Synthesis of crystal-phase and color tunable mixed anion co-doped titanium oxides and their controllable photocatalytic activity

Abstract

B and N mixed anions co-doped titania with various crystal phases such as anatase, brookite, and rutile were successfully synthesized by a hydrothermal synthesis followed by heat treatment in an ammonia gas atmosphere at 550–650°C (denoted as BN-Ana_x, BN-Bro_x, and BN-Rut_x, x is the treatment temperature). The colors of as-prepared BN-Ana, BN-Bro, and BN-Rut are red, yellow-green, and cyan-green, respectively. The color changing mechanism of titania was related to their various band gap structure and the existence of B-N bonding. The nitridation temperature exhibits effective color changing compared to that of nitridation time. The different phases of the mixed anion co-doped titania possess different photocatalytic deNO _x activity. The BN-Ana and BN-Rut show poor photocatalytic deNO _x activity, while the BN-Bro shows excellent photocatalytic deNO _x activity, better than that of standard titania photocatalyst Degussa P25. The colorful titania with low-photocatalytic activity is heavy metal elements free, indicating their possible applications as nontoxic color pigments or novel cosmetic raw materials.

Keywords

colorful titania / toxic elements free / mixed anion compounds / pigment / photocatalytic activity / cosmetic application

References

[1] Zhang P, Yin S, Sato T. Synthesis of high-activity TiO₂ photocatalyst via environmentally friendly and novel microwave assisted hydrothermal process. Appl. Catal. B, 2009, 89(1–2): 118.

[2] Yin S, Asakura Y. Recent research progress on mixed valence state tungsten based materials. Tungsten, 2019, 1(1): 5.

[3] A. Hermawan, N.L.W. Septiani, A. Taufik, B. Yuliarto, and S. Yin, Advanced strategies to improve performances of molybdenum-based gas sensors, Nano-Micro Lett., 13(2021), No. 1, art. No. 207.

[4] J. Cao, T. Hasegawa, Y. Asakura, et al., Synthesis and color tuning of titanium oxide inorganic pigment by phase control and mixed-anion co-doping, Adv. Powder Technol., 33(2022), No. 5, art. No. 103576.

[5] Yin S. Creation of advanced optical responsive functionality of ceramics by green processes. J. Ceram. Soc. Jpn., 2015, 123(1441): 823.

[6] Xue Y, Yin S. Element doping: A marvelous strategy for pioneering the smart applications of VO₂. Nanoscale, 2022, 14(31): 11054.

[7] A. Hermawan, T. Amrillah, A. Riapanitra, W.J. Ong, and S. Yin, Prospects and challenges of MXenes as emerging sensing materials for flexible and wearable breath-based biomarker diagnosis, Adv. Healthcare Mater., 10(2021), No. 20, art. No. 2100970.

[8] Yin S, Hasegawa T. Morphology control of transition metal oxides by liquid-phase process and their material development. KONA Powder Part. J., 2023, 40, 94.

[9] Hermawan A, Son H, Asakura Y, Mori T, Yin S. Synthesis of morphology controllable aluminum nitride by direct nitridation of γ-AlOOH in the presence of N₂H₄ and their sintering behavior. J. Asian Ceram. Soc., 2018, 6(1): 63.

[10] Hermawan A, Asakura Y, Yin S. Morphology control of aluminum nitride (AlN) for a novel high-temperature hydrogen sensor. Int. J. Miner. Metall. Mater., 2020, 27(11): 1560.

[11] Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future. Nature, 2012, 488(7411): 294.

[12] Olabi AG, Mahmoud M, Soudan B, Wilberforce T, Ramadan M. Geothermal based hybrid energy systems, toward eco-friendly energy approaches. Renewable Energy, 2020, 147, 2003.

[13] Panwar NL, Kaushik SC, Kothari S. Role of renewable energy sources in environmental protection: A review. Renewable Sustainable Energy Rev., 2011, 15(3): 1513.

[14] Liu G, Yin LC, Wang J, et al. A red anatase TiO₂ photocatalyst for solar energy conversion. Energy Environ. Sci., 2012, 5(11): 9603.

[15] Liu G, Pan J, Yin L, et al. Heteroatom-modulated switching of photocatalytic hydrogen and oxygen evolution preferences of anatase TiO₂ microspheres. Adv. Funct. Mater., 2012, 22(15): 3233.

[16] Wang D, Wang S, Li B, Zhang Z, Zhang Q. Tunable band gap of N, V co-doped Ca:TiO₂B (CaTi₅O₁₁) for visible-light photocatalysis. Int. J. Hydrogen Energy, 2019, 44(10): 4716.

[17] Li X, Liu Y, Yang P, Shi Y. Visible light-driven photocatalysis of W, N co-doped TiO₂. Particuology, 2013, 11(6): 732.

[18] Komatsuda S, Asakura Y, Vequizo JJM, Yamakata A, Yin S. Enhanced photocatalytic NO_x decomposition of visible-light responsive F-TiO₂/(N, C)-TiO₂ by charge transfer between F-TiO₂ and (N, C)-TiO₂ through their doping levels. Appl. Catal. B, 2018, 238, 358.

[19] Gao HT, Liu YY, Ding CH, Dai DM, Liu GJ. Synthesis, characterization, and theoretical study of N, S-codoped nano-TiO₂ with photocatalytic activities. Int. J. Miner. Metall. Mater., 2011, 18(5): 606.

[20] Pienutsa N, Yannawibut K, Phattharaphongmanee J, Thonganantakul O, Srinives S. Titanium dioxide-graphene composite electrochemical sensor for detection of hexavalent chromium. Int. J. Miner. Metall. Mater., 2022, 29(3): 529.

[21] Wang HH, Liu WX, Ma J, et al. Design of (GO/TiO₂)_N one-dimensional photonic crystal photocatalysts with improved photocatalytic activity for tetracycline degradation. Int. J. Miner. Metall. Mater., 2020, 27(6): 830.

[22] Z. Gu, Z. Cui, Z. Wang, et al., Carbon vacancies and hydroxyls in graphitic carbon nitride: Promoted photocatalytic NO removal activity and mechanism, Appl. Catal. B, 279(2020), art. No. 119376.

[23] C. Noda, Y. Asakura, K. Shiraki, A. Yamakata, and S. Yin, Synthesis of three-component C₃N₄/rGO/C-TiO₂ photocatalyst with enhanced visible-light responsive photocatalytic deNO activity, Chem. Eng. J., 390(2020), art. No. 124616.

[24] Z. Gu, B. Zhang, Y. Asakura, et al., Alkali-assisted hydrothermal preparation of g-C₃N₄/rGO nanocomposites with highly enhanced photocatalytic NO_x removal activity, Appl. Surf. Sci., 521(2020), art. No. 146213.

[25] H. Li, S. Yin, Y. Wang, and T. Sato, Current progress on persistent fluorescence-assisted composite photocatalysts, Funct. Mater. Lett., 6(2013), No. 6, art. No. 1330005.

[26] X. Wu, S. Yin, Q. Dong, et al., UV, visible and near-infrared lights induced NO_x destruction activity of (Yb, Er)-NaYF₄/C-TiO₂ composite, Sci. Rep., 3(2013), art. No. 2918.

[27] Wu X, Yin S, Dong Q, Sato T. Blue/green/red colour emitting up-conversion phosphors coupled C-TiO₂ composites with UV, visible and NIR responsive photocatalytic performance. Appl. Catal. B, 2014, 156–157, 257.

[28] Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y. Visible-light photocatalysis in nitrogen-doped titanium oxides. Science, 2001, 293(5528): 269.

[29] Lin H, Li L, Zhao M, et al. Synthesis of high-quality brookite TiO₂ single-crystalline nanosheets with specific facets exposed: Tuning catalysts from inert to highly reactive. J. Am. Chem. Soc., 2012, 134(20): 8328.

[30] Inagawa A, Uehara N. Development of colorimetric analysis with smartphones-captured images based on RGB-spectrum conversion methods. Bunseki Kagaku, 2020, 69(12): 693.

[31] Japanese Industrial Standard. Fine ceramics (advanced ceramics, advanced technical ceramics)- Test Method for Air Purification Performance of Photocatalytic Materials-Part 1: Removal of Nitric Oxide, 2016, Tokyo, Japanese Standards Association.

[32] Ivanov VV, Blokhina IA, Kirik SD. Synthesis of TiB₂ by carbothermal reduction of oxides at lowered temperatures. Russ J. Appl. Chem., 2013, 86(11): 1650.

[33] Ghanbari A, Sakaki M, Faeghinia A, Bafghi MS, Yanagisawa K. Synthesis of nanocrystalline TiB₂ powder from TiO₂, B₂O₃ and Mg reactants through microwave-assisted self-propagating high-temperature synthesis method. Bull. Mater. Sci., 2016, 39(4): 925.

[34] Finazzi E, Di Valentin C, Pacchioni G. Boron-doped anatase TiO₂: Pure and hybrid DFT calculations. J. Phys. Chem. C, 2009, 113(1): 220.

[35] Du Y, Wang Z, Chen H, Wang HY, Liu G, Weng Y. Effect of trap states on photocatalytic properties of boron-doped anatase TiO₂ microspheres studied by time-resolved infrared spectroscopy. Phys. Chem. Chem. Phys., 2019, 21(8): 4349.

[36] Di Valentin C, Pacchioni G, Selloni A, Livraghi S, Giamello E. Characterization of paramagnetic species in N-doped TiO₂ powders by EPR spectroscopy and DFT calculations. J. Phys. Chem. B, 2005, 109(23): 11414.

[37] Zhang Z, Wang X, Long J, Gu Q, Ding Z, Fu X. Nitrogen-doped titanium dioxide visible light photocatalyst: Spectroscopic identification of photoactive centers. J. Catal., 2010, 276(2): 201.

[38] Kanazawa T, Kato K, Yamaguchi R, et al. Cobalt aluminate spinel as a cocatalyst for photocatalytic oxidation of water: Significant hole-trapping effect. ACS Catal., 2020, 10(9): 4960.

[39] Miyoshi A, Kato K, Yokoi T, et al. Nano vs. bulk rutile TiO₂: N, F in Z-scheme overall water splitting under visible light. J. Mater. Chem. A, 2020, 8(24): 11996.

[40] M. Landmann, E. Rauls, and W.G. Schmidt, The electronic structure and optical response of rutile, anatase and brookite TiO₂, J. Phys. Condens. Matter, 24(2012), No. 19, art. No. 195503.

[41] C. Di Valentin, G. Pacchioni, and A. Selloni, Origin of the different photoactivity of N-doped anatase and rutile TiO₂, Phys. Rev. B, 70(2004), No. 8, art. No. 085116.

[42] A. Bjelajac, R. Petrović, M. Popović, et al., Doping of TiO₂ nanotubes with nitrogen by annealing in ammonia for visible light activation: Influence of pre- and post-annealing in air, Thin Solid Films, 692(2019), art. No. 137598.

[43] Hwang HM, Oh S, Shim JH, et al. Phase-selective disordered anatase/ordered rutile interface system for visible-light-driven, metal-free CO₂ reduction. ACS Appl. Mater. Interfaces, 2019, 11(39): 35693.

[44] Colón G, Hidalgo MC, Navio JA. Photocatalytic deactivation of commercial TiO₂ samples during simultaneous photoreduction of Cr(VI) and photooxidation of salicylic acid. J. Photochem. Photobiol. A, 2001, 138(1): 79.

[45] Yu H, Liu L, Wang X, Wang P, Yu J, Wang Y. The dependence of photocatalytic activity and photoinduced self-stability of photosensitive AgI nanoparticles. Dalton Trans., 2012, 41(34): 10405.

[46] Chen X, Liu L, Yu PY, Mao SS. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science, 2011, 331(6018): 746.