Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be exte...Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be extended to further enhance their photocatalytic activity for H_(2)evolution.Herein,we present a successful attempt to selectively dope lanthanide ions into the{101}facets of ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets through a facile one-step solvothermal method.The lanthanide doping slightly extended the light-harvesting region and markedly improved the charge-separated states of the TiO_(2)nanosheets as evidenced by UV-vis absorption and steady-state/transient photoluminescence spectra.Upon simulated sunlight irradiation,we observed a 4.2-fold enhancement in the photocatalytic H_(2)evolution activity of optimal Yb^(3+)-doped TiO_(2)nanosheets compared to that of their undoped counterparts.Furthermore,when Pt nanoparticles were used as cocatalysts to reduce the H_(2)overpotential in this system,the photocatalytic activity enhancement factor increased to 8.5.By combining these results with those of control experiments,we confirmed that the extended charge-separated states play the main role in the enhancement of the photocatalytic H_(2)evolution activity of lanthanide-doped TiO_(2)nanosheets with coexposed{001}/{101}facets.展开更多
基金This work was supported by a grant from the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)of the Korean government(2021R1A3B1068304).The authors also acknowledge the support provided by a grant from the NRF funded by MSIT of the Korean government(RS-2023-00243840)and Brain Pool program(RS-2023-00222393).D.W.Boukhvalov acknowledges support from Jiangsu Innovative and Entrepreneurial Talents Project,and the Ministry of Science and Education of Russian Federation(FEUZ-2023-0013).
文摘通过氮掺杂TiO_(2)(N-TiO_(2))浸渍蜂窝过滤器构建了一系列原型光催化空气净化器(AP(N_(x)-C_(y)))系统,并用于在UV-LED光(1 W)照射条件下光催化分解0.5-5 ppm甲醛(CH_(2)O)蒸汽.在上述催化过滤器系统中,Nx和Cy分别代表N/Ti摩尔比(0-20)和N-TiO_(2)浓度(2-20 mg mL^(-1)).光催化分解实验结果表明,AP(N_(10)-C_(10))的性能最好,其催化CH2O转化为CO_(2)的转化率最高,循环反应10次后CO_(2)产率仍达到89.2%,在干燥空气中的清洁空气输送速率为9.45 L min^(-1).N10-C10的电荷载流子寿命(τa:1.70 ns)优于其他样品(如纯TiO_(2)的电荷载流子寿命为1.37 ns),这表明N缺陷(No)有助于降低带隙(3.10 eV)和产生氧空位OVs-Ti^(3+),这与密度泛函理论(DFT)模拟结果一致.采用原位漫反射红外傅里叶变换、电子顺磁共振和DFT分析等多种方法研究了CH_(2)O的光催化氧化途径.结果表明,氧化过程涉及多个能量有利的中间步骤(例如CH2O以CH_(2)O_(2)的形式在TiO_(2)-OV{110}表面的桥连O/OH基团上发生放热共价吸附,随后通过催化脱氢/氧化反应直接生成CO_(2):CH_(2)O_(2)/HCOO^(-)+•OH→H_(2)O+CO_(2)).这些步骤与具有N杂质的{101}表面上化学活性Ti原子的态密度计算结果一致.预计No缺陷和OVs的存在将通过降低活化能垒来影响反应能量和中间产物,从而在加湿条件下实现有效的矿化.综上,本文为设计和构建先进的光催化系统,并用于环境空气中醛类挥发性有机物(VOCs)的有效矿化提供了新思路.
文摘Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be extended to further enhance their photocatalytic activity for H_(2)evolution.Herein,we present a successful attempt to selectively dope lanthanide ions into the{101}facets of ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets through a facile one-step solvothermal method.The lanthanide doping slightly extended the light-harvesting region and markedly improved the charge-separated states of the TiO_(2)nanosheets as evidenced by UV-vis absorption and steady-state/transient photoluminescence spectra.Upon simulated sunlight irradiation,we observed a 4.2-fold enhancement in the photocatalytic H_(2)evolution activity of optimal Yb^(3+)-doped TiO_(2)nanosheets compared to that of their undoped counterparts.Furthermore,when Pt nanoparticles were used as cocatalysts to reduce the H_(2)overpotential in this system,the photocatalytic activity enhancement factor increased to 8.5.By combining these results with those of control experiments,we confirmed that the extended charge-separated states play the main role in the enhancement of the photocatalytic H_(2)evolution activity of lanthanide-doped TiO_(2)nanosheets with coexposed{001}/{101}facets.
