Zn<sup>2+</sup>促进TiO<sub>2</sub>煅烧过程晶型转变的掺杂机制研究

摘要硫酸法钛白生产工艺中,高温煅烧是生成稳定晶型的重要阶段。锌盐处理剂的加入可以降低锐钛晶型向金红石转变的温度,然而其促进作用的内在机理目前尚不明确。以钛白工艺中间物料二洗偏钛酸为原料,硫酸锌为盐处理剂,在马弗炉里高温煅烧至600~900 ℃。利用XRD、HRTEM和XPS等分析手段研究了Zn²⁺在煅烧过程中对TiO₂晶型转变的影响和掺杂机制。结果表明,不同的Zn²⁺初始浓度以及煅烧温度对Zn²⁺在TiO₂晶型转变的作用机制和Zn²⁺的存在状态具有显著影响。当Zn²⁺质量分数小于1%时,Zn²⁺以取代模式掺入TiO₂晶格中,置换Ti⁴⁺,使晶胞参数变大并形成氧空位;且随着Zn²⁺浓度的增加,过量的Zn²⁺在TiO₂表面形成新物种ZnTiO₃。取代掺杂和ZnTiO₃通过不同的作用机理都可以降低相变温度,促进锐钛向金红石的相转变。

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	王伟
	路瑞芳
	王晨光
	党乐平
	郝琳
	卫宏远

关键词：晶型转变 Zn²⁺离子取代掺杂 ZnTiO₃

Abstract： High temperature calcination is an important stage in the production of titanium dioxide by sulfuric acid method. Zinc salt treatment can reduce the temperature of polymorphic transition. But the internal mechanism is still unclear. Using metatitanic acid and zinc sulfate as raw materials and salt treatment agents, the calcination is performed in a muffle furnace at 600 to 900 ℃. The effect of Zn²⁺ on polymorphic transition and doping mechanism were discussed by XRD, HRTEM and XPS. The results show that the concentration of Zn²⁺ and the calcination temperature significantly affect the doping mechanism and existence state of Zn²⁺ in the polymorphic transition. When the concentration of Zn²⁺ is less than 1%, Zn²⁺ is incorporated into the TiO₂ lattice in substitution mode, replacing Ti⁴⁺, increasing the cell parameters and forming oxygen vacancies. And with the increase of Zn²⁺ concentration, excessive Zn²⁺ forms ZnTiO₃ on the surface of TiO₂. Substitutional doping and ZnTiO₃ can reduce the phase transition temperature and promote polymorphic transition from anatase to rutile through different doping mechanisms.

Keywords： polymorphic transition Zn²⁺ ions substitution doping ZnTiO₃

Received 2022-02-17;

Fund:国家重点研发计划(2018YFC0808600);国家自然科学基金项目(22108019)。

Corresponding Authors: 郝琳,副研究员,E-mail:haolin@tju.edu.cn。 Email: haolin@tju.edu.cn

About author: 王伟(1995-),女,硕士研究生,现从事偏钛酸盐处理和煅烧方面的研究。

引用本文:

王伟, 路瑞芳, 王晨光, 党乐平, 郝琳, 卫宏远.Zn²⁺促进TiO₂煅烧过程晶型转变的掺杂机制研究[J]. 化学工业与工程, 2024,41(4): 55-64

WANG Wei, LU Ruifang, WANG Chenguang, DANG Leping, HAO Lin, WEI Hongyuan.The doping mechanism of Zn²⁺ promoting the polymorphic transition of TiO₂ during calcination[J]. Chemcial Industry and Engineering, 2024,41(4): 55-64

[1] 唐振宁. 钛白粉的生产与环境治理[M]. 北京: 化学工业出版社, 2000 TANG Zhenning. Production and environmental treatment of titanium dioxide[M]. Beijing: Chemical Industry Press, 2000(in Chinese)
[2] JOSE S, JOSHY D, NARENDRANATH S B, et al. Recent advances in infrared reflective inorganic pigments[J]. Solar Energy Materials and Solar Cells, 2019, 194: 7-27
[3] VAN DRIEL B A, KOOYMAN P J, VAN DEN BERG K J, et al. A quick assessment of the photocatalytic activity of TiO₂ pigments—From lab to conservation studio![J]. Microchemical Journal, 2016, 126: 162-171
[4] GIRALDI T R, ALMEIDA D J, BAGGIO C M, et al. Anatase-to-rutile transition in Co-doped TiO₂ pigments[J]. Journal of Sol-Gel Science and Technology, 2017, 83(1): 115-123
[5] 吴胜财, 罗弦, 龙永富, 等. 二氧化硅掺杂对二氧化钛晶型转变机理的影响[J]. 材料工程, 2020, 48(11): 99-107 WU Shengcai, LUO Xian, LONG Yongfu, et al. Effects of silicon doping on phase transformation mechanism of titanium dioxide[J]. Journal of Materials Engineering, 2020, 48(11): 99-107(in Chinese)
[6] 姜贵民, 严继康, 杨钢, 等. TiO₂晶型转变(A→R)的影响因素[J]. 材料导报, 2016, 30(19): 95-100 JIANG Guimin, YAN Jikang, YANG Gang, et al. Influencing factors of crystal phase transformation(A→R) of TiO₂[J]. Materials Review, 2016, 30(19): 95-100(in Chinese)
[7] SONG Y, WANG H. Using polyvinyl alcohol to improve the deacidification performance of titanium white waste acid: Pilot tests[J]. Waste Management, 2019, 87: 13-20
[8] SONG M, LU Z, LI D. Phase transformations among TiO₂ polymorphs[J]. Nanoscale, 2020, 12(45): 23183-23190
[9] XU J, HUANG J, ZHANG S, et al. Understanding the surface reduction of nano rutile and anatase: Selective breaking of Ti—O bonds[J]. Materials Research Bulletin, 2020, 121: 110617
[10] GESENHUES U, RENTSCHLER T. Crystal growth and defect structure of Al³⁺-doped rutile[J]. Journal of Solid State Chemistry, 1999, 143(2): 210-218
[11] HO D Q, KIM S. Role of aluminum doping in anatase-to-rutile transformation from thermodynamic view point[J]. Physica Status Solidi Rapid Research Letters, 2018, 12(12): 1800234
[12] 王书亮, 刘洪学, 曾人杰. Mg²⁺掺杂对TiO₂粉末晶型转变的影响与机理[J]. 厦门大学学报(自然科学版), 2005, 44(6): 806-809 WANG Shuliang, LIU Hongxue, ZENG Renjie. Effects of Mg²⁺ doping on polymorphic transition of TiO₂ powders and mechanism[J]. Journal of Xiamen University (Natural Science), 2005, 44(6): 806-809(in Chinese)
[13] 马维平. 偏钛酸煅烧过程中氢氧化钾作用研究[J]. 钢铁钒钛, 2019, 40(4): 35-38 MA Weiping. Effect of potassium hydroxide on calcination of metatitanic acid[J]. Iron Steel Vanadium Titanium, 2019, 40(4): 35-38(in Chinese)
[14] 马维平, 王斌, 吴健春. 磷酸对制备金红石型钛白粉的影响[J]. 钢铁钒钛, 2019, 40(3): 30-33 MA Weiping, WANG Bin, WU Jianchun. Effect of phosphoric acid on preparation of rutile titanium dioxide[J]. Iron Steel Vanadium Titanium, 2019, 40(3): 30-33(in Chinese)
[15] 吴健春, 路瑞芳, 马维平. 锌系与铝系盐处理钛白差异分析[J]. 钢铁钒钛, 2020, 41(2): 29-32 WU Jianchun, LU Ruifang, MA Weiping. Analysis of difference between zinc salt and aluminum salt treated titanium dioxide[J]. Iron Steel Vanadium Titanium, 2020, 41(2): 29-32(in Chinese)
[16] TIAN C. Orthogonal interactions and synergistic effects of salt treatment and calcination on rutile titanium dioxide pigment preparation[J]. Materials Chemistry and Physics, 2020, 249: 123125
[17] 容尔益, 朱家文, 陈葵, 等. 煅烧晶种和磷、镁对二氧化钛晶体的影响[J]. 无机盐工业, 2016, 48(7): 21-24 RONG Eryi, ZHU Jiawen, CHEN Kui, et al. Effects of calcining seed, phosphate, and magnesium on titanium dioxide crystal[J]. Inorganic Chemicals Industry, 2016, 48(7): 21-24(in Chinese)
[18] WANG J, YU Y, LI S, et al. Doping behavior of Zr⁴⁺ ions in Zr⁴⁺-doped TiO₂ nanoparticles[J]. The Journal of Physical Chemistry C, 2013, 117(51): 27120-27126
[19] YU Y, WANG J, LI W, et al. Doping mechanism of Zn²⁺ ions in Zn-doped TiO₂ prepared by a sol-gel method[J]. CrystEngComm, 2015, 17(27): 5074-5080
[20] YANG Y, YU Y, WANG J, et al. Doping and transformation mechanisms of Fe³⁺ ions in Fe-doped TiO₂[J]. CrystEngComm, 2017, 19(7): 1100-1105
[21] ZHAO D, YU Y, CAO C, et al. The existing states of doped B³⁺ ions on the B doped TiO₂[J]. Applied Surface Science, 2015, 345: 67-71
[22] DING Y, ZHANG X, CHEN L, et al. Oxygen vacancies enabled enhancement of catalytic property of Al reduced anatase TiO₂ in the decomposition of high concentration ozone[J]. Journal of Solid State Chemistry France, 2017, 250: 121-127
[23] ABDULLAH S A, SAHDAN M Z, NAYAN N, et al. Neutron beam interaction with rutile TiO₂ single crystal (111): Raman and XPS study on Ti³⁺-oxygen vacancy formation[J]. Materials Letters, 2020, 263: 127143
[24] ZHU J, MU W, SU L, et al. Al-doped TiO₂ mesoporous material supported Pd with enhanced catalytic activity for complete oxidation of ethanol[J]. Journal of Solid State Chemistry, 2017, 248: 142-149
[25] MEHTA M, KODAN N, KUMAR S, et al. Hydrogen treated anatase TiO₂: A new experimental approach and further insights from theory[J]. Journal of Materials Chemistry A, 2016, 4(7): 2670-2681