JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS
·
2023
·
IF 4
Jiawei Zhao,Bin Wang,Yaru Zhao,Mingming Hou,Changhui Xin,Qian Li,Xin Yu
Strong visible-light absorption and high surface areas contribute to high-perform semiconductor photocatalysis . This work aims to fabricate self-doped Ti 3+ -TiO 2 microspheres and dye sensitized self-doped Ti 3+ -TiO 2 composites with high surface areas and visible-light absorption via one-pot solvothermal strategy for highly enhanced photocatalytic tetracycline degradation under visible-light irradiation. The experimental results showed that the obtained Ti 3+ -TiO 2 microspheres showed enhanced visible-light capture capacity and a larger surface area of 204.9 m 2 g −1 . Besides, the obtained Eosin Y/Ti 3+ -TiO 2 composites showed efficient visible-light absorption and highly boosted photocatalytic performance towards tetracycline degradation. The highest rate constant for Eosin Y/Ti 3+ -TiO 2 -9% composite reached as high as 0.06657 min −1 , approximately 8.09 times that of commercial TiO 2 , strongly demonstrating the significant roles of dye sensitization. Finally, a reasonable dye-sensitization visible-light photocatalytic mechanism was suggested.
研究领域:
材料科学
·
环境科学
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DOI
高影响因子
MATERIALS LETTERS
·
2015
·
IF 2.489
Jingzhong Zhao,Weiqiang Xing,Yang Li,Kathy Lu
Oxygen-deficient anatase TiO 2 sheets with dominant (001) facets are becoming a hot research topic due to their promising high activity in heterogeneous reactions . In this work, a series of (001) facets dominated TiO 2 with distributed oxygen vacancies and Ti 3+ was prepared by a simple hydrothermal method with the TiB 2 as a precursor. The as-prepared powders were characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), Transmission Electron Microscope (TEM), X-ray photoelectron spectroscopy (XPS) and UV–visible diffuse reflectance spectroscopy (UV–vis). The results show that the particle size of as-prepared TiO 2 increases and its band gap narrows with the hydrothermal temperature increasing from 140 °C to 180 °C. Besides, oxygen vacancies and Ti 3+ are generated during the TiB 2 hydrolysis, which leads to new absorption spectrum in the visible light region. Photocatalytic test shows that sample prepared at 180 °C presents the highest degradation efficiency.
研究领域:
材料科学
·
光催化
·
纳米材料
·
表面化学
·
半导体材料
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DOI
高影响因子
Catalysts
·
2020
·Vol. 10
·期 5
·539
·
IF 3.52
Lan Luo,Tingting Zhang,Xin Zhang,Rongping Yun,Yanjun Lin,Bing Zhang,Xu Xiang
Hydrogen production by photoreforming of biomass-derived ethanol is a renewable way of obtaining clean fuel. We developed a site-specific deposition strategy to construct supported Au catalysts by rationally constructing Ti3+defects inTiO2nanorods and Cu2O-TiO2p-n junction across the interface of two components. The Au nanoparticles (~2.5 nm) were selectively anchored onto either TiO2nanorods (Au@TiO2/Cu2O) or Cu2O nanocubes (Au@Cu2O/TiO2) or both TiO2and Cu2O (Au@TiO2/Cu2O@Au) with the same Au loading. The electronic structure of supported Au species was changed by forming Au@TiO2interface due to the adjacent Ti3+defects and the associated oxygen vacancies while unchanged in Au@Cu2O/TiO2catalyst. The p-n junction of TiO2/Cu2O promoted charge separation and transfer across the junction. During ethanol photoreforming, Au@TiO2/Cu2O catalyst possessing both the Au@TiO2interface and the p-n junction showed the highest H2production rate of 8548 μmol gcat−1h−1under simulated solar light, apparently superior to both Au@TiO2and Au@Cu2O/TiO2catalyst. The acetaldehyde was produced in liquid phase at an almost stoichiometric rate, and C−C cleavage of ethanol molecules to form CH4or CO2was greatly inhibited. Extensive spectroscopic results support the claim that Au adjacent to surface Ti3+defects could be active sites for H2production and p-n junction of TiO2/Cu2O facilitates photo-generated charge transfer and further dehydrogenation of ethanol to acetaldehyde during the photoreforming.Keywords:ethanol reforming;hydrogen production;Au catalyst;Ti3+defect;site-specific deposition
研究领域:
材料科学
·
催化化学
·
可再生能源
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DOI
高影响因子
ACS Catalysis
·
2019
·
IF 12.221
Jian Li,Yaping Lin,Xiulian Pan,Dengyun Miao,Ding Ding,Yi Cui,Jinhu Dong,Xinhe Bao
Strong metal–support interaction (SMSI) has been widely recognized for platinum-group metals on reducible oxide supports. Herein we report that the catalytic activity of Ni catalyst in CO2 methanation is significantly suppressed over conventional anatase (a-TiO2) support due to the SMSI-induced formation of a titania overlayer around the Ni nanoparticles. Furthermore, CO is the only product . In contrast, the NH3-treatment and H2-treatment of the a-TiO2 support enhance remarkably the activity of Ni, i.e., CO2 conversion increases by 1 order of magnitude and CO2 is hydrogenated almost exclusively to CH4. X-ray photoelectron spectroscopy (XPS), H2 and CO chemisorption, and low temperature electron paramagnetic resonance (EPR) reveal that the enhanced CO2 methanation activity may be related with the Ti3+ species in the bulk that are generated by reduction treatment, which likely have altered the SMSI between Ni and a-TiO2 support. This simple reduction treatment approach may be applicable to modulate the SMSI of other reducible oxide-supported metal catalysts.
研究领域:
催化化学
·
材料科学
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DOI
高影响因子
Energy Sources Part A-Recovery Utilization and Environmental Effects
·
2025
·
IF 2.2
Jieming Chen,Yuchun Zhang,Yao Li,Peng Fu,Zhiyu Li
Pure TiO2 exhibits limited responsiveness to visible light, while the doping of Ti3+ significantly enhances its absorption efficiency in the visible spectrum, improving the efficiency of photogenerated electron utilization. However, during the direct reduction of TiO2 using NaBH4, the instability of surface Ti3+ ions and their susceptibility to oxidation in air limit their performance in photocatalytic applications. Nitrogen doping into TiO2 effectively addresses this issue, improving the stability of Ti3+ ions and significantly enhancing visible-light-driven photocatalytic activity. Experimental results indicate that reducing 1 g of TiO2 with 0.2 g of NaBH4, followed by calcination in an ammonia environment at 300℃, yields a catalyst with optimal visible-light photocatalytic hydrogen evolution activity, achieving a hydrogen production rate of 847.8 μmol h−1 g−1, representing a 177-fold enhancement over pristine anatase TiO2. After modification, the band gap of the catalyst decreased from 3.2 eV to 2.83 eV. This study elucidates the synergistic effects among Ti3+ species, nitrogen dopants, and oxygen vacancies in TiO2-based photocatalysts, demonstrating their crucial roles in enhancing visible-light-driven hydrogen evolution.
研究领域:
材料科学
·
光催化
·
能源化学
·
纳米材料
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半导体催化
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环境功能材料
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Cheng Liu,Qi Chen,Yueling Chen,Jimmy C. Yu,Jionghua Wu,Ling Wu
Photocatalysis, which uses sunlight, N 2 and H 2 O to produce NH 3 , is a more sustainable approach to N 2 fixation than the Haber-Bosch process. However, its efficiency is severely limited by the difficulty of activating N N bonds. This work presents metal (M = Cu, Fe, V)-substituted MIL-125(Ti) (MIL-(MTi)) for photocatalytic N 2 fixation without using any sacrificial agents. Structural characterizations reveal that the active sites including oxygen vacancies (OV) and Ti 3+ species are formed by the resulting crystal distortion due to the partial substitution of Ti 4+ by other metal ions (Cu + , Fe 2+ , V 3+ ) in MIL-125(Ti). MIL-(CuTi) possesses a larger number of OV and Ti 3+ compared to MIL-(FeTi) and MIL-(VTi) due to the larger valence difference between Cu + and Ti 4+ . These active sites not only promote the adsorption and activation of N 2 and H 2 O, but also facilitate the photogenerated charge mobility. Photogenerated holes oxidize H 2 O to produce O 2 and H + . Photogenerated electrons reduce N 2 activated on Ti 3+ sites by combining with H + to form NH 4 + . Therefore, MIL-(CuTi) shows the highest NH 4 + production rate 46.5 µmol·h −1 ·g −1 , which is much higher than that (1.2 µmol·h −1 ·g −1 ) of the pristine MIL-125(Ti). This work provides a new insight into rational design for artificial N 2 fixation systems by the construction of the active site.
研究领域:
材料科学
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环境科学
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DOI
PubMed
高影响因子
Journal of the American Chemical Society
·
2026
·Vol. 148
·期 29
·31331-31342
·
IF 16.6
Sun Yuwen,Gong Kun,Li Tianyu,An Yunlei,Sun Qiwen,Lin Tiejun,Zhong Liangshu
Nonoxidative
ethane dehydrogenation (NOEDH) is a carbon
efficient
but thermodynamically severe route for ethene production. Solar-driven
NOEDH offers a promising alternative, yet achieving both high activity
and high ethene selectivity over noble metal-free catalysts without
external heating remains unresolved. Here, we reported that Ti 3+ -O acid–base pairs on reduced rutile TiO 2 enabled highly efficient full-spectrum solar-driven photothermal
NOEDH without any external heating. The optimally reduced TiO 2 at 750 ° C delivered an ethene production rate of 392.0
mmol g –1 h –1 , which was 1107 times
higher than that of pristine TiO 2 without reduction pretreatment.
The high activity with a C 2 H 4 selectivity of
94.9% surpassed the thermodynamic equilibrium limit and outperformed
previously reported systems. Comprehensive characterizations identified
surface Ti 3+ sites adjacent to lattice oxygen as Lewis
acid–base pairs that enhanced light absorption, promoted charge
carrier separation, and directly participated in the C–H bond
cleavage. Photogenerated electrons also preferentially accumulated
on the coordinatively unsaturated Ti 3+ -O sites, which weakened
ethene adsorption, thereby accelerating product desorption and suppressing
deep dehydrogenation and coke formation. The synergy between photogenerated
hot carriers and localized photothermal heating lowered the apparent
activation energy from 157.6 kJ mol –1 in the dark
to 75.0 kJ mol –1 under illumination. This work establishes
surface acid–base pairs on noble metal-free catalyst as a powerful
platform for sustainable light-driven alkane upgrading.
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PubMed
高影响因子
Materials
·
2026
·Vol. 19
·期 11
·2417
·
IF 3.7
Boyang Chen,Xinyu Liu,Yiyuan Liu,Zeliang Gao,Zhitai Jia,Wenxiang Mu
HighlightsFor the first time, a high-quality Ti3+-dopedβ-Ga2O3single crystal was successfully grown via the EFG method.The photoelectric properties ofβ-Ga2O3were effectively modulated via Ti3+doping, achieving a moderate semi-insulating state and a reduced bandgap.Ti3+-dopedβ-Ga2O3crystal was fabricated into X-ray detectors with a metal–semiconductor–metal (MSM) structure, demonstrating superior detection performance.Gallium oxide (Ga2O3) is emerging as a promising material for X-ray detectors due to its high sensitivity, high melting point, and stable physicochemical properties. However, intrinsic background shallow donors in raw materials hinder the preparation of high-resistance intrinsic crystals, making doping essential to tailor electrical properties. This study grew Ti3+-dopedβ-Ga2O3single crystals via the Edge-defined Film-fed Growth (EFG) method using Ti2O3as a dopant, achieving high resistivity and a moderate reduction in bandgap. High-resolution X-ray diffraction (HRXRD) showed a rocking curve full width at half maximum (FWHM) of 96.50 arcsec. Compared with the unintentionally doped (UID) crystal, the bandgap exhibited a slight reduction, decreasing from 4.76 eV to 4.59 eV. In the infrared transmission spectra, the onset wavelength of the decrease in transmittance for the Ti3+:β-Ga2O3crystal showed a distinct redshift relative to that of the UID crystal, indicating effective suppression of free electrons within the crystal. X-ray photoelectron spectroscopy (XPS) revealed that Ti3+incorporation minimally affected the valence states of Ga and O or the Ga/O ratio, with no significant shift in valence band maximum (EVBM). A metal–semiconductor–metal (MSM) structured X-ray detector fabricated on polished Ti3+:β-Ga2O3(100) substrate with Ti/Au electrodes exhibited a peak sensitivity of 943.16 μC/(Gy·cm2) at 40 V bias and 2.944 μGy/s dose rate, surpassing the upper sensitivity limit reported for semi-insulating doping bulkβ-Ga2O3detectors. The rise and fall times were 0.23 s and 0.30 s, respectively, with a minimum detectable limit (MDL) of 164.26 nGy/s, demonstrating its potential for high-performance X-ray detection applications.
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DOI
PubMed
高影响因子
Nature Communications
·
2019
·Vol. 10
·期 1
·1-12
·
IF 11.878
Cao Na,Chen Zheng,Zang Ketao,Xu Jie,Zhong Jun,Luo Jun,Xu Xin,Zheng Gengfeng
The electrochemical N 2 fixation to produce ammonia is attractive but significantly challenging with low yield and poor selectivity. Herein, we first used density function theory calculations to reveal adjacent bi-Ti 3+ pairs formed on anatase TiO 2 as the most active electrocatalytic centers for efficient N 2 lying-down chemisorption and activation. Then, by doping of anatase TiO 2 with Zr 4+ that has similar d -electron configuration and oxide structure but relatively larger ionic size, the adjacent bi-Ti 3+ sites were induced and enriched via a strained effect, which in turn enhanced the formation of oxygen vacancies. The Zr 4+ -doped anatase TiO 2 exhibited excellent electrocatalytic N 2 fixation performances, with an ammonia production rate (8.90 µg·h −1 ·cm −2 ) and a Faradaic efficiency of 17.3% at −0.45 V versus reversible hydrogen electrode under ambient aqueous conditions. Moreover, our work suggests a viewpoint to understand and apply the same-valance dopants in heterogeneous catalysis, which is generally useful but still poorly understood.
研究领域:
材料科学
·
电化学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2026
·
IF 6.7
Yan Hao,Zhaoyue Wang,Wenxia Wu,Yixin Zeng,Ao Li,Ming Deng,Jie Wang,Shoulei Xu,Wen Deng
Achieving a high concentration of optically active Ti 3+ ions remains a central challenge in Ti:sapphire laser crystal growth. Here, we present a comparative study investigating the influence of growth conditions on Ti 3+ concentration and luminescence in Ti:Al 2 O 3 single crystals. Three Ti:Al 2 O 3 single crystals with identical nominal Ti content (0.30 mol%) were grown under varying starting materials and atmospheres: (1) using 0.30 mol% Ti metal powder, grown in a reducing atmosphere (93% Ar + 7% H 2 ), denoted as the Ti: Al 2 O 3 (Ar+H 2 ) crystal; (2) using 0.30 mol% TiO 2 powder, grown in a pure Ar atmosphere, denoted as Ti: Al 2 O 3 (Ar); and (3) using 0.30 mol% TiO 2 powder, grown in a pure O 2 atmosphere, denoted as Ti: Al 2 O 3 (O 2 ). The balance material in three cases was Al 2 O 3 powder. XPS results indicate that the ratio of the Ti³ ⁺ and Ti 4+ concentrations (Ti 3+ /Ti 4+ ) follows the order: Ti: Al 2 O 3 (Ar+H 2 ) > Ti: Al 2 O 3 (Ar) > Ti: Al 2 O 3 (O 2 ). The Ti: Al 2 O 3 (Ar+H 2 ) crystal, which exhibits the highest Ti³ ⁺ concentration, shows the strongest characteristic Ti³ ⁺ photoluminescence emission broad band (Ti 3+ : 2 E → 2 T 2 ) centered at 700 nm under both 468 nm and X‑ray excitation, as well as the highest transmittance (83%). These findings demonstrate that the reducing atmosphere combined with metallic Ti precursor most effectively promotes Ti³ ⁺ incorporation and optimizes photoluminescence properties, positioning Ti: Al 2 O 3 (Ar+H 2 ) as a promising gain medium for ultrafast and ultra‑intense laser applications. In contrast, the Ti: Al 2 O 3 (O 2 ) crystal exhibits the highest thermoluminescence (TL) intensity, which is attributed to its highest Ti 4+ concentration. In the oxygen atmosphere, oxygen incorporation at high temperature increases Ti 4+ concentration and simultaneously generates aluminum vacancies (V Al ) as charge compensators, thereby enhancing the density of TL‑active centers.
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高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Zipeng Zou,Fangyuan Wang,Siyu Yang,Lu Wu,Yanhong Tu,Jiahao Dai,Jiping Su,Hongpeng Huang,Xiaohui Luo,Jianping Qiu,Yi Mao
To address the escalating antibiotic contamination in aquatic environments, this study developed Ti 3+ self-doped TiO 2 nanotube arrays/g-C 3 N 4 heterojunction photoanodes (TiO 2-x NTAs/g-C 3 N 4 ) via an integrated in situ synthesis strategy combining electrochemical oxidation, reduction, and chemical vapor deposition. Comprehensive characterization verified g-C 3 N 4 being uniformed dispersed on TiO 2 nanotube surfaces, with Ti 3+ doping significantly improving charge carrier separation efficiency. The photoelectrocatalytic system, utilizing the composite material and platinum as the photoanode and the cathode, respectively, achieved outstanding performance in the degradation of enrofloxacin (ENR). Compared with photocatalytic (72.4%) and electrocatalytic (10.4%) process within 120 min, photoelectrocatalytic process demonstrated the strongest degradation activity (85.4%) with significant synergy. The prepared TiO 2-x NTAs/g-C 3 N 4 photoanode showed robust stability, maintaining nearly unchanged ENR degradation efficiency over 10 cycles. Radical quenching experiments and electron paramagnetic resonance analysis identified the photogenerated holes (h⁺) and superoxide radicals ( • O 2 ⁻) as the dominant reactive species. The synergistic interplay between Ti 3+ doping and heterojunction engineering enabled dual optimization of photon utilization and interfacial charge dynamics. Density functional theory calculations coupled with product analysis elucidated three primary degradation pathways: piperazine ring cleavage, quinolone group oxidation, and defluorination. This work provides mechanistic insights into antibiotic degradation and advances material paradigms for photoelectrocatalytic water remediation.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2017
·
IF 6.216
Yan Cao,Zipeng Xing,Yingcai Shen,Zhenzi Li,Xiaoyan Wu,Xu Yan,Jinlong Zou,Shilin Yang,Wei Zhou
Mesoporous black Ti 3+ /N-TiO 2 spheres with high crystallinity are fabricated by a facile evaporation-induced self-assembly (EISA) method, using urea as nitrogen resource, combined with a mild calcinations (350 °C) after an in-situ hydrogenation under an argon atmosphere. The prepared materials are characterized by X-ray diffraction, Raman, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results indicate the prepared sample is uniform mesoporous black Ti 3+ /N-TiO 2 spheres with high crystallinity of anatase, high surface area of ∼100 m 2 g −1 , large pore size of 6.5 nm and narrow band gap of 2.11 eV, could be easily controlled with the diameter from 200 to 800 nm. Meanwhile, the photoresponse extends to near-infrared region owing to Ti 3+ and N codoping. The visible-light-driven photocatalytic degradation ratio of methyl orange is up to 96% and photocatalytic hydrogen production rate is ∼150 μmol h −1 , which are several times higher than that of pristine TiO 2 . Besides, the possible photocatalytic mechanism is proposed. The excellent photocatalytic activity can be ascribed to N and Ti 3+ doping resulting in high visible light utilization and enhanced separation of photogenerated charge carriers, and the mesoporous networks offering more surface active sites.
研究领域:
材料科学
·
环境科学
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DOI
高影响因子
危险品化学品经营许可证（带存储）