Surfaces and Interfaces
·
2026
·
IF 6
Huiyu Yan,Yong You,Yingtian Zhang,Yiming Liu
Crystal phase governs the formation of surface acid sites, including Ti 3+ sites, and methane adsorption on TiO 2 . • Localized surface acid sites ( e.g. , Ti 3+ ), rather than oxygen vacancies, are the dominant sites for CH 4 adsorption and activation. • Crystal phase engineering enhances photothermal methane coupling via interface regulation. Photothermal non-oxidative coupling of methane (NOCM) offers an attractive route for the direct conversion of methane into value-added C 2 hydrocarbons and hydrogen under relatively mild conditions. However, the catalytic performance is strongly limited by the inefficient adsorption and activation of methane over semiconductor supports. Herein, the crystal phase of TiO 2 was engineered to regulate the surface electronic structure and methane adsorption behavior of Pd/TiO 2 photocatalysts for photothermal NOCM. TiO 2 supports with anatase and rutile phases, denoted TiO 2 (A) and TiO 2 (R), were prepared by calcination, and subsequently loaded with Pd species by photodeposition. Among the investigated catalysts, Pd/TiO 2 (A)-500 exhibited the highest C 2 H 6 production rate of 112.4 μmol·g –1 ·h –1 at 150 °C under Xe lamp irradiation together with excellent catalytic stability. Photoelectrochemical characterization demonstrated that TiO 2 (A) significantly promoted the separation and transfer of photogenerated charge carriers. Although TiO 2 (R) possessed a higher concentration of oxygen vacancies, comprehensive state-of-the-art in situ spectral characteristics revealed substantially weaker methane adsorption due to the migration of vacancy-induced electrons into subsurface Ti sites, resulting in fewer surface acid sites, such as Ti 3+ sites. These also confirmed that the enhanced surface Ti 3+ species on TiO 2 (A) facilitated methane adsorption and activation, promoted the generation of · CH 3 intermediates, and consequently accelerated C C coupling toward ethane formation. This work reveals the decisive role of TiO 2 crystal phase in regulating methane adsorption and activation during photothermal NOCM, providing new insights into the rational design of semiconductor supports for efficient solar-driven methane valorization. Crystal phase engineering of TiO 2 regulates surface acid sites to enhance methane adsorption and promote photothermal catalytic non-oxidative coupling of methane Download: Download high-res image (253KB) Download: Download full-size image
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Kejin Jiao,Shujie Liu,Yanyan Ma,Shuo Chen,Liying Wei,Jianhua Yan
Lithium (Li) metal battery is a promising next generation energy storage system due to its high energy density , but what hinders its commercialization is the safety hazard of Li-anode, especially under high current densities. Here, we report a dual strategy of using electronic conductive black TiO 2−x nanofiber films to construct composite Li-metal anodes with stable 3D networks and applying an in-situ polymerized ionic conductive gel-electrolyte to construct efficient quasi-solid-state Li-batteries (QSSLBs). The 3D nanofibrous Li-anode shows a stable and small nucleation barrier and can run stably (>1600 h) at a high current density of 10 mA/cm 2 . When matching with high-loading cathodes of LiFePO 4 , the QSSLBs exhibit excellent long-term cycling stability (>500 cycles) and high-rate capability (>1 C). In addition, the in-situ polymerization strategy can be incorporated with the commercial lamination manufacturing to produce 63-Ah pouch cells of LiFePO 4 ||graphite, which deliver a high initial Coloumbic efficiency, a large energy density at 0.3 C, excellent rate capability from 0.25 to 2 C, and long-term cycling performance at 0.3 and 1 C, showing potential commercial prospects.
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ANALYTICAL CHEMISTRY
·
2014
·
IF 5.825
Gao-Chao Fan,Li Han,Hua Zhu,Jian-Rong Zhang,Jun-Jie Zhu
An ultrasensitive photoelectrochemical sandwich immunoassay was developed to detect matrix metalloproteinase-2 (MMP-2, antigen, Ag) based on CdS:Mn/CdTe cosensitized TiO2 nanotubes (TiO2-NTs) and signal amplification of SiO2@Ab2 conjugates. Specifically, the TiO2-NTs electrode was first deposited with CdS:Mn by successive ionic layer adsorption and reaction technique and then further coated with CdTe quantum dots (QDs) via the layer-by-layer method, forming TiO2-NTs/CdS:Mn/CdTe cosensitized structure, which was employed as a matrix to immobilize capture MMP-2 antibodies (Ab1); whereas, SiO2 nanoparticles were coated with signal MMP-2 antibodies (Ab2) to form SiO2@Ab2 conjugates, which were used as signal amplification elements via the specific antibody–antigen immunoreaction between Ag and Ab2. The ultrahigh sensitivity of this immunoassay derived from the two major reasons as below. First, the TiO2-NTs/CdS:Mn/CdTe cosensitized structure could adequately absorb the light energy, dramatically promote electron transfer, and effectively inhibit the electron–hole recombination, resulting in significantly enhanced photocurrent intensity of the sensing electrode. However, in the presence of target Ag, the immobilized SiO2@Ab2 conjugates could evidently increase the steric hindrance of the sensing electrode and effectively depress the electron transfer, leading to obviously decreased photocurrent intensity. Accordingly, the well-designed photoelectrochemical immunoassay exhibited a low detection limit of 3.6 fg/mL and a wide linear range from 10 fg/mL to 500 pg/mL for target Ag detection. Meanwhile, it also presented good reproducibility, specificity, and stability and might open a new promising platform for the detection of other important biomarkers.
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高影响因子
Journal of Materials Chemistry C
·
2017
·Vol. 5
·期 25
·6224-6233
·
IF 5.256
Lin Zhou,Kai Yu,Fan Yang,Hui Cong,Nan Wang,Jun Zheng,Yuhua Zuo,Chuanbo Li,Buwen Cheng,Qiming Wang
In the current work, we fabricate an all-inorganic perovskite quantum dot-based photodetector with bifunctional linker molecules, which is highly superior to its counterpart without the linker. The ultrahigh on/off ratio of 105 is two orders of magnitude higher than that of the device without the ligand treatment. Moreover, the responsivity increases from ∼2.2 A W−1 to ∼24.5 A W−1 and the detectivity from 3.5 × 1012 Jones to 8.9 × 1013 Jones. To gain further insight into the effect of ligand-exchange by bifunctional linker molecules besides surface passivation, we divide the electron transfer process into two parts, the electron transfer from quantum dots (QDs) to the linker and from the linker to TiO2. Injection of photoexcited electrons from colloidal CsPbBr3 QDs into TiO2 nanoparticles by bifunctional linker molecules is found to be much faster. Continuous-wave and time-resolved fluorescence spectra exhibit strong quenching for CsPbBr3 QDs assembled by the linker or coupled to TiO2 nanoparticles, which is consistent with electron transfer for QDs. From the results of the transient absorption measurement and fluorescence lifetime, the electron transfer time of QDs–TiO2 linked by the bifunctional molecules is calculated to be within 40 ns, while that from QDs to TiO2 particles directly is estimated to be ∼290 ns. This indicates that much faster electron injection occurs under the effect of the electron linker. In addition, the linker molecule modification can improve the adsorption of mp-TiO2 to capture more QDs.
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Journal of Materials Chemistry C
·
2020
·Vol. 8
·期 10
·3476-3482
·
IF 7.059
Jiaxing Wu,Panzhe Qiao,Haoze Li,Yachao Xu,Wutao Yang,Fan Yang,Kuo Lin,Kai Pan,Wei Zhou
Two-dimensional (2D) ultrathin mesoporous anatase TiO2 nanosheets with engineered surface defects (SDUATNs) are prepared by evaporation-induced self-assembly, solvothermal and surface hydrogenation reduction strategies. The as-prepared SDUATNs possess a comparatively large specific surface area of 100.4 m2 g−1, a main pore size of 9.7 nm, and a pore volume of 0.36 cm3 g−1. After surface hydrogenation, the narrowed bandgap of 2.97 eV expands the photoresponse from the ultraviolet to the visible-light region as a result of efficient surface defect engineering. The SDUATNs exhibit excellent photocatalytic hydrogen production performance (3.73 mmol h−1 g−1), which is about 3-fold higher than that of pristine ultrathin mesoporous anatase TiO2 nanosheets (1.31 mmol h−1 g−1) under AM 1.5G irradiation. The improvement of the hydrogen evolution performance is attributed to the efficient engineered surface defects and the special 2D ultrathin structure reducing the bandgap, increasing sunlight utilization, providing adequate surface active sites, shortening the migration distance of charge carriers and thus favoring the spatial separation of photogenerated electron–hole pairs. The high stability also favors practical applications. This work presents new insight to enhance the photocatalytic performance and may provide valuable ideas to fabricate other high-performance 2D photocatalysts.
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CERAMICS INTERNATIONAL
·
2020
·
IF 3.83
Yuyuan Zhang,Huawen Hu,Wanwen Kang,Guojian Qiu,Ruiyin Liang,Lifang Deng,Haoran Yuan
This study is devoted to the scalable fabrication of a high-performance composite photocatalyst by incorporation of the visible-light-active CdS flowers (with sharp edges exposed) onto a TiO 2 nanotube array (TNA) film on the Ti foil substrate. To evaluate the visible-light-harvesting performance of the prepared hierarchical architecture consisting of the CdS flowers, TNAs, and Ti foil, we subsequently assembled a photoelectrochemical (PEC) cell with membrane electrode assemblies fabricated innovatively by thermocompression. The CdS flowers can efficiently harvest the visible light energy , while TiO 2 collects photoelectrons, effectively separating of the photoexcited electron-hole pairs and hence enhancing the photocatalysis efficiency in the photoelectrochemical conversion and yield of hydrogen production from water splitting. An impressive hydrogen production rate of 22.44 μmol▪h −1 ▪cm −2 was obtained in the PEC cell with the CdS flowers-sensitized TNA film under simulated solar light with an active irradiation area of around 42 cm 2 , thus showing great potential for practical applications.
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ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Yang Zeng,Lan Jiang,Xiaoxin Zhang,Songhai Xie,Yan Pei,Gongbing Zhou,Weiming Hua,Minghua Qiao,Zhen-Hua Li,Baoning Zong
Catalytic hydrogenolysis of biomass-derived glycerol to 1,3-propanediol (1,3-PDO) represents an important process for the sustainable production of value-added chemicals. However, there is a dearth of understanding of the effect of the polymorph of the support on this reaction. Herein, two Pt–WOx/TiO2 catalysts supported on rutile TiO2 (r-TiO2) and anatase TiO2 (a-TiO2) polymorphs were prepared to investigate the crystal phase effect of TiO2 on the structural property and catalytic performance in glycerol hydrogenolysis. The TiO2 polymorph was identified to impose profound effects on the size of the Pt nanoparticles (NPs) and the dispersion and location of the WOx species, which originated from the discrepancies in the crystal structures between the PtO2 and the TiO2 polymorphs and the discrepancies in the interactions of WOx with different TiO2 polymorphs. In glycerol hydrogenolysis, the Pt–WOx/r-TiO2 catalyst gave a 1,3-PDO selectivity of 51.2% at a glycerol conversion to liquid products of 74.5%, yielding 38.1% of 1,3-PDO. In contrast, the Pt–WOx/a-TiO2 catalyst showed much inferior glycerol conversion and 1,3-PDO selectivity, yielding only 1.0% of 1,3-PDO under identical reaction conditions. The superior catalytic performance of the Pt–WOx/r-TiO2 catalyst is attributed to the r-TiO2 polymorph that facilitates a faster hydrogen spillover than the a-TiO2 polymorph from the Pt NPs to the reaction intermediate on the WOx species, which is substantiated by an even higher 1,3-PDO yield of 44.8% over the physically mixed Pt/r-TiO2 + WOx/r-TiO2 catalyst. This work demonstrates the critical role of the polymorph of the TiO2 support in the design of efficacious Pt–WOx-based catalysts for glycerol hydrogenolysis to 1,3-PDO.
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RSC Advances
·
2018
·Vol. 8
·期 7
·3433-3442
·
IF 2.936
Yumeng Zhou,Lijing Zhang,Shengyang Tao
The preparation of porous TiO2 as a carrier for the Fenton reaction is reported. Porous TiO2 is an excellent carrier to load with elemental iron due to the large specific surface area and negative surface charge. Porous TiO2 was synthesized in the form of a hierarchically porous silica monolith that was used as a microreactor, and a block copolymer served as a template for mesoporous forms. The crystalline TiO2 growing in confined spaces maintained the porous structure and high crystallinity. The surface area of our synthesized porous TiO2 can reach 205 m2 g−1. The zeta potential of the TiO2 was as low as −36.5 mV (pH 7). Elemental iron was highly and uniformly dispersed over the channel of the porous TiO2 via an impregnation method and served as the catalyst for the Fenton reaction. In the Fenton reaction, the synthesized catalyst performed strong catalytic activity during the degradation of wastewater containing an ultrahigh concentration of aqueous dye, at 400 ppm. The aqueous dye solution was degraded over 95% in 30 min, and the catalyst could be reused many times.
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高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2022
·Vol. 29
·期 23
·34861-34873
·
IF 5.19
Humayun Muhammad,Shu Lang,Pi Wenbo,Xia Hui,Khan Abbas,Zheng Zhiping,Fu Qiuyun,Tian Yahui,Luo Wei
The design of highly efficient photoca talysts for clean energy production and environmental remediation are the grand challenges of scientific research. Herein, TiO 2 @MIL53Fe and CeO 2 @MIL53Fe composite photocatalysts are synthesized via solvothermal technique. The SEM and TEM micrographs reveal that TiO 2 and CeO 2 nanoparticles are vertically grown onto the surface of MIL53Fe MOF. Further, HRTEM micrograph confirmed the formation of heterojunction. It has been investigated that the resultant TiO 2 @MIL53Fe and CeO 2 @MIL53Fe photocatalysts exhibit remarkably improved visible light activities for H 2 production and 2,4-dichlorophenol (2,4-DCP) degradation in comparison to the bare MIL53Fe photocatalyst. The enhanced photoactivities of the fabricated TiO 2 @MIL53Fe and CeO 2 @MIL53Fe photocatalysts are attributed to significantly promoted charge separation as confirmed via the surface photo voltage (SPV) and photoluminescence (PL) results. Further, the photocatalysts exhibit high stability and reusability as confirmed via the recyclable tests. This work will promote the design of MOF-based efficient photocatalysts for clean energy production and environment purification.
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高影响因子
RSC Advances
·
2024
·Vol. 14
·期 2
·1488-1500
·
IF 3.9
Zhuo Yang,Jinshan Wang,Aimin Li,Chao Wang,Wei Ji,Elísabet Pires,Wenzhong Yang,Su Jing
In this study, fcSe@TiO2 and [Cu2I2(fcSe)2]n@TiO2 nanosystems based on ferrocenylselenoether and its cuprous cluster were developed and characterized by X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM), energy dispersive X-ray spectroscopy (EDX), and electron paramagnetic resonance (EPR). Under optimized conditions, 0.2 g L−1 catalyst, 20 mM H2O2, and initial pH 7, good synergistic visible light photocatalytic tetracycline degradation and Cr(VI) reduction were achieved, with 92.1% of tetracycline and 64.5% of Cr(VI) removal efficiency within 30 minutes. Mechanistic studies revealed that the reactive species ˙OH, ˙O2−, and h+ were produced in both systems through the mutual promotion of Fenton reactions and photogenerated charge separation. The [Cu2I2(fcSe)2]n@TiO2 system additionally produced 1O2 from Cu+ and ˙O2−. The advantages of the developed nanosystems include an acidic surface microenvironment provided by Se⋯H+, resourceful product formation, tolerance of complex environments, and excellent adaptability in refractory N-cyclic organics.
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高影响因子
Journal of Cleaner Production
·
2022
·
IF 11.072
Feng Long,Xincheng Cao,Peng Liu,Xia Jiang,Jianchun Jiang,Xiaolei Zhang,Junming Xu
Efficient deoxygenation for the bio-derived fatty acid is paramount to producing diesel-like alkane and usually requires harsh reaction conditions. Here, we reported an efficient conversion system for the photocatalytic conversion of fatty acid over Pt/TiO 2 catalysts and acid conversion higher than 99.0% (yield nearly 84.5%) under the mild conditions 30 °C, 0.1 MPa H 2, and 365 nm light. X-ray photoelectron spectroscopy (XPS) and Density Functional Theory (DFT) calculations suggest that the oxygen vacancies TiO 2 can achieve the charge transfer from TiO 2 support to Pt clusters. The electron-rich Pt cluster can promote hydrogen spillover to form a hydrogen-rich surface. Thus, it leads to the photo-decarboxylation C n-1 alkyl radical being amenable to proton hydrogenation to produce C n-1 alkane. Detailed characterization demonstrates that 0.50 wt% Pt/TiO 2 has superior photocatalytic performance. Introducing the Pt atoms can promote the formation the oxygen vacancies and reverse charge transfer, which determines the acid adsorption and conversion mechanism.
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Catalysts
·
2021
·Vol. 11
·期 2
·184
·
IF 4.146
Huang Zhou,Fengjiao He
β-NaYF4:Yb,Er,Gd fluorescent nanorods were successfully coupled to a reduced TiO2(UCNPs@R-TiO2) nanocomposite and applied to visible-light catalytic sterilization under 980 nm near-infrared (NIR) light illumination. The UCNPs (β-NaYF4:Yb,Er,Gd) absorb the NIR light and emit red and green light. The visible light can be absorbed by the R-TiO2(Eg = 2.8 eV) for the photocatalytic reaction. About 98.1% ofEscherichia coliwere effectively killed upon 12 min of NIR light irradiation at a minimum inhibitory concentration (MIC) of 40 μg/mL UCNPs@R-TiO2nanocomposite. The bactericidal properties were further evaluated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis. We found that the high bactericidal activity was due to the synergistic effect between the UCNPs and R-TiO2. Moreover, the UCNPs show excellent upconversion luminance properties, and the introduction of visible-light-absorbed R-TiO2nanoparticles (2.8 eV) was conducive to the efficient separation and utilization of photogenerated electron-hole pairs.
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