Abstract
The development of TiO2–x photocatalysts will be discussed in this chapter. TiO2–x can be obtained by the incorporation of H atoms or the removal of oxygen atoms on the surface and/or in the bulk of TiO2 photocatalysts. It has been proved to be an efficient environmental and energy conversion–storage material, which can be used in photodegradation of organic compounds, photocatalytic hydrogen generation from water splitting, photoreduction of CO2, lithium-ion batteries, oxygen reduction reaction, and dye-sensitized solar cells. Firstly, the preparation methods of TiO2–x are carefully discussed and scientifically classified into two main categories, where the reactions take place under reducing or oxidizing atmosphere. In order to further improve the activities of TiO2–x catalysts, modification approaches are then introduced, such as doping with nonmetal elements, grafting with metals, compositing with other materials, designing of ordered morphology, special facet exposure, etc. Finally, the current challenges and limits of TiO2–x are also proposed, and new catalyst systems are encouraged for practical applications in the near future.
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References
Fujishima A, Honda K (1972) Electrochemical photolysis of water at a semiconductor electrode. Nature 238(5358):37–38
Komaguchi K, Nakano H, Araki A, Harima Y (2006) Photoinduced electron transfer from anatase to rutile in partially reduced TiO2 (P-25) nanoparticles: an ESR study. Chem Phys Lett 428(4–6):338–342
Diebold U, Anderson JF, Ng KO, Vanderbilt D (1996) Evidence for the tunneling site on transition-metal oxides: TiO2(110). Phys Rev Lett 77(7):1322–1325
Cronemeyer DC (1959) Infrared absorption of reduced rutile TiO2 single crystals. Phys Rev 113(5):1222–1226
Epling WS, Peden CHF, Henderson MA, Diebold U (1998) Evidence for oxygen adatoms on TiO2 (110) resulting from O2 dissociation at vacancy sites. Surf Sci 412-413(0):333–343
Di Valentin C, Pacchioni G, Selloni A (2009) Reduced and n-type doped TiO2: nature of Ti3+ species. J Phys Chem C 113(48):20543–20552
Jiang Z, Zhang W, Jin L, Yang X, Xu F, Zhu J, Huang W (2007) Direct XPS evidence for charge transfer from a reduced rutile TiO2(110) surface to Au clusters. J Phys Chem C 111(33):12434–12439
Deskins NA, Rousseau R, Dupuis M (2011) Distribution of Ti3+ surface sites in reduced TiO2. J Phys Chem C 115(15):7562–7572
Petrik NG, Zhang Z, Du Y, Dohnálek Z, Lyubinetsky I, Kimmel GA (2009) Chemical reactivity of reduced TiO2(110): the dominant role of surface defects in oxygen chemisorption. J Phys Chem C 113(28):12407–12411
Diebold U, Lehman J, Mahmoud T, Kuhn M, Leonardelli G, Hebenstreit W, Schmid M, Varga P (1998) Intrinsic defects on a TiO2(110)(1×1) surface and their reaction with oxygen: a scanning tunneling microscopy study. Surf Sci 411(1–2):137–153
Fang W, Xing M, Zhang J (2017) Modifications on reduced titanium dioxide photocatalysts: a review. J Photochem Photobiol C 32:21–39
Chen X, Liu L, Yu P, Mao S (2011) Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 331(6018):746–750
Wang G, Wang H, Ling Y, Tang Y, Yang X, Fitzmorris RC, Wang C, Zhang J, Li Y (2011) Hydrogen-treated TiO2 nanowire arrays for photoelectrochemical water splitting. Nano Lett 11(7):3026–3033
Cai J, Wang Y, Zhu Y, Wu M, Zhang H, Li X, Jiang Z, Meng M (2015) In situ formation of disorder-engineered TiO2(B)-anatase heterophase junction for enhanced photocatalytic hydrogen evolution. ACS Appl Mater Inter 7(45):24987–24992
Hu W, Zhou W, Zhang K, Zhang X, Wang L, Jiang B, Tian G, Zhao D, Fu H (2016) Facile strategy for controllable synthesis of stable mesoporous black TiO2 hollow spheres with efficient solar-driven photocatalytic hydrogen evolution. J Mater Chem A 4(19):7495–7502
Lu H, Zhao B, Pan R, Yao J, Qiu J, Luo L, Liu Y (2014) Safe and facile hydrogenation of commercial Degussa P25 at room temperature with enhanced photocatalytic activity. RSC Adv 4(3):1128–1132
Xing M, Fang W, Nasir M, Ma Y, Zhang J, Anpo M (2013) Self-doped Ti3+-enhanced TiO2 nanoparticles with a high-performance photocatalysis. J Catal 297(0):236–243
Ren R, Wen Z, Cui S, Hou Y, Guo X, Chen J (2015) Controllable synthesis and tunable photocatalytic properties of Ti3+-doped TiO2. Sci Rep 5:10714
Fang W, Xing M, Zhang J (2014) A new approach to prepare Ti3+ self-doped TiO2 via NaBH4 reduction and hydrochloric acid treatment. Appl Catal B 160(0):240–246
Zhao Z, Zhang X, Zhang G, Liu Z, Qu D, Miao X, Feng P, Sun Z (2015) Effect of defects on photocatalytic activity of rutile TiO2 nanorods. Nano Res 8(12):4061–4071
Tan H, Zhao Z, Niu M, Mao C, Cao D, Cheng D, Feng P, Sun Z (2014) A facile and versatile method for preparation of colored TiO2 with enhanced solar-driven photocatalytic activity. Nanoscale 6(17):10216–10223
Zhang H, Xing Z, Zhang Y, Li Z, Wu X, Liu C, Zhu Q, Zhou W (2015) Ni2+ and Ti3+ co-doped porous black anatase TiO2 with unprecedented-high visible-light-driven photocatalytic degradation performance. RSC Adv 5(129):107150–107157
Liu X, Xing Z, Zhang H, Wang W, Zhang Y, Li Z, Wu X, Yu X, Zhou W (2016) Fabrication of 3D mesoporous black TiO2/MoS2/TiO2 nanosheets for visible-light-driven photocatalysis. ChemSusChem 9(10):1118–1124
Ma C, Pang G, He G, Li Y, He C, Hao Z (2016) Layered sphere-shaped TiO2 capped with gold nanoparticles on structural defects and their catalysis of formaldehyde oxidation. J Environ Sci 39:77–85
Mao C, Zuo F, Hou Y, Bu X, Feng P (2014) In situ preparation of a Ti3+ self-doped TiO2 film with enhanced activity as photoanode by N2H4 reduction. Angew Chem 126(39):10653–10657
Cheng X, Cheng Q, Li B, Deng X, Li J, Wang P, Zhang B, Liu H, Wang X (2015) One-step construction of N/Ti3+ codoped TiO2 nanotubes photoelectrode with high photoelectrochemical and photoelectrocatalytic performance. Electrochim Acta 186:442–448
Su J, Zou X, Zou Y, Li G, Wang P, Chen J (2013) Porous titania with heavily self-doped Ti3+ for specific sensing of CO at room temperature. Inorg Chem 52(10):5924–5930
Xing M, Zhang J, Chen F, Tian B (2011) An economic method to prepare vacuum activated photocatalysts with high photo-activities and photosensitivities. Chem Commun 47(17):4947–4949
Lu G, Linsebigler A, Yates JT (1994) Ti3+ defect sites on TiO2(110): production and chemical detection of active sites. J Phys Chem 98(45):11733–11738
Fang W, Zhou Y, Dong C, Xing M, Zhang J (2016) Enhanced photocatalytic activities of vacuum activated TiO2 catalysts with Ti3+ and N co-doped. Catal Today 266:188–196
Zhou Y, Liu Y, Liu P, Zhang W, Xing M, Zhang J (2015) A facile approach to further improve the substitution of nitrogen into reduced TiO2-x with an enhanced photocatalytic activity. Appl Catal B 170(0):66–73
Wang Z, Yang C, Lin T, Yin H, Chen P, Wan D, Xu F, Huang F, Lin J, Xie X, Jiang M (2013) Visible-light photocatalytic, solar thermal and photoelectrochemical properties of aluminium-reduced black titania. Energy Environ Sci 6(10):3007–3014
Yang C, Wang Z, Lin T, Yin H, Lü X, Wan D, Xu T, Zheng C, Lin J, Huang F, Xie X, Jiang M (2013) Core-shell nanostructured “Black” rutile titania as excellent catalyst for hydrogen production enhanced by sulfur doping. J Am Chem Soc 135(47):17831–17838
Cui H, Zhao W, Yang C, Yin H, Lin T, Shan Y, Xie Y, Gu H, Huang F (2014) Black TiO2 nanotube arrays for high-efficiency photoelectrochemical water-splitting. J Mater Chem A 2(23):8612–8616
Zheng J, Ji G, Zhang P, Cao X, Wang B, Yu L, Xu Z (2015) Facile aluminum reduction synthesis of blue TiO2 with oxygen deficiency for lithium-ion batteries. Chemistry 21(50):18309–18315
Zheng Z, Huang B, Meng X, Wang J, Wang S, Lou Z, Wang Z, Qin X, Zhang X, Dai Y (2013) Metallic zinc- assisted synthesis of Ti3+ self-doped TiO2 with tunable phase composition and visible-light photocatalytic activity. Chem Commun 49(9):868–870
Pei D, Gong L, Zhang A, Zhang X, Chen J, Mu Y, Yu H (2015) Defective titanium dioxide single crystals exposed by high-energy {001} facets for efficient oxygen reduction. Nat Commun 6:8696
Fu R, Gao S, Xu H, Wang Q, Wang Z, Huang B, Dai Y (2014) Fabrication of Ti3+ self-doped TiO2(A) nanoparticle/TiO2(R) nanorod heterojunctions with enhanced visible-light-driven photocatalytic properties. RSC Adv 4(70):37061–37069
Zhao Z, Tan H, Zhao H, Lv Y, Zhou LJ, Song Y, Sun Z (2014) Reduced TiO2 rutile nanorods with well-defined facets and their visible-light photocatalytic activity. Chem Commun 50(21):2755–2757
Chen J, Song W, Hou H, Zhang Y, Jing M, Jia X, Ji X (2015) Ti3+ self-doped dark rutile TiO2 ultrafine nanorods with durable high-rate capability for lithium-ion batteries. Adv Funct Mater 25(43):6793–6801
Sinhamahapatra A, Jeon JP, Yu JS (2015) A new approach to prepare highly active and stable black titania for visible light-assisted hydrogen production. Energy Environ Sci 8(12):3539–3544
Kitamura T, Shibata K, Takeda K (1993) In-flight reduction of Fe2O3, Cr2O3, TiO2 and Al2O3 by Ar-H2 and Ar-CH4 plasma. ISIJ Int 33(11):1150–1158
Bullard D, Lynch D (1997) Reduction of titanium dioxide in a nonequilibrium hydrogen plasma. Metall Mater Trans B Process Metall Mater Process Sci 28(6):1069–1080
Palmer RA, Doan TM, Lloyd PG, Jarvis BL, Ahmed NU (2002) Reduction of TiO2 with hydrogen plasma. Plasma Chem Plasma Process 22(3):335–350
Lepcha A, Maccato C, Mettenbörger A, Andreu T, Mayrhofer L, Walter M, Olthof S, Ruoko TP, Klein A, Moseler M, Meerholz K, Morante JR, Barreca D, Mathur S (2015) Electrospun black titania nanofibers: influence of hydrogen plasma-induced disorder on the electronic structure and photoelectrochemical performance. J Phys Chem C 119(33):18835–18842
An HR, Park SY, Kim H, Lee CY, Choi S, Lee SC, Seo S, Park EC, Oh YK, Song CG, Won J, Kim YJ, Lee J, Lee HU, Lee YC (2016) Advanced nanoporous TiO2 photocatalysts by hydrogen plasma for efficient solar-light photocatalytic application. Sci Rep 6:29683
Wang Z, Yang C, Lin T, Yin H, Chen P, Wan D, Xu F, Huang F, Lin J, Xie X, Jiang M (2013) H-doped black titania with very high solar absorption and excellent photocatalysis enhanced by localized surface plasmon resonance. Adv Funct Mater 23(43):5444–5450
Tian Z, Cui H, Zhu G, Zhao W, Xu J, Shao F, He J, Huang F (2016) Hydrogen plasma reduced black TiO2-B nanowires for enhanced photoelectrochemical water-splitting. J Power Sources 325:697–705
Kim HJ, Kim J, Hong B (2013) Effect of hydrogen plasma treatment on nano-structured TiO2 films for the enhanced performance of dye-sensitized solar cell. Appl Surf Sci 274:171–175
Siuzdak K, Szkoda M, Lisowska-Oleksiak A, Karczewski J, Ryl J (2016) Highly stable organic–inorganic junction composed of hydrogenated titania nanotubes infiltrated by a conducting polymer. RSC Adv 6(39):33101–33110
Panomsuwan G, Watthanaphanit A, Ishizaki T, Saito N (2015) Water-plasma-assisted synthesis of black titania spheres with efficient visible-light photocatalytic activity. Phys Chem Chem Phys 17(21):13794–13799
Zhu W, Wang C, Chen J, Li Y, Wang J (2014) Enhanced field emission from Ti3+ self-doped TiO2 nanotube arrays synthesized by a facile cathodic reduction process. Appl Surf Sci 301:525–529
Zhang Z, Hedhili MN, Zhu H, Wang P (2013) Electrochemical reduction induced self-doping of Ti3+ for efficient water splitting performance on TiO2 based photoelectrodes. Phys Chem Chem Phys 15(37):15637–15644
Zhang Z, Tan X, Yu T, Jia L, Huang X (2016) Time-dependent formation of oxygen vacancies in black TiO2 nanotube arrays and the effect on photoelectrocatalytic and photoelectrochemical properties. Int J Hydrog Energy 41(27):11634–11643
Swaminathan J, Subbiah R, Singaram V (2016) Defect-rich metallic titania (TiO1.23)–an efficient hydrogen evolution catalyst for electrochemical water splitting. ACS Catal 6(4):2222–2229
Mo LB, Wang Y, Bai Y, Xiang Q, Li Q, Yao W, Wang J, Ibrahim K, Wang H, Wan C, Cao J (2015) Hydrogen impurity defects in rutile TiO2. Sci Rep 5:17634
Liu N, Schneider C, Freitag D, Zolnhofer EM, Meyer K, Schmuki P (2016) Noble-metal-free photocatalytic H2 generation: active and inactive ‘black’ TiO2 nanotubes and synergistic effects. Chemistry 22(39):13810–13814
Chen W, He KF, Wang Y, Chan HLW, Yan Z (2013) Highly mobile and reactive state of hydrogen in metal oxide semiconductors at room temperature. Sci Rep 3:3149
Wang R, Hashimoto K, Fujishima A, Chikuni M, Kojima E, Kitamura A, Shimohigoshi M, Watanabe T (1997) Light-induced amphiphilic surfaces. Nature 388(6641):431–432
Wang R, Hashimoto K, Fujishima A, Chikuni M, Kojima E, Kitamura A, Shimohigoshi M, Watanabe T (1998) Photogeneration of highly amphiphilic TiO2 surfaces. Adv Mater 10(2):135–138
Mezhenny S, Maksymovych P, Thompson TL, Diwald O, Stahl D, Walck SD, Yates JT Jr (2003) STM studies of defect production on the TiO2(110)-(1×1) and TiO2(110)-(1×2) surfaces induced by UV irradiation. Chem Phys Lett 369(1–2):152–158
Shultz AN, Jang W, Hetherington WM, Baer DR, Wang L, Engelhard MH (1995) Comparative second harmonic generation and X-ray photoelectron spectroscopy studies of the UV creation and O2 healing of Ti3+ defects on (110) rutile TiO2 surfaces. Surf Sci 339(1–2):114–124
Coronado JM, Maira AJ, Conesa JC, Yeung KL, Augugliaro V, Soria J (2001) EPR study of the surface characteristics of nanostructured TiO2 under UV irradiation. Langmuir 17(17):5368–5374
Li L, Chen Y, Jiao S, Fang Z, Liu X, Xu Y, Pang G, Feng S (2016) Synthesis, microstructure, and properties of black anatase and B phase TiO2 nanoparticles. Mater Design 100:235–240
Wu Q, Huang F, Zhao M, Xu J, Zhou J, Wang Y (2016) Ultra-small yellow defective TiO2 nanoparticles for co-catalyst free photocatalytic hydrogen production. Nano Energy 24:63–71
Zuo F, Bozhilov K, Dillon RJ, Wang L, Smith P, Zhao X, Bardeen C, Feng P (2012) Active facets on titanium(III)-doped TiO2: an effective strategy to improve the visible-light photocatalytic activity. Angew Chem Int Ed 51(25):6223–6226
Liu Y, Quan B, Ji G, Zhang H (2016) One-step synthesis of Ti3+ doped TiO2 single anatase crystals with enhanced photocatalytic activity towards degradation of methylene blue. Mater Lett 162:138–141
Cai J, Za H, Lv K, Sun J, Deng K (2014) Ti powder-assisted synthesis of Ti3+ self-doped TiO2 nanosheets with enhanced visible-light photoactivity. RSC Adv 4(38):19588–19593
Yang H, Sun C, Qiao S, Zou J, Liu G, Smith SC, Cheng H, Lu G (2008) Anatase TiO2 single crystals with a large percentage of reactive facets. Nature 453(7195):638–641
Liu X, Gao S, Xu H, Lou Z, Wang W, Huang B, Dai Y (2013) Green synthetic approach for Ti3+ self-doped TiO2-x nanoparticles with efficient visible light photocatalytic activity. Nanoscale 5(5):1870–1875
Liu X, Xu H, Grabstanowicz LR, Gao S, Lou Z, Wang W, Huang B, Dai Y, Xu T (2014) Ti3+ self-doped TiO2-x anatase nanoparticles via oxidation of TiH2 in H2O2. Catal Today 225(0):80–89
Wang X, Li Y, Liu X, Gao S, Huang B, Dai Y (2015) Preparation of Ti3+ self-doped TiO2 nanoparticles and their visible light photocatalytic activity. Chin J Catal 36(3):389–399
Wu C, Gao Z, Gao S, Wang Q, Xu H, Wang Z, Huang B, Dai Y (2016) Ti3+ self-doped TiO2 photoelectrodes for photoelectrochemical water splitting and photoelectrocatalytic pollutant degradation. J Energ Chem 25(4):726–733
Grabstanowicz LR, Gao S, Li T, Rickard RM, Rajh T, Liu D, Xu T (2013) Facile oxidative conversion of TiH2 to high-concentration Ti3+-self-doped rutile TiO2 with visible-light photoactivity. Inorg Chem 52(7):3884–3890
Xin X, Xu T, Yin J, Wang L, Wang C (2015) Management on the location and concentration of Ti3+ in anatase TiO2 for defects-induced visible-light photocatalysis. Appl Catal B 176-177:354–362
Zhu G, Shan Y, Lin T, Zhao W, Xu J, Tian Z, Zhang H, Zheng C, Huang F (2016) Hydrogenated blue titania with high solar absorption and greatly improved photocatalysis. Nanoscale 8(8):4705–4712
Liu M, Qiu X, Miyauchi M, Hashimoto K (2011) Cu(II) oxide amorphous nanoclusters grafted Ti3+ self-doped TiO2: an efficient visible light photocatalyst. Chem Mater 23(23):5282–5286
Fang W, Khrouz L, Zhou Y, Shen B, Dong C, Xing M, Mishra S, Daniele S, Zhang J (2017) Reduced {001}-TiO2-x photocatalysts: noble-metal-free CO2 photoreduction for selective CH4 evolution. Phys Chem Chem Phys 19(21):13875–13881
Zhu Q, Peng Y, Lin L, Fan C, Gao G, Wang R, Xu A (2014) Stable blue TiO2-x nanoparticles for efficient visible light photocatalysts. J Mater Chem A 2(12):4429–4437
Qiu M, Tian Y, Chen Z, Yang Z, Li W, Wang K, Wang L, Wang K, Zhang W (2016) Synthesis of Ti3+ self-doped TiO2 nanocrystals based on Le Chatelier’s principle and their application in solar light photocatalysis. RSC Adv 6(78):74376–74383
Chen X, Liu L, Liu Z, Marcus MA, Wang W, Oyler NA, Grass ME, Mao B, Glans PA, Yu P, Guo J, Mao S (2013) Properties of disorder-engineered black titanium dioxide nanoparticles through hydrogenation. Sci Rep 3:1510
Naldoni A, Allieta M, Santangelo S, Marelli M, Fabbri F, Cappelli S, Bianchi CL, Psaro R, Dal Santo V (2012) Effect of nature and location of defects on bandgap narrowing in black TiO2 nanoparticles. J Am Chem Soc 134(18):7600–7603
Khan MM, Ansari SA, Pradhan D, Ansari MO, Han DH, Lee J, Cho MH (2014) Band gap engineered TiO2 nanoparticles for visible light induced photoelectrochemical and photocatalytic studies. J Mater Chem A 2(3):637–644
Liu Y, Wang J, Yang P, Matras-Postolek K (2015) Self-modification of TiO2 one-dimensional nano-materials by Ti3+ and oxygen vacancy using Ti2O3 as precursor. RSC Adv 5(76):61657–61663
Zuo F, Wang L, Wu T, Zhang Z, Borchardt D, Feng P (2010) Self-doped Ti3+ enhanced photocatalyst for hydrogen production under visible light. J Am Chem Soc 132(34):11856–11857
Diebold U (2003) The surface science of titanium dioxide. Surf Sci Rep 48(5–8):53–229
Fang W, Dappozze F, Guillard C, Zhou Y, Xing M, Mishra S, Daniele S, Zhang J (2017) Zn-assisted TiO2-x photocatalyst with efficient charge separation for enhanced photocatalytic activities. J Phys Chem C 121:17068
Livraghi S, Chiesa M, Paganini MC, Giamello E (2011) On the nature of reduced states in titanium dioxide as monitored by electron paramagnetic resonance. I: the anatase case. J Phys Chem C 115(51):25413–25421
Sekiya T, Kurita S (2008) Defects in anatase titanium dioxide. In: Ohno K, Tanaka M, Takeda J, Kawazoe Y (eds) Nano- and micromaterials, vol 9. Springer, Berlin/Heidelberg, pp 121–141
Qiu B, Zhou Y, Ma Y, Yang X, Sheng W, Xing M, Zhang J (2015) Facile synthesis of the Ti3+ self-doped TiO2-graphene nanosheet composites with enhanced photocatalysis. Sci Rep 5:8591
Giannakas AE, Antonopoulou M, Deligiannakis Y, Konstantinou I (2013) Preparation, characterization of N-I co-doped TiO2 and catalytic performance toward simultaneous Cr(VI) reduction and benzoic acid oxidation. Appl Catal B 140:636–645
Wendt S, Schaub R, Matthiesen J, Vestergaard EK, Wahlström E, Rasmussen MD, Thostrup P, Molina LM, Lægsgaard E, Stensgaard I, Hammer B, Besenbacher F (2005) Oxygen vacancies on TiO2(110) and their interaction with H2O and O2: a combined high-resolution STM and DFT study. Surf Sci 598(1–3):226–245
Fischer S, Schierbaum K-D, Göpel W (1997) Surface defects and platinum overlayers on TiO2(110) surfaces: STM and photoemission studies. Vacuum 48(7–9):601–605
Chen C, Chen T, Chen C, Lai Y, You J, Chou T, Chen C, Lee J (2012) Effect of Ti3+ on TiO2-supported Cu catalysts used for CO oxidation. Langmuir 28(26):9996–10006
Zhang C, Xie Y, Ma J, Hu J, Zhang C (2015) A composite catalyst of reduced black TiO2-x/CNT: a highly efficient counter electrode for ZnO-based dye-sensitized solar cells. Chem Commun 51(98):17459–17462
Liao W, Murugananthan M, Zhang Y (2015) Synthesis of Z-scheme g-C3N4-Ti3+/TiO2 material: an efficient visible light photoelectrocatalyst for degradation of phenol. Phys Chem Chem Phys 17(14):8877–8884
Ioannidou E, Ioannidi A, Frontistis Z, Antonopoulou M, Tselios C, Tsikritzis D, Konstantinou I, Kennou S, Kondarides DI, Mantzavinos D (2016) Correlating the properties of hydrogenated titania to reaction kinetics and mechanism for the photocatalytic degradation of bisphenol A under solar irradiation. Appl Catal B 188:65–76
Qin X, He F, Chen L, Meng Y, Liu J, Zhao N, Huang Y (2016) Oxygen-vacancy modified TiO2 nanoparticles as enhanced visible-light driven photocatalysts by wrapping and chemically bonding with graphite-like carbon. RSC Adv 6(13):10887–10894
Xing M, Li X, Zhang J (2014) Synergistic effect on the visible light activity of Ti3+ doped TiO2 nanorods/boron doped graphene composite. Sci Rep 4:5493
Wang J, Yang P, Huang B (2015) Self-doped TiO2-x nanowires with enhanced photocatalytic activity: facile synthesis and effects of the Ti3+. Appl Surf Sci 356:391–398
Liu N, Schneider C, Freitag D, Hartmann M, Venkatesan U, Müller J, Spiecker E, Schmuki P (2014) Black TiO2 nanotubes: cocatalyst-free open-circuit hydrogen generation. Nano Lett 14(6):3309–3313
Yan X, Xing Z, Cao Y, Hu M, Li Z, Wu X, Zhu Q, Yang S, Zhou W (2017) In-situ C-N-S-tridoped single crystal black TiO2 nanosheets with exposed {001} facets as efficient visible-light-driven photocatalysts. Appl Catal B 219:572–579
Zheng J, Bao S, Zhang X, Wu H, Chen R, Jin P (2016) Pd–MgNix nanospheres/black-TiO2 porous films with highly efficient hydrogen production by near-complete suppression of surface recombination. Appl Catal B 183:69–74
Liu L, Zhao C, Li Y (2012) Spontaneous dissociation of CO2 to CO on defective surface of Cu(I)/TiO2–x nanoparticles at room temperature. J Phys Chem C 116(14):7904–7912
Sasan K, Zuo F, Wang Y, Feng P (2015) Self-doped Ti3+-TiO2 as a photocatalyst for the reduction of CO2 into a hydrocarbon fuel under visible light irradiation. Nanoscale 7(32):13369–13372
Zhang L, Wang W, Jiang D, Gao E, Sun S (2015) Photoreduction of CO2 on BiOCl nanoplates with the assistance of photoinduced oxygen vacancies. Nano Res 8(3):821–831
Yin G, Bi Q, Zhao W, Xu J, Lin T, Huang F (2017) Efficient conversion of CO2 to methane Photocatalyzed by conductive black titania. ChemCatChem:n/a-n/a
Fu R, Wang Q, Gao S, Wang Z, Huang B, Dai Y, Lu J (2015) Effect of different processes and Ti/Zn molar ratios on the structure, morphology, and enhanced photoelectrochemical and photocatalytic performance of Ti3+ self-doped titanium-zinc hybrid oxides. J Power Sources 285:449–459
Li K, Huang Z, Zeng X, Huang B, Gao S, Lu J (2017) Synergetic effect of Ti3+ and oxygen doping on enhancing photoelectrochemical and photocatalytic properties of TiO2/g-C3N4 heterojunctions. ACS Appl Mater Interfaces 9(13):11577–11586
Zhu Y, Shah MW, Wang C (2017) Insight into the role of Ti3+ in photocatalytic performance of shuriken-shaped BiVO4/TiO2-x heterojunction. Appl Catal B 203:526–532
Zhang X, Zuo G, Lu X, Tang C, Cao S, Yu M (2017) Anatase TiO2 sheet-assisted synthesis of Ti3+ self-doped mixed phase TiO2 sheet with superior visible-light photocatalytic performance: roles of anatase TiO2 sheet. J Colloid Interface Sci 490:774–782
Duan Y, Zhang M, Wang L, Wang F, Yang L, Li X, Wang C (2017) Plasmonic Ag-TiO2−x nanocomposites for the photocatalytic removal of NO under visible light with high selectivity: the role of oxygen vacancies. Appl Catal B 204:67–77
Singh AP, Kodan N, Mehta BR, Dey A, Krishnamurthy S (2016) In-situ plasma hydrogenated TiO2 thin films for enhanced photoelectrochemical properties. Mater Res Bull 76:284–291
Zhang Q, Wang L, Feng J, Xu H, Yan W (2014) Enhanced photoelectrochemical performance by synthesizing CdS decorated reduced TiO2 nanotube arrays. Phys Chem Chem Phys 16(42):23431–23439
Zheng J, Liu Y, Ji G, Zhang P, Cao X, Wang B, Zhang C, Zhou X, Zhu Y, Shi D (2015) Hydrogenated oxygen-deficient blue anatase as anode for high-performance lithium batteries. ACS Appl Mater Inter 7(42):23431–23438
Wang C, Wang F, Zhao Y, Li Y, Yue Q, Liu Y, Liu Y, Elzatahry AA, Al-Enizi A, Wu Y, Deng Y, Zhao D (2016) Hollow TiO2-x porous microspheres composed of well-crystalline nanocrystals for high-performance lithium-ion batteries. Nano Res 9(1):165–173
Shang M, Hu H, Lu G, Bi Y (2016) Synergistic effects of SrTiO3 nanocubes and Ti3+ dual-doping for highly improved photoelectrochemical performance of TiO2 nanotube arrays under visible light. J Mater Chem A 4(16):5849–5853
Su T, Yang Y, Na Y, Fan R, Li L, Wei L, Yang B, Cao W (2015) An insight into the role of oxygen vacancy in hydrogenated TiO2 nanocrystals in the performance of dye-sensitized solar cells. ACS Appl Mater Inter 7(6):3754–3763
Pan S, Liu X, Guo M, Sf Y, Huang H, Fan H, Li G (2015) Engineering the intermediate band states in amorphous Ti3+-doped TiO2 for hybrid dye-sensitized solar cell applications. J Mater Chem A 3(21):11437–11443
Byeon A, Boota M, Beidaghi M, Aken KV, Lee JW, Gogotsi Y (2015) Effect of hydrogenation on performance of TiO2(B) nanowire for lithium ion capacitors. Electrochem Commun 60:199–203
Sang-Joon P, Jeong-Pyo L, Jong Shik J, Hyun R, Hyunung Y, Byung Youn Y, Chang Soo K, Kyung Joong K, Yong Jai C, Sunggi B, Woo L (2013) In situ control of oxygen vacancies in TiO2 by atomic layer deposition for resistive switching devices. Nanotechnology 24(29):295202
Yabuuchi N, Kubota K, Dahbi M, Komaba S (2014) Research development on sodium-ion batteries. Chem Rev 114(23):11636–11682
Chen J, Ding Z, Wang C, Hou H, Zhang Y, Wang C, Zou G, Ji X (2016) Black anatase titania with ultrafast sodium-storage performances stimulated by oxygen vacancies. ACS Appl Mater Inter 8(14):9142–9151
Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y (2001) Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293(5528):269–271
Di Valentin C, Pacchioni G, Selloni A, Livraghi S, Giamello E (2005) Characterization of paramagnetic species in N-doped TiO2 powders by EPR spectroscopy and DFT calculations. J Phys Chem B 109(23):11414–11419
Sayed FN, Jayakumar OD, Sasikala R, Kadam RM, Bharadwaj SR, Kienle L, Schürmann U, Kaps S, Adelung R, Mittal JP, Tyagi AK (2012) Photochemical hydrogen generation using nitrogen-doped TiO2-Pd nanoparticles: facile synthesis and effect of Ti3+ incorporation. J Phys Chem C 116(23):12462–12467
Hoang S, Berglund SP, Hahn NT, Bard AJ, Mullins CB (2012) Enhancing visible light photo-oxidation of water with TiO2 nanowire arrays via cotreatment with H2 and NH3: synergistic effects between Ti3+ and N. J Am Chem Soc 134(8):3659–3662
Zhou Y, Yi Q, Xing M, Shang L, Zhang T, Zhang J (2016) Graphene modified mesoporous titania single crystals with controlled and selective photoredox surfaces. Chem Commun 52(8):1689–1692
Chen Y, Cao X, Lin B, Gao B (2013) Origin of the visible-light photoactivity of NH3-treated TiO2: effect of nitrogen doping and oxygen vacancies. Appl Surf Sci 264:845–852
Zhang K, Zhou W, Chi L, Zhang X, Hu W, Jiang B, Pan K, Tian G, Jiang Z (2016) Black N/H-TiO2 nanoplates with a flower-like hierarchical architecture for photocatalytic hydrogen evolution. ChemSusChem 9(19):2841–2848
Li B, Zhao Z, Zhou Q, Meng B, Meng X, Qiu J (2014) Highly efficient low-temperature plasma-assisted modification of TiO2 nanosheets with exposed {001} facets for enhanced visible-light photocatalytic activity. Chem Eur J 20(45):14763–14770
Li G, Li J, Li G, Jiang G (2015) N and Ti3+ co-doped 3D anatase TiO2 superstructures composed of ultrathin nanosheets with enhanced visible light photocatalytic activity. J Mater Chem A 3(44):22073–22080
Lin T, Yang C, Wang Z, Yin H, Lu X, Huang F, Lin J, Xie X, Jiang M (2014) Effective nonmetal incorporation in black titania with enhanced solar energy utilization. Energy Environ Sci 7(3):967–972
Feng N, Liu F, Huang M, Zheng A, Wang Q, Chen T, Cao G, Xu J, Fan J, Deng F (2016) Unravelling the efficient photocatalytic activity of boron-induced Ti3+ species in the surface layer of TiO2. Sci Rep 6:34765
Xing M, Zhang J, Qiu B, Tian B, Anpo M, Che M (2015) A brown mesoporous TiO2-x/MCF composite with an extremely high quantum yield of solar energy photocatalysis for H2 evolution. Small 11(16):1920–1929
Xing J, Chen J, Li Y, Yuan W, Zhou Y, Zheng L, Wang H, Hu P, Wang Y, Zhao H, Wang Y, Yang H (2014) Stable isolated metal atoms as active sites for photocatalytic hydrogen evolution. Chem Eur J 20(8):2138–2144
Yuan X, Wang X, Liu X, Ge H, Yin G, Dong C, Huang F (2016) Ti3+-promoted high oxygen-reduction activity of Pd nanodots supported by black titania nanobelts. ACS Appl Mater Inter 8(41):27654–27660
Bonneviot L, Haller GL (1988) EPR characterization of Ti3+ ions at the metal-support interface in PtTiO2 catalysts. J Catal 113(1):96–105
Lian Z, Wang W, Li G, Tian F, Schanze KS, Li H (2016) Pt-enhanced mesoporous Ti3+/TiO2 with rapid bulk to surface electron transfer for photocatalytic hydrogen evolution. ACS Appl Mater Inter
Pillay D, Hwang GS (2005) Growth and structure of small gold particles on rutile TiO2(110). Phys Rev B 72(20):205422
Albuquerque AR, Bruix A, dos Santos IMG, Sambrano JR, Illas F (2014) DFT study on Ce-doped anatase TiO2: nature of Ce3+ and Ti3+ centers triggered by oxygen vacancy formation. J Phys Chem C 118(18):9677–9689
Bennett T, Adnan RH, Alvino JF, Kler R, Golovko VB, Metha GF, Andersson GG (2015) Effect of gold nanoclusters on the production of Ti3+ defect sites in titanium dioxide nanoparticles under ultraviolet and soft X-ray radiation. J Phys Chem C 119(20):11171–11177
Zhao J, Li Y, Zhu Y, Wang Y, Wang C (2016) Enhanced CO2 photoreduction activity of black TiO2-coated Cu nanoparticles under visible light irradiation: role of metallic Cu. Appl Catal A-Gen 510:34–41
Pan X, Xu YJ (2013) Fast and spontaneous reduction of gold ions over oxygen-vacancy-rich TiO2: a novel strategy to design defect-based composite photocatalyst. Appl Catal A-Gen 459:34–40
Chen P (2016) A novel synthesis of Ti3+ self-doped Ag2O/TiO2(p–n) nanoheterojunctions for enhanced visible photocatalytic activity. Mater Lett 163:130–133
Li M, Liu H, Liu T, Qin Y (2017) Design of a novel dual Z-scheme photocatalytic system composited of Ag2O modified Ti3+ self doped TiO2 nanocrystals with individual exposed (001) and (101) facets. Mater Charact 124:136–144
Cui Y, Ma Q, Deng X, Meng Q, Cheng X, Xie M, Li X, Cheng Q, Liu H (2017) Fabrication of Ag-Ag2O/reduced TiO2 nanophotocatalyst and its enhanced visible light driven photocatalytic performance for degradation of diclofenac solution. Appl Catal B 206:136–145
Yin H, Wang X, Wang L, Nie Q, Zhang Y, Yuan Q, Wu W (2016) Ag/AgCl modified self-doped TiO2 hollow sphere with enhanced visible light photocatalytic activity. J Alloys Compd 657:44–52
Colón G, Maicu M, Hidalgo MC, Navío JA (2006) Cu-doped TiO2 systems with improved photocatalytic activity. Appl Catal B 67(1–2):41–51
Liu L, Gao F, Zhao L, Li Y (2013) Tailoring Cu valence and oxygen vacancy in Cu/TiO2 catalysts for enhanced CO2 photoreduction efficiency. Appl Catal B 134(0):349–358
Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically thin carbon films. Science 306(5696):666–669
Geim AK, Novoselov KS (2007) The rise of graphene. Nat Mater 6(3):183–191
Wang C, Meng D, Sun J, Memon J, Huang Y, Geng J (2014) Graphene wrapped TiO2 based catalysts with enhanced photocatalytic activity. Adv Mater Interfaces 1(4):1300150
Li L, Yu L, Lin Z, Yang G (2016) Reduced TiO2-graphene oxide heterostructure as broad spectrum-driven efficient water-splitting photocatalysts. ACS Appl Mater Inter 8(13):8536–8545
Cao S, Liu T, Tsang Y, Chen C (2016) Role of hydroxylation modification on the structure and property of reduced graphene oxide/TiO2 hybrids. Appl Surf Sci 382:225–238
Fu G, Zhou P, Zhao M, Zhu W, Yan S, Yu T, Zou Z (2015) Carbon coating stabilized Ti3+-doped TiO2 for photocatalytic hydrogen generation under visible light irradiation. Dalton Trans 44(28):12812–12817
Liu Y, Xing M, Zhang J (2014) Ti3+ and carbon co-doped TiO2 with improved visible light photocatalytic activity. Chin J Catal 35(9):1511–1519
Yi Q, Zhou Y, Xing M, Zhang J (2016) Vacuum activation-induced Ti3+ and carbon co-doped TiO2 with enhanced solar light photo-catalytic activity. Res Chem Intermed 42(5):4181–4189
Li K, Gao S, Wang Q, Xu H, Wang Z, Huang B, Dai Y, Lu J (2015) In-situ-reduced synthesis of Ti3+ self-doped TiO2/g-C3N4 heterojunctions with high photocatalytic performance under LED light irradiation. ACS Appl Mater Inter 7(17):9023–9030
Lu D, Zhang G, Wan Z (2015) Visible-light-driven g-C3N4/Ti3+-TiO2 photocatalyst co-exposed {001} and {101} facets and its enhanced photocatalytic activities for organic pollutant degradation and Cr(VI) reduction. Appl Surf Sci 358:223–230
Liu X, Xing Z, Zhang Y, Li Z, Wu X, Tan S, Yu X, Zhu Q, Zhou W (2017) Fabrication of 3D flower-like black N-TiO2-x@MoS2 for unprecedented-high visible-light-driven photocatalytic performance. Appl Catal B 201:119–127
Wen M, Zhang S, Dai W, Li G, Zhang D (2015) In situ synthesis of Ti3+ self-doped mesoporous TiO2 as a durable photocatalyst for environmental remediation. Chin J Catal 36(12):2095–2102
Wei S, Wu R, Xu X, Jian J, Wang H, Sun Y (2016) One-step synthetic approach for core-shelled black anatase titania with high visible light photocatalytic performance. Chem Eng J 299:120–125
Wang S, Yang X, Wang Y, Liu L, Guo Y, Guo H (2014) Morphology-controlled synthesis of Ti3+ self-doped yolk-shell structure titanium oxide with superior photocatalytic activity under visible light. J Solid State Chem 213:98–103
Zhu G, Xu J, Zhao W, Huang F (2016) Constructing black titania with unique nanocage structure for solar desalination. ACS Appl Mater Inter 8(46):31716–31721
Qi D, Lu L, Xi Z, Wang L, Zhang J (2014) Enhanced photocatalytic performance of TiO2 based on synergistic effect of Ti3+ self-doping and slow light effect. Appl Catal B 160:621–628
Xin L, Liu X (2015) Black TiO2 inverse opals for visible-light photocatalysis. RSC Adv 5(88):71547–71550
Yu J, Low J, Xiao W, Zhou P, Jaroniec M (2014) Enhanced photocatalytic CO2-reduction activity of anatase TiO2 by coexposed {001} and {101} facets. J Am Chem Soc 136(25):8839–8842
Xing M, Yang B, Yu H, Tian B, Bagwasi S, Zhang J, Gong X (2013) Enhanced photocatalysis by Au nanoparticle loading on TiO2 single-crystal (001) and (110) facets. J Phys Chem Lett 4(22):3910–3917
Si L, Huang Z, Lv K, Tang D, Yang C (2014) Facile preparation of Ti3+ self-doped TiO2 nanosheets with dominant {001} facets using zinc powder as reductant. J Alloys Compd 601:88–93
Wang W, Lu C, Ni Y, Song J, Su M, Xu Z (2012) Enhanced visible-light photoactivity of {001} facets dominated TiO2 nanosheets with even distributed bulk oxygen vacancy and Ti3+. Catal Commun 22(0):19–23
Wang W, Ni Y, Lu C, Xu Z (2012) Hydrogenation of TiO2 nanosheets with exposed {001} facets for enhanced photocatalytic activity. RSC Adv 2(22):8286–8288
Chen S, Li D, Liu Y, Huang W (2016) Morphology-dependent defect structures and photocatalytic performance of hydrogenated anatase TiO2 nanocrystals. J Catal 341:126–135
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Zhang, J., Tian, B., Wang, L., Xing, M., Lei, J. (2018). Preparation of Reduced TiO2–x for Photocatalysis. In: Photocatalysis. Lecture Notes in Chemistry, vol 100. Springer, Singapore. https://doi.org/10.1007/978-981-13-2113-9_4
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