高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (4): 978.doi: 10.7503/cjcu20200619
收稿日期:
2020-08-31
出版日期:
2021-04-10
发布日期:
2021-02-03
通讯作者:
杜芳林
E-mail:dufanglin@qust.edu.cn
基金资助:
Received:
2020-08-31
Online:
2021-04-10
Published:
2021-02-03
Contact:
DU Fanglin
E-mail:dufanglin@qust.edu.cn
Supported by:
摘要:
二氧化钛(TiO2)材料由于其低成本、 天然丰度高、 对环境友好、 具有良好的化学稳定性和优异的光学性能越来越受到关注. 其中, 有序介孔TiO2材料因其高比表面积、 大的孔体积、 可调的孔结构和形态, 在物理、 化学和材料科学等方面得到广泛应用. 本文总结了通过合理控制钛前体水解和交联速率合成有序介孔TiO2材料的重要进展, 同时讨论了其在光催化分解水产氢方面的应用, 并对该领域的发展趋势和所面临的挑战提出了展望.
中图分类号:
TrendMD:
徐安琪, 李彬, 杜芳林. 有序介孔TiO2的合成及光解水产氢应用. 高等学校化学学报, 2021, 42(4): 978.
XU Anqi, LI Bin, DU Fanglin. Synthesis of Ordered Mesoporous TiO2 and Their Application for Hydrogen Production from Photocatalytic Water-splitting. Chem. J. Chinese Universities, 2021, 42(4): 978.
Fig.1 Mechanism and characterization of mesoporous single crystal TiO2 synthesized by evaporation?driven directional assembly method[87](A) Schematic representation of the formation process of hierarchically mesoporous TiO2 microspheres with single-crystal like pore wall through evaporation-driven oriented assembly; (B) SEM image of a single ultramicrotomed, radially-oriented hierarchically mesoporous TiO2 microspheres; (C) TEM image of a single ultramicrotomed, hierarchically mesoporous TiO2 microspheres. Inset of (C): the SAED pattern taken from the cylindrical pore bundlesregion with [010] incidence.Copyright 2015, American Association for the Advancement of Science.
Fig.2 Mechanism and characterization of mesoporous anatase single crystal synthesized by volatilization?driven directional assembly[88](A) Schematic representation of the formation process of the olive-like mesoporous TiO2 mesocrystals through the evaporation-driven oriented assembly process, schematic representation of the formation process of the olive-shaped mesoporous TiO2 single-crystals SC-FDU-19 after heat treating in air at 400 ℃ and schematic representation of the formation process of the olive-shaped mesoporous TiO2 single-crystals SC-FDU-19 after heat treating in air at 400 ℃; (B) SEM image of the mesoporous TiO2 mesocrystals FDU-19; (C) SEM images of the mesoporous single-crystals SC-FDU-19; (D) TEM image of the obtained ultrathin SN-FDU-19 nanosheets; (E) HRTEM images of an individual TiO2 nanosheet recorded along the [001] axis and the corresponding crystallographic structure of the (001) surface(inset), Ti and O atoms are represented by blue and red spheres, respectively.Copyright 2015, American Chemical Society.
Fig.3 Mechanism diagram and characterization of the mixed?phase mesoporous TiO2 microspheres synthesized by the coordination?induced self?assembly method[89](A) Schematic illustration of the synthesis process of meso-TiO2 microspheres via a facile coordination-mediated self-assembly strategy; FESEM(B―D); TEM(E); HRTEM(F) images and SAED patterns(G) of the mesoporous TiO2 prepared by the coordination-mediated self-assembly method.Copyright 2019, Royal Society of Chemistry.
Fig.4 Synthesis of single?layer two?dimensional ordered mesoporous TiO2 nanosheets by hydrothermally induced solvent?constrained self?assembly method[114](A) Schematic illustration of the formation process for the single-layered 2D ordered mesoporous TiO2 nanosheets via hydrothermal-induced solvent-confined monomicelle assembly; (B) SEM images of the single-layered 2D mesoporous TiO2 nanosheets prepared by hydrothermal-induced solvent-confined monomicelle assembly approach at 100 °C for 10 h after the calcination in N2 at 350 °C for 6 h; (C, D) TEM images of the free-standing hierarchically mesoporous TiO2 nanosheets.Copyright 2018, American Chemical Society.
Fig.5 Mechanism diagram and characterization of single crystal mesoporous TiO2 synthesized by crystal orientation growth method[124](A) Synthesis of mesoporous single-crystal-like TiO2; (B, C) HRTEM images of mesoporous single crystals grown within the SBA-15 and KIT-6 followed by removal of the scaffold; (D) high-resolution TEM(HRTEM) image of the edge of TiO2 crystal showing highly ordered lattices recorded from [001] orientation and embedded mesoporous networks.Copyright 2011, John Wiley and Sons.
Fig.6 Mechanism diagram and characterization of the synthesis of three?dimensional ordered macroporous TiO2 containing mesopores by the dual template method[128](A) Schematic illustration for the synthesis of ordered hierarchically mesoporous TiO2 microparticles by using P(St-MMA-SPMAP) spheres and P123 as hard and soft templates; SEM(B) and TEM(C) images of hierarchically mesoporous TiO2 microparticles.Copyright 2014, Royal Society of Chemistry.
Fig.7 Mechanism diagram and characterization of three?dimensional ordered mesoporous TiO2 single crystal synthesized by self?assembly method of confined microemulsion[129](A) Schematic representation of the formation process of hierarchically mesoporous TiO2 bouquet-posy-like superstructures through confined-microemulsion self-assembly process; (B) TEM images of the Level-1 hierarchically mesoporous TiO2 superstructure; (C) the SAED pattern taken from the dotted square area marked in panel (B); (D) HRTEM image taken from the area of the cylindrical mesopore bundles of an ultramicrotomed Level-1 mesoporous TiO2 superstructure with [110] incidence; (E, F) SEM images of a single ultramicrotomed Level-2 mesoporous TiO2 superstructure; (G) TEM image of a single Level-2 mesoporous TiO2 superstructure.Copyright 2016, American Chemical Society.
Fig.8 Mechanism diagram and characterization of mesoporous TiO2 hollow microspheres synthesized by solvent evaporation?driven self?assembly method[139](A) Schematic representation of the formation process for hierarchically macro/mesoporous TiO2 hollow microspheres by using 3DOM and Pluronic F127 as the hard and soft template, respectively; SEM(B,C), TEM(D) and HRTEM(E) images of the hierarchically macro/mesoporous TiO2 hollow microspheres.Copyright 2016, Wiley-VCH.
Fig.9 Characterization and performance of mesoporous black TiO2 synthesized by the evaporation?induced self?assembly (EISA) method combined with an ethylenediamine encircling process[145](A, B) Representative TEM images along [100] and [110] planes; (C) HRTEM images of the ordered mesoporous black TiO2 materials after hydrogen gas annealing at 500 ℃; (D) normalized X-ray absorption near-edge structure; (E) normalized Fourier transforms of the extended X-ray absorption ?ne structure spectra for the ordered mesoporous black TiO2 materials a and pristine ordered mesoporous TiO2 materials b at the Ti Kedge, the A1 prepeak is owing to t2g band-like state, while A2 and A3 are due to eg band-like states; (F) the photocatalytic hydrogen evolution rates under single-wavelength light and the corresponding QE.Copyright 2014, American Chemical Society.
Fig.10 Characterization and properties of two?dimensional ultra?thin mesoporous anatase TiO2 nanosheets synthesized by volatilization?induced self?assembly method, solvothermal method and surface hydrogenation reduction method[170]SEM(A, B) and HRTEM(C) images and Ti2p XPS spectra(D) of the 2D ultrathin mesoporous anatase TiO2 nanosheets with engineered surface defects; (E) valence band spectra of the 2D ultrathin mesoporous anatase TiO2 nanosheets with engineered surface defects; (F) photocatalytic hydrogen generation rate by TiO2 calcined at di?erent temperatures.Copyright 2020, Royal Society of Chemistry.
Fig.11 Characterization and properties of rutile and anatase TiO2 mesoporous single crystals with controlled morphology synthesized by hard template method[175]SEM(A, B) and TEM(C, D) images of mesoporous TiO2 short nanorod and mesoporous TiO2 nanosheets; (E, F) the correspon-ding pore size distribution derived from adsorption isotherm of RMSC-0.3 and A-MSC-0.3(HF: 0.05 mol/L); (G) hydrogen evolution curves of R-SC, R-MSC-0.3, A-SC (HF: 0.05 mol/L) and A-MSC-0.3(HF: 0.05 mol/L).Copyright 2013, American Chemical Society.
Fig.12 Characterization and performance of Mg?TiO2 ultra?thin hollow spheres synthesized by ion adsorption and template method[191]SEM(A), TEM(B) and HRTEM(C) images of 0.5% Mg-TiO2 hollow spheres; (D) the XRD patterns of Mg-TiO2 hollow sphere with 0, 0.1%, 0.5%, 1% Mg concentration, respectively; (E) UV-Vis absorbance spectra of Mg-TiO2 hollow sphere with 0, 0.1%, 0.5%, 1% Mg doping concentration, respectively; (F) transient IR absorption-excitation energy scanning spectra for 0.1%, 0.5%, 1% Mg-TiO2 hollow spheres, pure anatase and rutile TiO2.Copyright 2017, Elsevier.
Fig.13 Characterization and properties of mesoporous TiO2?NiSx materials synthesized by hydrothermal method[160]SEM(A, B) and TEM(C) images of TiO2-NiSx-3% hybrid; (D) photoluminescence spectra of different photocatalysts; (E) N2 adsorption-desorption isotherms of TiO2 and TiO2-NiSx-3%; (F) hydrogen evolution rate of different catalysts.Copyright 2019, Elsevier.
Fig.14 Characterization and performance of edge?enriched ultrathin MoS2 embedded yolk?shell TiO2[212](A) Schematic illustration for the synthesis process of yolk-shell TiO2 with ultrathin MoS2 flakes embedded in it; (B, C) HRTEM images of UMT-0.14 after biological sliced treatment: small-scale area; (D) photoactivity comparison by various photocatalysts(TiO2, S-TiO2, Pt-TiO2, UMT-0.14, and BMT-0.14).Copyright 2019, Wiley-VCH.
Fig.15 Characterization and performance of layered hollow black TiO2/MoS2/CdS series heterojunction photocatalyst[5]SEM(A), HRTEM(B) and TEM(C) images of TiO2/MoS2/CdS tandem heterojunctions microspheres; (D) corresponding pore size distribution curves of TiO2/MoS2/CdS tandem heterojunctions; (E) ultraviolet-visible absorption spectra; (F) the comparison of photocatalytic H2 production activity of different photocatalysts under visible light irradiation.Copyright 2018, Wiley-VCH.
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