Ti 4+ /F − is a promising strategy to improve the electrochemical properties of P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 , providing a facile tactic to develop high performance cathode materials for SIBs.

研究领域: 材料科学 · 电化学 · 能源存储 · 无机化学 · 固态化学 · 电池技术
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TALANTA · 2019 · IF 4.916

Hydrophilic phytic acid-functionalized magnetic dendritic mesoporous silica nanospheres with immobilized Ti4+: A dual-purpose affinity material for highly efficient enrichment of glycopeptides/phosphopeptides

Yayun Hong,Qiliang Zhan,Yu Zheng,Chenlu Pu,Hongli Zhao,Minbo Lan

In this work, magnetic mesoporous silica microspheres (Mag-MSMs) with ordered radial mesochannels were fabricated by a self-assembly synthesis in chlorobenzene-water mixed system. Then, the obtained Mag-MSMs were modified with polyethyleneimine (PEI), phytic acid (PA) and Ti 4+ (denoted as Mag-MSMs@PEI-PA-Ti 4+ ) via layer by layer (LbL) assembly. Due to the excellent hydrophilicity of PEI and PA and the large amount of Ti 4+ , the Mag-MSMs@PEI-PA-Ti 4+ possessed combined properties of hydrophilic interaction liquid chromatography (HILIC)- and immobilized metal ion affinity chromatography (IMAC)-based materials, which could be used as a dual-purpose material for N-glycopeptides or phosphopeptides enrichment. The proposed Mag-MSMs@PEI-PA-Ti 4+ exhibited an outstanding performance for N-glycopeptides enrichment (selectivity: IgG/BSA = 1:1000; sensitivity: 0.5 fmol/μL IgG) and phosphopeptides enrichment (selectivity: α-casein/BSA=1:5000; sensitivity: 0.2 fmol/μL α-casein). Furthermore, after enrichment with Mag-MSMs@PEI-PA-Ti 4+ , a total of 276 N-glycopeptides assigned to 132 glycoproteins were identified from 2 μL human serum and 1645 phosphopeptides corresponding to 704 phosphoproteins were identified from 200 μg HeLa cell extracts.

研究领域: 分析化学 · 蛋白质组学 · 生物医学工程
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TALANTA · 2023 · IF 6.1

A nitrogen-doped graphene tube composite based on immobilized metal affinity chromatography for the capture of phosphopeptides

Kexuan Wang,Ajuan Yu,Yu Gao,Miao Chen,Hang Yuan,Shusheng Zhang,Gangfeng Ouyang

A novel immobilized metal affinity chromatography (IMAC) functional composite, [email protected] @ [email protected] 4+ , was fabricated based on ultrathin magnetic nitrogen-doped graphene tube ( [email protected] ) after chelated Ti 4+ with polydopamine, following as a magnetic solid-phase extraction sorbent for rapidly selective enrichment and mass spectrometry identification of phosphorylated peptides. After optimized, the composite exhibited high specificity in the enrichment of phosphopeptides from the digest mixture of β -casein and bovine serum albumin (BSA). The robust method presented the low detection limits (1 fmol, 200 μL) and excellent selectivity (1:100) in the molar ration mixture of β -casein and BSA digests. Furthermore, the selective enrichment of phosphopeptides in the complex bio-samples, was successfully carried out. The results showed that 28 phosphopeptides were finally detected in mouse brain, and 2087 phosphorylated peptides were identified in the HeLa cells extracts with specific selectivity of 95.6%. The enrichment performance of [email protected] @ [email protected] 4+ was satisfactory, suggesting that the functional composite provided a potential application in the enrichment of trace phosphorylated peptides from the complex biological matrix.

研究领域: 分析化学 · 生物化学 · 蛋白质组学 · 生物技术
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FUEL · 2025 · IF 7.5

Interface engineering of Fe/TiO2 derived from kaoline impurities for selective 5-hydroxymethylfurfural hydrogenation to 2,5-dihydroxymethylfuran: The effect of Fe2+-Ov-Ti4+ sites synergy

Shijie Ma,Hangcheng Song,Jun Chen,Shuyan Yu,Hongyu Zhao

Biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) is a pivotal process in biomass valorization, however, it is hindered by the high cost of noble metal catalysts and environmental hazards posed by toxic copper-chromium systems. Herein, we report an unexpected discovery that naturally occurring Fe-Ti impurities in kaolinite act as a highly efficient heterogeneous catalyst for this reaction, challenging the conventional notion that impurities are detrimental to catalytic performance. Through hydrothermal synthesis and controlled reduction, Fe species are highly dispersed on the TiO 2 rutile surface, forming a synergistic Fe 2+ -oxygen vacancy-Ti 4+ (Fe 2+ -O v –Ti 4+ ) interface. The catalyst exhibits outstanding activity and selectivity under mild conditions (50 °C, 0.6  MPa H 2 ), achieving 97.6 % HMF conversion and 93.3 % DHMF selectivity, significantly outperforming catalysts based on kaolin and pure TiO 2 . Kinetic analysis reveals an apparent activation energy of 50.14  kJ/mol and a near first-order dependence on HMF concentration. Combined DFT calculations and in situ DRIFTS spectra confirm that the Fe 2+ -O v interface facilitates the adsorption of the HMF aldehyde group (adsorption energy −0.56  eV) and lowers the energy barrier for H 2 dissociation to 0.06  eV, enabling highly selective C=O hydrogenation. Moreover, the reaction benefits from the strong polarity of water and the hydrogen-bonding capacity, which further enhances catalytic performance. The catalyst retains over 90 % activity after 10 cycles, demonstrating excellent stability. This work not only provides a sustainable route for high-value utilization of kaolin-associated metal impurities, but also offers theoretical insights into the rational design of non-precious metal catalysts for biomass transformation.

研究领域: 催化化学 · 生物质能源 · 材料科学 · 环境友好化学 · 表面科学
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JOURNAL OF SEPARATION SCIENCE · 2024 ·Vol. 47 ·期 13 ·2400154 · IF 2.8

One-step enrichment and stepwise elution of glycoproteins and phosphoproteins by hydrophilic Ti4+-immobilized dendrimer poly(glycidyl methacrylate) microparticles functionalized with polyethylenimine and phytic acid

Hao Wang,Simin Li,Xinyan Wang,Xinyue Li,Minzhi Jiang,Shiying Chen,Zaiqi Hu,Haitian Li,Yuzhen Xu,Lei Jin

Glycosylation and phosphorylation rank as paramount post-translational modifications, and their analysis heavily relies on enrichment techniques. In this work, a facile approach was developed for the one-step simultaneous enrichment and stepwise elution of glycoproteins and phosphoproteins. The core of this approach was the application of the novel titanium (IV) ion immobilized poly(glycidyl methacrylate) microparticles functionalized with dendrimer polyethylenimine and phytic acid. The microparticles possessed dual enrichment capabilities due to their abundant titanium ions and hydroxyl groups on the surface. They demonstrate rapid adsorption equilibrium (within 30 min) and exceptional adsorption capacity for β-casein (1107.7 mg/g) and horseradish peroxidase (438.6 mg/g), surpassing that of bovine serum albumin (91.7 mg/g). Furthermore, sodium dodecyl sulfate-polyacrylamide gel electrophoresis was conducted to validate the enrichment capability. Experimental results across various biological samples, including standard protein mixtures, non-fat milk, and human serum, demonstrated the remarkable ability of these microparticles to enrich low-abundance glycoproteins and phosphoproteins from biological samples.

研究领域: 生物化学 · 蛋白质组学
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ANALYTICA CHIMICA ACTA · 2021 · IF 6.558

Design and application of hydrophilic bimetallic metal-organic framework magnetic nanoparticles for rapid capture of exosomes

Chenhui Zhang,Yini Pan,Yameng Zhao,Peiyao Wang,Lingyi Zhang,Weibing Zhang

Functional materials with good biocompatibility have been widely used in the study of genomics, proteomics and disease diagnosis, which has improved the progress of life science. In this paper, the material not only exhibited a strong affinity to the phosphate groups on the exosomal membrane due to the coexistence of Zr–O clusters and Ti 4+ , but also owned great hydrophilicity to reduce non-specific adsorption of contaminated proteins, achieving the separation and purification of exosomes from complex biosamples. The model exosomes extracted by ultracentrifugation (UC) were used to evaluate the feasibility of Fe 3 O 4 @UiO-66-NH 2 @PA-Ti 4+ capturing exosomes. The process of Fe 3 O 4 @UiO-66-NH 2 @PA-Ti 4+ capturing exosomes was simple to operate with a high recovery rate (97.3%) within a short time (5 min). Then Fe 3 O 4 @UiO-66-NH 2 @PA-Ti 4+ was further applied to capture exosomes in media and urine followed by the downstream proteomics analysis. 348 and 284 exosomal proteins were identified for cell medium and urine, respectively. This work shows great potential of the material for subsequent function research of disease-related exosomes by separating exosomes rapidly and efficiently.

研究领域: 材料科学 · 生物技术 · 生物化学 · 纳米技术 · 诊断学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Design and construction of an O-Au-O coordination environment in Au single atom-doped Ti4+ defected TiO2 for an enhanced oxidative ability of lattice oxygen for Hg0 oxidation

Zhilei Guo,Guohua Jing,Sara A. Tolba,Chung-shin Yuan,Yu-Hua Li,Xiaowei Zhang,Zhiwei Huang,Huawang Zhao,Xiaomin Wu,Huazhen Shen,Wenjie Xia

Transition metal oxide (TMO)-decorated TiO 2 catalysts excel at low-temperature Hg 0 oxidation. However, TMOs are typically found in large nanoparticles (NPs), resulting in a lower atom utilization efficiency. The current paper presents the design of an Au single atom (SA)-doped Ti 4+ defected TiO 2 (Au SAC-Ti 1-x O 2 ) and investigations concerning the influence of an O-Au-O coordination environment on Hg 0 oxidation. Au SAC-Ti 1-x O 2 was designed using an O-Au-O coordination environment and the O-Au-O orbital interaction was elucidated using density functional theory (DFT). The enhanced oxidative capability of lattice oxygen atoms and the interaction between Hg 0 and oxygen atoms were investigated. The O-Au-O coordination environment containing Au SAC Ti 1-x O 2 was then synthesized and characterized using X-ray absorption fine structure (XAFS), X-ray photoelectron spectroscopy (XPS), etc. Finally, Hg 0 oxidation catalytic activity was determined. Due to the increasing population of Au-O antibonding orbital interactions in the valence band, the bond order of O-Au-O in Au SAC Ti 1-x O 2 decreased significantly, thereby enhancing the oxidation ability of its adjacent oxygen atoms. Au SA and ultra-small Au clusters coexisted on a Ti 1-x O 2 catalyst, and the Hg 0 -oxidation efficiency at 150–200 °C was 14 times and 1.5 times greater than those of TiO 2 and 0.1 % Au/TiO 2 , respectively. Furthermore, Au SAC Ti 1-x O 2 was more resistant to the inhibition of SO 2 and NO. It provides an efficient method for developing highly active SA catalysts for Hg 0 oxidation.

研究领域: 催化化学 · 环境科学 · 材料化学 · 理论与计算化学
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Energy Storage Materials · 2023 · IF 20.4

High-performance lithium metal batteries based on composite solid-state electrolytes with high ceramic content

Xiaoyu Zhang,Jinhuan Wang,Dongqi Hu,Wei Du,Chuanxin Hou,Huiyu Jiang,Yuting Wei,Xiao Liu,Fuyi Jiang,Jianchao Sun,Hua Yuan,Xiaoyu Huang

The large scale application of solid state lithium metal batteries based on NASICON-type Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP) electrolyte has been hindered by insufficient ion conductivity and interface instability due to the spontaneous Ti 4+ reduction reaction between Li metal and LATP. To address these issues, Li 1.7 Al 0.3-x Bi x Ti 1.7 (PO 4 ) 3 (0 ≤  x  ≤ 0.03) (LABTP) electrolytes were prepared, and the influence of Bi substitution on the microstructure and conductivity of LATP were investigated. Suitable amount of Bi substitution accelerates densification and improves the ionic conductivity . Furthermore, unlike commonly used polyethylene oxide (PEO) and polyvinylidene difluoride (PVDF), polyvinylbutyral (PVB)-based quasi-solid electrolytes with LABTP is first-time proposed to improve the compatibility and stability of the LATP/Li interface. The synergistic effect of Bi doping and PVB reduces the reduction reaction of Ti 4+ . Small voltage hysteresis is observed in the corresponding Li||Li symmetric cells. The solid-state Li|LABTP@PVB|LiFePO 4 full cell can deliver a high capacity of 146.2 mAh g −1 and a stable cycling performance without reduction after 200 cycles.

研究领域: 材料科学 · 电化学 · 电池技术
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