Low pressure rapid hydrogenation induced oxygen vacancy to enhance the photocatalytic degradation performance of TiO2
CHEN Fenglei1, YANG Wanlin2, ZHU Junkui2, WEI Qiuping2, ZHANG Long3, LI Jing2, MA Li1
1. State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China; 2. School of Materials Science and Engineering, Central South University, Changsha 410083, China; 3. School of Materials Science and Engineering, Changsha University of Science and Technology, Changsha 410114, China
Abstract：A tube furnace was used to perform low-pressure rapid hydrogenation treatment on TiO2 photocatalyst (P25) at 300, 400, and 500 ℃, and the effects of hydrogenation temperature on the phase structure, photoelectrochemical performance, and catalytic degradation activity of the sample were studied. The results show that the oxygen vacancy concentration, photogenerated carrier separation efficiency, visible light absorption performance, carrier concentration, and photocatalytic activity of P25 appear to first increase and then decrease as the hydrogenation temperature increases. P25 hydrogenated at 400 ℃ for 1 h has the best performance above. BET (Brunauer-Emmett-Teller) specific surface area of P25 is not sensitive to the change of hydrogenation temperature, indicating that low-pressure rapid hydrogenation can introduce oxygen vacancies while avoiding loss of specific surface area, inhibit the recombination of electron-hole pairs, improve light absorption performance and carrier concentration, thereby improving P25 photocatalytic performance. After hydrogenation treatment at 400 ℃ for 1 h, the reaction rate constant of P25 is 1.63 times than that of untreated P25.
[1] WANG T, PAN X, BEN W, et al.Adsorptive removal of antibiotics from water using magnetic ion exchange resin[J]. Journal of Environmental Sciences, 2017, 52: 111-117. [2] ZHENG Y, LIN L H, WANG B, et al.Graphitic carbon nitride polymers toward sustainable photoredox catalysis[J]. Angewandte Chemie-International Edition, 2015, 54(44): 12868-12884. [3] BAI S, JIANG J, ZHANG Q, et al.Steering charge kinetics in photocatalysis: intersection of materials syntheses, characterization techniques and theoretical simulations[J]. Chemical Society Reviews, 2015, 44(10): 2893-2939. [4] LIU B, CHENG K, NIE S, et al.Ice-water quenching induced Ti3+ self-doped TiO2 with surface lattice distortion and the increased photocatalytic activity[J]. The Journal of Physical Chemistry C, 2017, 121(36): 19836-19848. [5] WANG W, LU C H, NI Y R, et al.Enhanced visible-light photoactivity of {001} facets dominated TiO2 nanosheets with even distributed bulk oxygen vacancy and Ti3+[J]. Catalysis Communications, 2012, 22: 19-23. [6] 刘保顺, 何鑫, 赵修建, 等. 热处理对TiO2溅射薄膜结构和光谱性能的影响[J]. 稀有金属材料与工程, 2005(9): 1451-1454. LIU Baoshun, HE Xin, ZHAO Xiujian, et al.The effect of the d-electron transition on UV-Vis spectra and PL spectra of TiO2 films[J]. Rare Materials and Engineering, 2005(9): 1451-1454. [7] 官仁发, 肖亚, 刘启明, 等. Cu/Ag掺杂TiO2包覆SiO2纳米复合材料的结构与光催化性能[J]. 粉末冶金材料科学与工程, 2018, 23(1): 101-109. GUAN Renfa, XIAO Ya, LIU Qiming, et al.Synthesis and photocatalytic property of SiO2 nanopowder coated by Cu/Ag-doped TiO2[J]. Materials Science and Engineering of Powder Metallurgy, 2018, 23(1): 101-109. [8] LI D, HANEDA H, LABHSETWAR N K, et al.Visible-light-driven photocatalysis on fluorine-doped TiO2 powders by the creation of surface oxygen vacancies[J]. Chemical Physics Letters, 2005, 401(4/6): 579-584. [9] ZUO F, WANG L, WU T, et al.Self-doped Ti3+ enhanced photocatalyst for hydrogen production under visible light[J]. Journal of the American Chemical Society, 2010, 132(34): 11856-11857. [10] LIU H, MA H T, LI X Z, et al.The enhancement of TiO2 photocatalytic activity by hydrogen thermal treatment[J]. Chemosphere, 2003, 50(1): 39-46. [11] PERIYAT P, BAIJU K V, MUKUNDAN P, et al.Aqueous colloidal sol-gel route to synthesize nanosized ceria-doped titania having high surface area and increased anatase phase stability[J]. Journal of Sol-Gel Science and Technology, 2007, 43(3): 299-304. [12] CHEN X, LIU L, YU P Y, et al.Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals[J]. Science, 2011, 331(6018): 746-750. [13] ZHU Y, LIU D, MENG M.H2 spillover enhanced hydrogenation capability of TiO2 used for photocatalytic splitting of water: a traditional phenomenon for new applications[J]. Chemical Communications, 2014, 50(45): 6049-6051. [14] LESHUK T, PARVIZ R, EVERETT P, et al.Photocatalytic activity of hydrogenated TiO2[J]. ACS Applied Materials & Interfaces, 2013, 5(6): 1892-1895. [15] MYUNG S T, KIKUCHI M, YOON C S, et al.Black anatase titania enabling ultra high cycling rates for rechargeable lithium batteries[J]. Energy & Environmental Science, 2013, 6(9): 2609-2614. [16] KUTTY T R N, VIVEKANANDAN R, MURUGARAJ P. Precipitation of rutile and anatase (TiO2) fine powders and their conversion to MTiO3 (M=Ba, Sr, Ca) by the hydrothermal method[J]. Materials Chemistry and Physics, 1988, 19(6): 533-546. [17] MARIANA H R, ROBERTO C S, RUIZ F, et al.H2Ti3O7 nanotubes decorated with silver nanoparticles for photocatalytic degradation of atenolol[J]. Journal of Nanomaterials, 2017, 2017: 9610419. [18] LEBEDEV V A, KOZLOV D A, KOLESNIK I V, et al.The amorphous phase in titania and its influence on photocatalytic properties[J]. Applied Catalysis B: Environmental, 2016, 195: 39-47. [19] MEKASUWANDUMRONG O, CHAITAWORN S, PANPRANOT J, et al.Photocatalytic liquid-phase selective hydrogenation of 3-nitrostyrene to 3-vinylaniline of various treated-TiO2 without use of reducing gas[J]. Catalysts, 2019, 9(4): 329. [20] QIN X, JING L, TIAN G, et al.Enhanced photocatalytic activity for degrading Rhodamine B solution of commercial Degussa P25 TiO2 and its mechanisms[J]. Journal of Hazardous Materials, 2009, 172(2): 1168-1174. [21] HANAOR D A H, SORRELL C C. Review of the anatase to rutile phase transformation[J]. Journal of Materials Science, 2011, 46(4): 855-874. [22] LIU X, LI Y, DENG D, et al.A one-step nonaqueous sol-gel route to mixed-phase TiO2 with enhanced photocatalytic degradation of Rhodamine B under visible light[J]. Crystengcomm, 2016, 18(11): 1964-1975. [23] SING K S W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984)[J]. Pure and Applied Chemistry, 1985, 57(4): 603-619. [24] YU J, RAN J.Facile preparation and enhanced photocatalytic H2-production activity of Cu(OH)2 cluster modified TiO2[J]. Energy & Environmental Science, 2011, 4(4): 1364-1371. [25] TSAI C C, TENG H.Regulation of the physical characteristics of titania nanotube aggregates synthesized from hydrothermal treatment[J]. Chemistry of Materials, 2004, 16(22): 4352-4358. [26] YU J, YU J C, LEUNG M K P, et al. Effects of acidic and basic hydrolysis catalysts on the photocatalytic activity and microstructures of bimodal mesoporous titania[J]. Journal of Catalysis, 2003, 217(1): 69-78. [27] SAPUTERA W H, MUL G, HAMDY M S.Ti3+-containing titania: synthesis tactics and photocatalytic performance[J]. Catalysis Today, 2015, 246: 60-66. [28] SOO C W, LAI C W, PAN G T, et al.Effects of various hydrogenated temperatures on photocatalytic activity of mesoporous titanium dioxide[J]. Micro & Nano Letters, 2018, 13(1): 77-82. [29] PENG T Y, ZHAO D, DAI K, et al.Synthesis of titanium dioxide nanoparticles with mesoporous anatase wall and high photocatalytic activity[J]. Journal of Physical Chemistry B, 2005, 109(11): 4947-4952. [30] XIN X, XU T, YIN J, et al. Management on the location and concentration of Ti3+ in anatase TiO2 for defects-induced visible-light photocatalysis[J]. Applied Catalysis B: Environmental, 2015, 176/177: 354-362. [31] MA S, REISH M E, ZHANG Z, et al.Anatase-selective photoluminescence spectroscopy of P25 TiO2 nanoparticles: different effects of oxygen adsorption on the band bending of anatase[J]. The Journal of Physical Chemistry C, 2017, 121(2): 1263-1271. [32] HAN E, VIJAYARANGAMUTHU K, YOUN J S, et al.Degussa P25 TiO2 modified with H2O2 under microwave treatment to enhance photocatalytic properties[J]. Catalysis Today, 2018, 303: 305-312. [33] FINAZZI E, DI VALENTIN C, PACCHIONI G, et al.Excess electron states in reduced bulk anatase TiO2: comparison of standard GGA, GGA plus U, and hybrid DFT calculations[J]. Journal of Chemical Physics, 2008, 129(15): 154113. [34] CHATTERJEE S, KAR A K.Oxygen-vacancy-dependent photocatalysis for the degradation of MB dye using UV light and observation of förster resonance energy transfer (FRET) in pani-capped ZnO[J]. The Journal of Physical Chemistry C, 2020, 124(33): 18284-18301. [35] TIAN J, LENG Y, CUI H, et al.Hydrogenated TiO2 nanobelts as highly efficient photocatalytic organic dye degradation and hydrogen evolution photocatalyst[J]. Journal of Hazardous Materials, 2015, 299: 165-173.
2023, Vol. 28 
