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Acta Biomaterialia · 2022 · IF 10.633

Cancer cell membrane-coated C-TiO2 hollow nanoshells for combined sonodynamic and hypoxia-activated chemotherapy

Shipeng Ning,Xingliang Dai,Weiwei Tang,Qinglong Guo,Meng Lyu,Daoming Zhu,Wei Zhang,Haisheng Qian,Xiaxi Yao,Xianwen Wang

Sonodynamic therapy (SDT) is a promising strategy for tumor treatment that satisfies all requirements of penetrating deep-seated tissues without causing additional trauma. However, the hypoxic tumor microenvironment impairs the therapeutic effect of SDT. The synergistic treatment of oxygen concentration-dependent SDT and bio-reductive therapy has been proven to be an effective approach to improve the therapeutic efficiency of SDT by exploiting tumor hypoxia . Herein, a biomimetic drug delivery system (C-TiO 2 / [email protected] ) was successfully synthesized for combined SDT and hypoxia-activated chemotherapy, which was composed of tirapazamine (TPZ)-loaded C-TiO 2 hollow nanoshells (HNSs) as the inner cores and cancer cell membrane (CM) as the outer shells. C-TiO 2 HNSs coated with CM achieved tumor targeting via homologous binding. C-TiO 2 @CM as a nanocarrier loaded with TPZ in the presence of the trapping ability of CM and the special cavity structure of C-TiO 2 HNSs. Moreover, C-TiO 2 HNSs as sonosensitizers killed cancer cells under ultrasound (US) irradiation. Oxygen depletion during SDT induced a hypoxic environment in the tumor to activate the killing effect of co-delivered TPZ, thereby obtaining satisfactory synergistic therapeutic effects. In addition, C-TiO 2 @CM exhibited remarkable biocompatibility without manifest damage and toxicity to the blood and major organs of the mice. The study highlighted that C-TiO 2 / [email protected] served as a powerful biomimetic drug delivery system for effective SDT by exploiting tumor hypoxia. Statement of significance • C-TiO 2 @CM achieved tumor targeting via homologous binding. • C-TiO 2 hollow nanoshells could be used as a sonosensitizer and drug carrier for synergistic SDT and hypoxia-activated chemotherapy. • C-TiO 2 / [email protected] showed no obvious toxicity under the injection dose.

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MOLECULES · 2022 ·Vol. 27 ·期 21 ·7292 · IF 4.927

Carbon Quantum Dots Bridged TiO2/CdIn2S4 toward Photocatalytic Upgrading of Polycyclic Aromatic Hydrocarbons to Benzaldehyde

Jiangwei Zhang,Fei Yu,Xi Ke,He Yu,Peiyuan Guo,Lei Du,Menglong Zhang,Dongxiang Luo

Conversion of hazardous compounds to value-added chemicals using clean energy possesses massive industrial interest. This applies especially to the hazardous compounds that are frequently released in daily life. In this work, a S-scheme photocatalyst is optimized by rational loading of carbon quantum dots (CQDs) during the synthetic process. As a bridge, the presence of CQDs between TiO2and CdIn2S4improves the electron extraction from TiO2and supports the charge transport in S-scheme. Thanks to this, the TiO2/CQDs/CdIn2S4presents outstanding photoactivity in converting the polycyclic aromatic hydrocarbons (PAHs) released by cigarette to value-added benzaldehyde. The optimized photocatalyst performs 87.79% conversion rate and 72.76% selectivity in 1 h reaction under a simulated solar source, as confirmed by FT-IR and GC-MS. A combination of experiments and theoretical calculations are conducted to demonstrate the role of CQDs in TiO2/CQDs/CdIn2S4toward photocatalysis.Keywords:carbon quantum dots;photocatalysis;degradation;polycyclic aromatic hydrocarbons

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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Architecting Janus hydrogel evaporator with polydopamine-TiO2 photocatalyst for high-efficient solar desalination and purification

Jin Wen,Xiaoke Li,He Zhang,Size Zheng,Caini Yi,Liu Yang,Jinwen Shi

Solar-powered water distillation is one of the effective and promising ways of water purification. However, new high-efficiency evaporators are especially needed to reduce the energy requirement and improve water yields under natural sunlight. In this study, a Janus structured hydrogel with an interpenetrating double network was formed by polyvinyl alcohol and natural polysaccharide to speed up solar water purification. Due to its unique pore structure, water molecules can quickly escape from the surface of Janus hydrogel by molecular dynamics simulations. The Janus evaporator worked stably and the evaporation rate was achieved to 3.53 kg·m −2 ·h −1 under 1 sun illumination, which was attributed to the outstanding water transport capacity and thermal localization capacity. Meanwhile, the Janus-based solar evaporator exhibited excellent durability in wide acid–base range (pH 1–13) and salinity range (0–350‰), and long term (30 days). The daily yield of the Janus hydrogel reached 24.5 kg·m −2 ·h −1 in outdoor tests. The Janus evaporator enables efficient desalination and purification of other unconventional water sources, and can degrade more than 95% of organic dyes (trypan blue and Congo red) as a result of the synergistic effect of Polydopamine (PDA) /TiO 2 nanoparticles. This Janus structured hydrogel evaporator opens up potential applications in desalination and wastewater treatment.

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Electronic Materials Letters · 2022 ·Vol. 19 ·期 1 ·94-107 · IF 3.151

Visible Light Induced g-C3N4/TiO2/Ti3C2 Ternary Z-scheme Heterojunction Photocatalyst for Efficient Degradation

Luo Menghao,Feng Hange,Hu Yuechuan,Chen Keke,Dong Zibo,Xue Shaolin

Abstract Photocatalytic degradation has received considerable emphasis since it shows significant possibilities in environmental pollution. In this work, ternary Z-scheme heterojunction g-C 3 N 4 /TiO 2 /Ti 3 C 2 photocatalysts are designed and fabricated. The Z-scheme heterojunctions formed on the surfaces of g-C 3 N 4 and TiO 2 dramatically modify the photocatalytic performances of the compound under illumination. Meanwhile, in this process, multilayer Ti 3 C 2 , as the transport medium of Z-scheme heterojunction, is tightly bonded to TiO 2 generated by hydrothermal oxidation and g-C 3 N 4 with large specific surface area, which effectively facilitates the space charge separation and depresses the charge recombination. When the addition amount of TiO 2 /Ti 3 C 2 is 80 mg and calcined at 450 ℃ for 4 h, g-C 3 N 4 /TiO 2 /Ti 3 C 2 has the greatest photocatalytic performance, and the kinetic constant for degradation methyl orange (MO) was about 3.62 times that of g-C 3 N 4 and 14.55 times that of Ti 3 C 2 , respectively. This work illustrates that g-C 3 N 4 /TiO 2 /Ti 3 C 2 has outstanding potential and offers novel insights for designing and synthesizing new ternary heterojunction materials. Graphical Abstract

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MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING · 2022 · IF 4.644

Adsorption and catalytic removal of methyl orange from water by PIL-GO/TiO2/Fe3O4 composites

Hongfei Liu,Kexu Wang,Dongke Zhang,Dishun Zhao,Jianhua Zhai,Wenguang Cui

In this paper, an organic-inorganic hybrid material was synthesized via a simple but effective method, the novel material PGO-TiO 2 /Fe 3 O 4 (PGTF) was produced by loading TiO 2 and Fe 3 O 4 onto polymeric ionic liquid(PIL) functionalized graphene oxide(GO). The successful synthesis of PGTF and related structural feature were confirmed by a series of characterizations. The results of UV diffuse reflectance (DRS) demonstrated that the incorporation of PGO-Fe 3 O 4 to TiO 2 shifted the light absorption of TiO 2 from ultraviolet (UV) to visible region. The band gap energy of the PGTF reduced to1.92 eV as compared to TiO 2 (3.12 eV). Different materials were used to remove methyl orange (MO) from the aqueous solution. The results showed that PGTF had a superior capacity to remove dye due to the synergistic effects of adsorption and photocatalysis . The excellent adsorption properties may result from the high specific surface area of GO and the –NH 2 in the PIL. The polyionic liquid absorbed electrons due to the electrostatic action of the cation head in the polyionic liquid and GO which had high conductivity favored electron transport . The photocatalytic effectiveness increased as a result of the separation of photoexcited electron-hole pairs. The Langmuir model was investigated to evaluate the adsorption equilibrium behavior of MO dyes by PGTF. The maximum adsorption capacity( Q m ax ) was 67.88 mg/g for MO dyes. The pseudo-second-order kinetic model, with a correlation coefficient of 0.999, provided a good fit for the adsorption kinetic processes. The adsorption rate constant K 2 obtained by this model is 0.0072 g/(mg*min). The degradation rate constant of PGTF for MO in the photocatalytic stage was 0.00881 min −1 , which exhibited 3.7, 7.5 and 3 times higher than that of TiO 2 , FT and GTF. The main reactive species in the degradation process were O 2 − 、·OH、h + . PGTF had excellent repeatability because of the presence of Fe 3 O 4 . They can be easily separated from the water. These results indicated that the PGTF composites hold great potential for removing MO from wastewater.

CAS / MDL: 13822-56-5
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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Boosting photocatalytic activity of C-F-TiO2 nanosheets derived from in-situ pyrolysis of MXene

Qi Zhao,Ye Yuan,Luyan Zhang,Liang Qiao,Cheng Ding,Kangshun Wang,Hongpeng Li,Jun Ma,Panpan Wang,Tianming Chen,Feihong Wang

Nonmetal doping is widely used in the modification of titanium dioxides (TiO 2 ) for photocatalytic applications. As a typical two-dimensional layered nanomaterial, the excellent physical and chemical properties of MXene materials have been the focus of current research. In this study, carbon and fluorine co-doped MXene derived TiO 2 nanosheets (labelled as C-F-TiO 2 ) were successfully synthesized and used as catalysts for degrading 2,4,6-trichlorophenol (2,4,6-TCP) under UV light irradiation. The C-F-TiO 2 with ultrathin nanosheet structure enhanced light absorption range and decreased the bandgaps. The degradation efficiency of 2,4,6-TCP by C-F-TiO 2 was over 99 % in 90 min, and the degradation rate was more than twice that of commercial TiO 2 . The degradation rate still remained about 90 % in 90 min after five cycles. The results of quenching experiments and electron spin resonance (ESR) illustrated that more reactive oxygen species (ROS) were generated in the C-F-TiO 2 /UV system, which was 1.5 times that of commercial pure TiO 2 , and • O 2 – was the dominant ROS for 2,4,6-TCP degradation. This study provided insight to utilize physicochemical characteristics of MXene to synthesize non-metal co-doped TiO 2 nanosheet as a catalyst, exhibiting excellent reactivity in the potential application for organic pollutant degradation.

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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

Dissolution reaction of TiO2 in molten 6.58NaF-AlF3: A Raman spectroscopy and computational simulation study

Shuai Tang,Xianwei Hu,Jiangyu Yu,Aimin Liu,Zhongning Shi,Zhuo Li,Yifan Zhang,Zhaowen Wang

The NaF-AlF 3 -TiO 2 ternary system is often used in the molten salt electrolysis process to produce Al-Ti alloys. In order to explore the dissolution reaction of TiO 2 in NaF-AlF 3 melts, the ionic structure of (6.58NaF-AlF 3 )-TiO 2 molten salts was examined by Raman spectroscopy combined with computational simulation in the present study. The results indicated that when TiO 2 was added to 6.58NaF-AlF 3 molten salt, it first reacted with F - or AlF 6 3- with the following reactions: 2F - +2TiO 2  = Ti 2 O 4 F 2 2- , 4AlF 6 3- +6TiO 2  = 2Al 2 O 3  + 3Ti 2 O 2 F 6 2- +6F - , and then the generated Al 2 O 3 reacted with TiO 2 and F - or AlF 6 3- with the following reactions: Al 2 O 3  + 3TiO 2  + 21F - =3TiO 3 F 3 5- +2AlF 6 3- , Al 2 O 3  + 4AlF 6 3- =3Al 2 OF 8 4- , Al 2 O 3  + 4AlF 6 3- =3Al 2 OF 6 2- +6F - . In addition, Ti 2 O 2 F 6 2- , TiO 3 F 3 5- and Ti 2 O 4 F 2 2- clusters belonged to Cs, C2v and C1 point group, and the main characteristic Raman bands of these clusters were due to the stretching vibration of O 1 -Ti 3 -O 2 -Ti 4 , Ti 1 -O 7 and O 6 -Ti 2 -O 5 and/or O 7 -Ti 1 -O 8 , respectively. What’ more, the main characteristic Raman bands of Ti 2 O 2 F 6 2- , TiO 3 F 3 5- and Ti 2 O 4 F 2 2- were located at 790, 850 and 900 cm −1 , respectively.

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Nanomaterials · 2022 ·Vol. 12 ·期 21 ·3870 · IF 5.719

Catalytic Esterification of Levulinic Acid into the Biofuel n-Butyl Levulinate over Nanosized TiO2 Particles

Shuolin Zhou,Lu Wu,Junzhuo Bai,Min Lei,Min Long,Keying Huang

Levulinic esters, synthesized by the esterification of biomass-derived levulinic acid with various alcohols, is an important chemical that plays an essential role in the fields of biomass fuel additives, organic synthesis, and high value-added products. In the present work, the catalytic esterification of levulinic acid with n-butyl alcohol was selected as a typical model reaction to investigate the catalytic performance of an inexpensive commercial catalyst, titanium oxide nanoparticles. The influences of reaction time, reaction temperature, and catalyst loading on the conversion of levulinic acid to n-butyl levulinate were systematically examined through single-factor experiments. Additionally, the optimization of the reaction conditions was further investigated by a Box–Behnken design in response to the surface methodology. The desired product, n-butyl levulinate, with a good yield (77.6%) was achieved under the optimal conditions (reaction time of 8 h, reaction temperature of 120 °C, and catalyst dosage of 8.6 wt.%) when using titanium oxide nanoparticles as catalysts. Furthermore, it was found that addition of water to the catalytic system facilitated the reaction process, to some extent. This study reveals that the nanosized TiO2material,as an efficient solid acid catalyst, had good catalytic performance and stability for the esterification of levulinic acid after six consecutive uses.Keywords:TiO2nanoparticles;solid acid catalyst;n-butyl levulinate;esterification;response surface methodology

CAS / MDL: 13463-67-7 123-76-2
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Catalysts · 2022 ·Vol. 12 ·期 10 ·1286 · IF 4.501

Spillover Hydrogen on Electron-Rich Ni/m-TiO2 for Hydrogenation of Furfural to Tetrahydrofurfuryl Alcohol

Ravi Balaga,Kishore Ramineni,Xiaoqiang Zhang,Peifang Yan,Mahender Reddy Marri,Vijayanand Perupogu,Zongchao Conrad Zhang

Conversion of biomass-derived furfural (FFA) platform molecule to value-added tetrahydrofurfuryl alcohol (THFA) molecule is a sustainable route using an efficient non-noble metallic catalyst in water solvent. In this work, Ni in various loadings on mesoporous titanium dioxide (m-TiO2) was synthesized in one pot by Evaporation-Induced Self-Assembly (EISA). The synthesised catalysts were evaluated for the hydrogenation of furfural to tetrahydrofurfuryl alcohol. The catalysts were characterised using a combination of spectroscopic techniques such as XRD, H2-TPR, H2-TPD, XPS, SEM-EDX, TEM, and HR-TEM. The characterization results show that the Ni/m-TiO2materials exhibit enhanced electron-rich active sites, facilitated hydrogen spillover, uniform dispersion of small Ni particles (~5 nm), and strong metal support interaction between Ni and TiO2. Among the various Ni dopings, 7.5 wt.% Ni/m-TiO2catalyst exhibited the best performance and achieved 99.9% FFA conversion and 93.2% THFA selectivity in water solvent at 100 °C and under 2 MPa H2. Additionally, detailed kinetic studies, process parameters, the stability and reusability of the catalyst were also studied. The results demonstrated that the 7.5 wt.% Ni/m-TiO2catalyst is highly active and stable.Keywords:biomass;furfural hydrogenation;electron-rich Ni;SMSI;spillover

CAS / MDL: 13478-00-7
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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

Z-scheme Au@TiO2/Bi2WO6 heterojunction as efficient visible-light photocatalyst for degradation of antibiotics

Kejie Jin,Mian Qin,Xinyi Li,Rui Wang,Yang Zhao,Huan Wang

Semiconductor photocatalysis can be regarded as one of effective strategies to overcome the great challenges encountered with conventional technologies for environmental remediation. In this research, Z-scheme heterostructure composed of core–shell Au@TiO 2 nanoparticles and flower-like Bi 2 WO 6 nanosheets has been successfully prepared through the reverse micelle sol–gel method followed by a hydrothermal process. The structural characteristics, chemical compositions and photoelectrochemical properties of this ternary composite photocatalyst (Au@TiO 2 /Bi 2 WO 6 ) were further investigated in detail. Benefitted from the synergy of the heterojunction construction and metallic surface plasmon resonance effect, the Au@TiO 2 /Bi 2 WO 6 with an optimal mass ratio of Au@TiO 2 to Bi 2 WO 6 exhibited the significantly enhanced photocatalytic activity for degradation of antibiotics under visible-light irradiation, in which the degradation efficiency of sulfamethoxazole (SMX) and tetracycline hydrochloride (TC) could be up to 96.9% and 95.0% within 75 min, respectively. The reaction rate constant for SMX and TC degradation was calculated to be around 0.0425 min −1 and 0.0314 min −1 , which has 7.2 times and 1.9 times enhancement compared with single Bi 2 WO 6 , respectively. In addition, the cyclic stability and photocatalytic mechanism of Au@TiO 2 /Bi 2 WO 6 were further verified. Our primary results provide a feasible strategy to develop core–shell heterostructured photocatalysts with superior performance for the efficient removal of low-concentration antibiotics in water.

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ChemCatChem · 2022 ·Vol. 14 ·期 19 ·e202200756 · IF 5.497

Atomic-Layer-Deposited Oxygen-Deficient TiO2 on Carbon Cloth: An Efficient Electrocatalyst for Nitrogen Fixation

Xiaobo Ma,Qiyu Zhang,Lijun Gao,Yating Zhang,Chao Hu

Graphical Nitrogen fixation : Oxygen-vacancy-rich TiO 2 supported on carbon cloth (V-TiO 2 /CC) are prepared by atomic layer deposition technique coupled with annealing process, and used as a high-performance electrocatalyst for N 2 reduction to NH 3 . The as-obtained V-TiO 2 /CC shows a Faradaic efficiency as high as 31.6 % and a yield of 3.4 μg h −1 cm −2 in 0.5 M LiOH aqueous electrolyte. Electrochemical nitrogen reduction reaction (NRR) is a promising alternative to the traditional Haber-Bosch process for ammonia production, but plagued by the high bonding energy of N≡N and the hydrogen evolution side reaction. Recent studies show that enhancing the adsorption and activation of N 2 on the catalyst is the key to improving the NRR performance, and the introduction of oxygen vacancies on the surface of metal oxides is an effective way to design high-performance catalysts. Here, TiO 2 with different thicknesses was deposited on conductive carbon cloth by atomic layer deposition, and then oxygen vacancies were introduced on the catalyst surface by an annealing process. The abundant oxygen vacancies on TiO 2 surface are found to be beneficial for enhancing the NRR activity of the catalysts. Moreover, the NRR activity is significantly influenced by the thickness of the deposited TiO 2 layer, and an over-thick TiO 2 layer leads to a decrease in the conductivity of the catalysts and hinders the charge transfer process. With the optimum thickness, the atomic-layer-deposited oxygen-deficient TiO 2 catalysts can achieve a Faradaic efficiency of 31.6 % and a yield of 3.4 μg h −1 cm −2 for ammonia production in 0.5 M LiOH aqueous electrolyte at 0 vs. RHE. It is anticipated that ultrathin semiconducting oxide catalysts synthesized by atomic layer deposition will have broad and promising applications for efficient electrochemical NRR. Introduction

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ACS Catalysis · 2022 · IF 13.7

Selective Photocatalytic Oxidation of Methane to Oxygenates over Cu–W–TiO2 with Significant Carrier Traps

Min Huang,Shuyi Zhang,Bo Wu,Yao Wei,Xing Yu,Yongping Gan,Tiejun Lin,Fei Yu,Fanfei Sun,Zheng Jiang,Liangshu Zhong

Direct selective methane photooxidation to liquid oxygenates with high productivity and selectivity under mild reaction conditions is highly urgent but remains challenging. Herein, a Cu and W codoped TiO2 (Cu–W–TiO2) photocatalyst was fabricated to enable aerobic oxidation of methane into oxygenates with limited formation of CO2 under ambient temperature. A high oxygenate productivity of 34.5 mmol g–1 with a remarkable selectivity of 97.1% was achieved over the Cu–W–TiO2 photocatalyst. Based on structural characterizations and mechanism studies, it was suggested that the Cu species acted as hole traps, while oxygen vacancies and the W6+-dopant state worked as electron traps. The inhibited recombination of photogenerated carriers contributed to enhanced photocatalytic efficiency. The modulated electronic and band structure promoted the activation of methane and hindered the overoxidation of oxygenates.

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