ACS Catalysis
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2013
·
IF 5.265
Wen-Juan Zhou,Raphael Wischert,Kai Xue,Yu-Ting Zheng,Belén Albela,Laurent Bonneviot,Jean-Marc Clacens,Floryan De Campo,Marc Pera-Titus,Peng Wu
Various types of Ti-containing zeolites, i.e., Ti-MWW, TS-1, Ti-MOR, and Ti-BEA, have been evaluated as candidates for the liquid-phase oxidation of cyclohexane using t-butyl hydroperoxide (TBHP, 7–8 wt %) as model oxidant. Ti-MWW zeolite displayed the highest activity for cyclohexanol and cyclohexanone (KA oil) with an overall selectivity higher than 90% at 80 °C, making this catalyst a candidate of choice for industrial KA oil production by deperoxidation of cyclohexyl hydroperoxide. The effect of the reaction temperature, reaction time, catalyst amount, and catalyst stability on Ti-MWW was surveyed in detail. The Ti-MWW catalyst showed a stable performance and could be recycled at least four times without detectable Ti leaching and loss of structural stability. The active sites for cyclohexane oxidation appeared to be located near external 12-ring cups in the Ti-MWW framework as suggested by a series of position-selective poisoning tests with tripropyl- and triphenylamine, impelling cyclohexane diffusion within the internal 10-ring channels. EPR experiments supported by DFT calculations suggested the coexistence of both Ti(IV)-OO• (peroxyl) and Ti(IV)-O• (oxyl) species generated through bimolecular pathways, implying simultaneously (SiO)3Ti(OOtBu) species and tBuOOH. The catalytic activity was strongly inhibited in the presence of alkenes, leading to the preferential formation of the epoxidation product with no detectable formation of radicals. Notably, this is the first time that oxyl species have been detected particularly with the help of DFT calculations. Predicted differences of g tensors between peroxyl and oxyl species at various hydration levels in the presence of cyclohexane were consistent with the EPR spectra.
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CHEMICAL ENGINEERING JOURNAL
·
2017
·
IF 6.216
Haiyan Song,Jiang-An You,Bin Li,Chunxia Chen,Jie Huang,Jin Zhang
Novel titanosilicate composites with bimodal mesopores using molecular sieves Ti-HMS and Ti-KIL-2 as structural components were successfully synthesized by two-step and dual-template methods in a comparative study. The as-synthesized Ti-HMS/KIL-2 samples were characterized by a series of techniques including X-ray diffraction, UV–vis, N 2 sorption and scanning electronic microscopy, and their performance was tested in adsorptive denitrogenation for model fuel containing pyridine or quinoline. Although Ti-HMS/KIL-2 composites were constructed following the different pathway of self-assembly, most of them obtained coexisting properties and structures of Ti-HMS and Ti-KIL-2, as well as the intact framework Ti in tetrahedral coordination. A key finding is that the mesopores size of Ti-KIL-2 component in the composite can be regulated via the introduction of Ti-HMS precursor or organic template dodecylamine. Especially, the composites of dual-template method presented hierarchical mesopores with obvious bimodal distribution. In addition to constructing the hierarchical structure, introduction of Ti-HMS into Ti-KIL-2 matrix improved the adsorptive denitrogenation performance, which was influenced by the synthetic strategy of Ti-HMS/KIL-2. The target adsorbates achieved the best match with the adjustable pores of Ti-HMS/KIL-2. Therefore, (0.6 D )Ti-HMS/KIL-2 and (0.5 T )Ti-HMS/KIL-2 as the optimized adsorbents obtained remarkable adsorption efficiency respectively for pyridine and quinoline. Essence of the adsorptive denitrogenation process was revealed via the adsorption isotherms and the adsorption thermodynamics. Finally, Ti-HMS/KIL-2 composites achieved the improvement in hydrothermal stability and recyclability during adsorption of pyridine and quinoline, and exhibited the potential of industrial application.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Yu Hu,Xin Li,Xiaolin Zhang,Weiming Zhang,Bingcai Pan,Ming Hua
The salt ions (typically > 1000 mg/L) present in copper plating wastewater limit the application of ion exchange in the deep treatment of copper complexes (such as copper-pyrophosphate (Cu-PPi)). Metal nanoparticle immobilization is an effective method, and bimetallic nanoparticles have more potential than monometallic ones. In this study, bimetallic nanocomposite Ti-Zr-201 was successfully synthesized by confining Ti-Zr oxide nanoparticles in the pores of anion exchange polymer (D201). The obtained new adsorbent Ti-Zr-201 with bimetallic doped structure had more active sites (7.22 mmol/g), higher hydroxyl content (3.51 × 10 22 OH/ nm 2 ) and larger specific surface area (31.65 m 2 /g) than monometallic nanocomposite adsorbents (Zr-201 and Ti-201). The results showed that Ti-Zr-201 has better Cu-PPi adsorption capacity (24.82 mg Cu/g) than Zr-201 (21.48 mg Cu/g) and Ti-201 (21.71 mg Cu/g) in the high salt water (2000 mg/L NO 3 – ). Further mechanistic studies revealed that Cu-PPi removal as a whole was mainly realized via ternary complexation (Ti/Zr-O-Cu-PPi of Type-A, Ti/Zr-O-PPi-Cu of Type-B) and quaternary complexation (Ti/Zr-O-PPi-Cu-PPi of Type-B) both formed during the adsorption. The saturated Ti-Zr-201 can be regenerated more than 90% rapidly and had good stability. Moreover, the novel adsorbent also had a excellent removal effect on several other phosphorous copper complexes (tripolyphosphate, methyl dihydrogen phosphate, etc.). Therefore, the nanocomposite Ti-Zr-201 exhibited promising application on the deep removal of complex-state Cu with phosphorus ligands from high salty wastewater.
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APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Bingbing Cui,Guodong Fu
Given that heterojunction engineering is an effective method for improving the separation efficiency of photoexcited electrons in WO 3 -based photochromic systems, a series of solid-state photochromic Zr/Ti-MOF@WO 3 heterojunctions prepared via a facile hydrothermal strategy, where Zr/Ti-MOF with photosensitivity and chemical stability was selected as template to load WO 3 . Zr/Ti-MOF@WO 3 heterojunctions were verified as nanoparticles filled with thin layer structure and WO 3 was diffused into the Zr/Ti-MOF planar. The appropriate conductive band energies facilitate the transport of photostimulated electrons from Zr/Ti-MOF to WO 3 , resulting in a fast photresponse in color changes (it only takes 1 s). In addition, a carrier for information storage and data dynamic encryption was developed on the basis of the photochromic Zr/Ti-MOF@WO 3 heterojunctions. This work presents a promising way to improve the electron/holes separation efficiency by constructing unique heterojunctions and further explore novel WO 3 -based photochromic systems and broaden their applications in rewritable media and data security.
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Advanced Healthcare Materials
·
2025
·
IF 9.6
Minggang Yang,Yufan Zhang,Zhenhao Hou,Jianbo Wu,Fuwei Liu,Jun Wu,Kelvin W.K. Yeung,Wenhao Qian,Xuanyong Liu,Liang Kong,Yunpeng Li,Jiajun Qiu,Guocheng Wang
Antibiotic therapy is a key strategy for treating infections associated with orthopedic implants, yet its limited effectiveness and potential to disrupt bone healing highlight the need for innovative approaches. Herein, a TiO 2 -Graphene (TiO 2 -G) metastructure is developed on Ti implant surface using a hydrothermal method coupled with plasma-enhanced chemical vapor deposition (PECVD), showing strong near-infrared light (NIR) absorption. The antibiotic doxycycline (DOX) is successfully loaded onto TiO 2 -G and exhibited enhanced NIR release. The promising antibacterial efficacy is proven by both in vitro and in vivo tests with NIR irradiation for 5 min, which is ascribed to the synergistic photocatalytic activity of TiO 2 -G and NIR-responsive release of DOX. Interestingly, after 5 min of NIR irradiation, the TiO 2 -G metasurface neutralized the immediate negative effects of photodynamics and even upregulated the expression of osteogenic genes (osteocalcin (OPN), osteopontin (BSP), and bone sialoprotein (OCN)), with particularly enhanced effects observed on day 14. Moreover, the sustained release function of TiO 2 -G significantly mitigated the cytotoxicity of free antibiotics with antibacterial capabilities comparable to those of TiO 2 -G/DOX under NIR irradiation for 5 min. Consequently, the in vivo studies proved that the TiO 2 -G metastructure enhanced the osteointegration of the implant even in the absence of infection when loaded with DOX.
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Journal of Materials Chemistry A
·
2025
·
IF 9.5
Chen Su,Mingyu Li,Shuai Zhang,Weiqing Liu,Yuanzhang Wang,Peipei Li,Huanran Feng,Ming-Shui Yao,Weiwei Wu,Lu Zhang
The development of multifunctional hydrogels with enhanced mechanical, electrical, and electromagnetic properties has become a key focus in various advanced applications, including wearable electronics, strain sensors, and electromagnetic interference (EMI) shielding. However, challenges remain in achieving a balanced integration of stretchability, conductivity, and broadband microwave absorption within a single material. This study addresses these limitations by introducing a novel dual-crosslinked Ti₃C₂Tx MXene-based hydrogel designed for wearable sensor and EMI shielding applications. The PVA/MXene/PSS hydrogel is synthesized via a freeze-thaw crosslinking method to create a three-dimensional (3D) conductive network. Water retention and conductivity are enhanced through the synergistic effect between sodium chloride (NaCl) and formic acid (HCOOH), addressing key challenges such as water evaporation and MXene dispersion. The resulting hydrogel exhibits impressive mechanical stretchability (369% tensile strain), long-term stability (6000 s under 25% strain), and ultra-high strain sensitivity with a minimum detectable strain of 1%. It demonstrates gauge factors of 0.78 and 0.51 in the transverse and longitudinal directions for strains below 50%, respectively, and 0.28 and 0.37 for strains between 50% and 100%. Moreover, it demonstrates exceptional broadband microwave absorption with a peak reflection loss of −55.5 dB at 10.73 GHz, with an effective absorption bandwidth of 6.34 GHz. The combination of excellent mechanical, electrical, and microwave properties, along with superior stretchability and durability, makes this hydrogel a promising candidate for next-generation wearable sensors, flexible electronics, and electromagnetic interference shielding.
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ACS Nano
·
2025
·
IF 16
Xinqiang Hu,Maohua Chen,Huocheng Yang,Hao Wei,Bikun Zhou,Menghuan Li,Zhong Luo,Kaiyong Cai,Yan Hu
Ti-based implants are a mainstream treatment modality for bone fracture treatment, but their osseointegration is severely hampered by osteoporosis-associated biomineralization disorder. This study reports a multifunctional hydrogel-biovesicle composite coating capable of enhancing interfacial biomineralization in a cascade manner to facilitate Ti-based implant osteointegration. For this purpose, we first prepared azido-tagged osteoblast membrane vesicles through glycoengineering of live osteoblasts for loading calcitriol (VD3), which were then facilely conjugated to hydrogels composed of phosphorylated gelatin (P-gel) and dibenzocyclooctyne-modified carboxymethyl chitosan through click reaction. Notably, liquid nitrogen-assisted directional freezing fabrication technology was applied during hydrogel preparation to mimic the extracellular matrix (ECM) pattern in healthy osteons for enhancing Ca2+ influx and osteogenic differentiation of adherent osteoblasts, while the biovesicle-mediated in situ VD3 delivery could further boost cellular Ca/P metabolism and mineral precursor excretion to accelerate ECM mineralization. These functions could act in a cooperative manner to promote new bone formation at the bone-implant interface to accelerate Ti-based implant osteointegration, presenting a promising approach for osteoporotic bone fracture repair in the clinic.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2025
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IF 6.3
Xiufen Yang,Runzhi Han,LiWei Shi,YiXin Li,Changyong Lan,Leiming Chen,Chuanfu Huang
To address the persistent challenges of wide band gap (2.13 eV), high carrier recombination rates, and poor cycling stability in bismuth ferrite (BiFeO 3 BFO)-based photocatalysts, this study introduces an unprecedented La³⁺/Ti⁴⁺ dual-site doping strategy. La/Ti co-doped BFO nanoparticles (n% BLFTO) were synthesized using a sol-gel method. The synergistic effects of La³⁺-induced gradient oxygen vacancies (increased by 270%) and Ti³⁺/Ti⁴⁺ redox couples led to a significant band gap narrowing to 1.79 eV, extending visible light absorption to 450-700 nm. Remarkably, the optimized 30% BLFTO sample achieved a 98.9% degradation efficiency of Rhodamine B (Rh B) within 120 minutes-7.17% higher than pure BFO and maintained 95.92% efficiency after 12 cycles (2.98% decay), demonstrating exceptional stability rarely reported in prior works. In-situ X-ray Photoelectron Spectroscopy and Photoluminescence Spectroscopy analyses revealed that dual-doping synergistically modulates carrier dynamics via Fe²⁺/Fe³⁺ mixed valency and abundant oxygen vacancies, thereby prolonging carrier lifetimes and enhancing photocatalytic activity. This work pioneers a dual-doping framework that simultaneously enables highly efficient visible-light-driven degradation of Rh B and exceptional cycling stability, offering new insights for the design of robust photocatalysts for environmental remediation and renewable energy applications.
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Coatings
·
2025
·Vol. 15
·期 8
·948
·
IF 2.8
Liting Mu,Yiqi Lian,Shiyu Zheng,Shuo Chang,Ximeng Li,Changhai Sun,Hongbin Qiu
Titanium and its alloys are widely used in orthopedics because of their excellent mechanical properties and biocompatibility; however, their bioinert surface results in sluggish osseointegration and renders implants susceptible to bacterial infection. This study innovatively constructed a “CHP-Ti-MAO” composite coating, which aims to simultaneously improve early osseointegration and antibacterial performance. CHP micron coatings coated with hydroxyapatite (HA) and curcumin (Cur) at different PLGA concentrations (50%, 100%, and 150%) were deposited on the basis of calcium–phosphorus ceramic coatings prepared by micro-arc oxidation (MAO) following the emulsification-solvent volatilization method. It was found that increasing the concentration of PLGA can increase the particle size of the coating, enhance the hydrophilicity, and significantly improve the sustained release performance of the drug. Among them, the 100% PLGA concentration group performed the best: the drug-release half-life reached 75 h, and the corrosion current density was the lowest (9.5 × 10−9A/cm2), showing the best corrosion resistance. This group of coatings has a strong and long-term antibacterial effect on Escherichia coli, with an antibacterial rate of more than 95% at 24 h and more than 99% by day 17. The hemolysis rate of all coatings was lower than 5%, indicating good biocompatibility. This study confirmed that 100% CHP-Ti-MAO composite coating successfully solved the limitations of excessive pore size and insufficient antibacterial persistence of an MAO layer and also had excellent slow-release, corrosion resistance, and high-efficiency antibacterial capabilities, which provided an important basis for the development of a new generation of multifunctional titanium-based implants.
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ChemCatChem
·
2025
·
IF 3.9
Yu Tang,Kaiyang Xu,Lingfeng Weng,Yuanjie Xu,Li Tan,Lizhi Wu
Cyclopentanone (CPO) is a high-value platform chemical widely used in fuel, fragrances, and polymers, yet its sustainable production from biomass remains challenging. This work addresses this gap by developing efficient Ni/TiO 2 catalysts through crystal phase engineering of TiO 2 supports (anatase, rutile, mixed-phase P25) for aqueous-phase hydrogenative ring-rearrangement of furfural (FAL) to CPO. Crucially, the TiO 2 phase dictates the Ni–O–Ti interface structure, governing nickel speciation and reactivity. Ni supported on mixed-phase P25 achieves exceptional performance under industrially relevant conditions: 91.1% FAL conversion, 89.3% CPO selectivity, and specific rate of 71.6 h −1 , surpassing catalysts on pure anatase (9.1% conversion) or rutile (55.8% conversion). Physical mixture experiments confirm this superiority stems from the intrinsic interface of P25, not component blending. Characterization reveals that P25 stabilizes a multifunctional surface ensemble: metallic Ni⁰ (18.0% by XPS) enables hydrogenation, while cationic Ni 2+ facilitates acid-catalyzed dehydration and ring rearrangement. Simultaneously, sufficient metal–support interaction permits in situ regeneration of active sites. The optimized 1Ni/P25 demonstrates robust stability over five cycles with retained selectivity (>90%), showcasing practical durability. This study provides a scalable design strategy—support crystal phase tuning—to engineer cost-effective, multifunctional catalysts for industrial biomass upgrading, advancing green manufacturing of cyclic ketones without precious metals. Graphical This study investigates how the TiO 2 crystal phases (anatase, rutile, and P25) affect Ni-based catalysts in the conversion of furfural (FAL) to cyclopentanone (CPO). Ni/TiO 2 -P25 shows superior performance: 91.1% FAL conversion and 89.3% CPO selectivity, outperforming that on anatase and rutile. It stabilizes mixed-valence Ni (Ni° for hydrogenation, Ni 2+ for acid-catalyzed steps) via unique Ni–O–Ti interfaces, enabling efficient FAL conversion.
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CORROSION SCIENCE
·
2024
·
IF 7.4
Xin-Ran Li,Xian-Ze Meng,Qiu-Yu Huang,Jian Wang,Yu-Yua Xiao,Lian-Kui Wu,Fa-He Cao
Metal corrosion exhibits coupled multi-reaction features, making it challenging to quantitatively study the dissolution reaction with variable-valent cations, particularly in valence quantification. This work develops a novel scanning electrochemical microscopy mode and applies it to Ti dissolution study in acidic fluorides. This mode identifies the potential-dependent corrosion reactions and quantifies the valence evolution of Ti from HER to transpassive regions. Results provide direct electrochemical evidence for soluble Ti( z ≤3), for the first time, and revise the reported dissolution equation. The proposed mode overcomes the drawbacks of macro-electrochemical analysis based on coupling information and provides an effective quantitation method for anodic reactions .
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LANGMUIR
·
2024
·
IF 3.7
Yuanzhen He,Dengjie Zhong,Yunlan Xu,Ran Jiang,Jiayou Zhang,Pengfei Liao
A La-doped Ti/SnO2-Sb2O4 electrode with TiO2-NTs intermediate layer (Ti/TiO2-NTs/SnO2-Sb2O4-La) was created via the electrodeposition technique. The physicochemical and electrochemical properties of the electrode were analyzed through FESEM, XRD, XPS, CV, and LSV electrochemical tests. The results showed that TiO2-NTs were tightly packed on the surface of Ti substrate, thus improving the binding force of the SnO2-Sb2O4-La coating, offering greater specific surface area, more active spots, higher current response, and longer lifespan for the degradation of rhodamine B. The lifespan of the Ti/TiO2-NTs/SnO2-Sb2O4-La electrode reached 200 min (1000 mA cm–2, 1 M H2SO4), while the actual service life was up to 3699 h. Under the conditions of initial pH 3.0, Na2SO4 concentration of 0.1 M, current density of 30 mA cm–2, and initial rhodamine B concentration of 20 mg L–1, the color and TOC removal rate of rhodamine B reached 100% and 86.13% within 15 and 30 min, respectively. Rhodamine B was decomposed into acids, esters, and other molecular compounds under the action of •OH and SO4•– free radicals and electrocatalysis, and finally completely mineralized into CO2 and H2O. It is anticipated that this work will yield a novel research concept for producing DSA electrodes with superior catalytic efficacy and elevated stability.
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