利用镧系离子掺杂延长{001}/{101}晶面共暴露的TiO2纳米片电荷分离态以增强其光催化产氢性能

doi:10.1016/S1872-2067(18)63182-1

催化学报 ›› 2019, Vol. 40 ›› Issue (3): 413-423.DOI: 10.1016/S1872-2067(18)63182-1

利用镧系离子掺杂延长{001}/{101}晶面共暴露的TiO₂纳米片电荷分离态以增强其光催化产氢性能

朱永安^a,b, 张振翼^a, 吕娜^a, 华瑞年^a,b, 董斌^a

a 辽宁省光敏材料与器件重点实验室, 大连民族大学物理与材料工程学院, 新能源与稀土资源利用国家民委重点实验室, 辽宁大连 116600;
b 大连民族大学生命科学学院, 辽宁大连 116600

收稿日期:2018-08-26 修回日期:2018-10-09 出版日期:2019-03-18 发布日期:2019-02-22
通讯作者: 张振翼, 华瑞年
基金资助:
中国国家自然科学基金（51772041，11474046，61775024）；辽宁省自然基金（20170540190，201602191）；辽宁优秀人才计划（LR2015016，LR2017004）；大连优秀人才计划（2016RQ069）；大连科学与技术基础（2014J11JH134，2015J12JH201）；中央高校基本科研经费（wd01206）.

Prolonging charge-separation states by doping lanthanide-ions into {001}/{101} facets-coexposed TiO₂ nanosheets for enhancing photocatalytic H₂ evolution

Yongan Zhu^a,b, Zhenyi Zhang^a, Na Lu^a, Ruinian Hua^a,b, Bin Dong^a

a Key Laboratory of New Energy and Rare Earth Resource Utilization of State Ethnic Affairs Commission, Key Laboratory of Photosensitive Materials and Devices of Liaoning Province, School of Physics and Materials Engineering, Dalian Nationalities University, Dalian 116600, Liaoning, China;
b College of Life Science, Dalian Nationalities University, Dalian 116600, Liaoning, China

Received:2018-08-26 Revised:2018-10-09 Online:2019-03-18 Published:2019-02-22
Supported by:
This work was supported by the National Natural Science Foundation of China (51772041, 11474046, 61775024), the Natural Science Foundation of Liaoning Province (20170540190, 201602191), the Program for Liaoning Excellent Talents in University (LNET) (LR2015016, LR2017004), the Program for Dalian Excellent Talents (2016RQ069), the Science and the Technique Foundation of Dalian (2014J11JH134, 2015J12JH201), and the Fundamental Research Funds for the Central Universities (wd01206).

摘要/Abstract

摘要：

随着工业化的快速发展，化石燃料等不可再生能源的快速消耗，人类将面临不可预测的能源危机.寻找有效的方法来解决能源短缺问题已成为当今的重要研究课题.氢能是一种可以替代化石燃料的清洁可再生能源.利用半导体光催化分解水制氢技术可以将太阳能转化为氢能.目前，在已开发的半导体光催化材料中，TiO₂因具有无毒、稳定、廉价等优点而备受光催化领域关注.但是，在实际应用方面，TiO₂的光催化效率受限于其低的光子利用率和较高的光生电子-空穴复合率.许多研究表明，TiO₂不同晶面的协同作用有利于光生载流子的迁移分离，并且适量的掺杂能够捕获光生电子，从而抑制其复合.而镧系元素因其特殊4f电子结构受到广泛的关注.采用物理或化学方法将镧系离子引入TiO₂晶格中，可以影响光生电子和空穴的动力学过程，延长光生载流子的分离状态，从而提高光催化活性.
本文通过简单溶剂热法成功合成了镧系离子掺杂{001}/{101}面共暴露的TiO₂纳米片.X-射线粉末衍射（XRD）、X-射线光电子能谱（XPS）和高分辨透射电子显微镜（HRTEM）的表征结果证明了镧系离子选择性掺杂在TiO₂纳米片{101}面上.结合紫外可见吸收光谱、稳态荧光、瞬态荧光衰减曲线、光电流及莫特-肖特基曲线等手段对镧系离子掺杂TiO₂光催化剂进行了表征，结果表明，镧系离子掺杂TiO₂纳米片增强了对光的吸收，同时延长光生载流子的分离状态，阻碍光生电子和空穴的复合.考察其光催化分解水制氢的性能.研究表明，在相同掺杂量（0.5 mol% RE³⁺=Ho³⁺，Er³⁺，Tm³⁺，Yb³⁺，Lu³⁺）的TiO₂纳米片中，Yb³⁺-TiO₂纳米片光催化剂具有优异的产氢活性，在模拟太阳光照射1h后产氢量是纯TiO₂的4.25倍.同时讨论了不同浓度助催化剂Pt作用下的Yb³⁺-TiO₂纳米片产氢效果，当Pt含量量为0.3 wt%时，光解水产氢活性最佳，Pt/Yb³⁺-TiO₂纳米片的产氢量是Yb³⁺-TiO₂的2倍，纯TiO₂的8.5倍.光催化分解水产氢活性的显著提高可以归因于光生电子-空穴对在TiO₂纳米片{001}/{101}面的快速分离，以及镧系离子4f电子轨道对电子的捕获和杂质能级的产生减小了禁带宽度，这不仅延长了光生载流子的分离状态，增加了H⁺还原成H₂的机会，而且还可以拓展可见光的吸收范围.可见，利用镧系离子掺杂TiO₂和共暴露{001}/{101}面协同作用是一种实现TiO₂基光催化活性提高的有效方法之一.镧系离子掺杂的策略对提高半导体纳米材料的光催化活性有显著的影响，可能在光催化、光电化学和太阳能电池领域有更广泛的应用.

关键词: 光催化, 产氢, 镧系离子掺杂, TiO₂, 共暴露面, {001}面, 纳米片

Abstract:

Ultrathin TiO₂ nanosheets with coexposed {001}/{101} facets have attracted considerable attention because of their high photocatalytic activity. However, the charge-separated states in the TiO₂ nanosheets must be extended to further enhance their photocatalytic activity for H₂ evolution. Herein, we present a successful attempt to selectively dope lanthanide ions into the {101} facets of ultrathin TiO₂ 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 TiO₂ 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 H₂ evolution activity of optimal Yb³⁺-doped TiO₂ nanosheets compared to that of their undoped counterparts. Furthermore, when Pt nanoparticles were used as cocatalysts to reduce the H₂ 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 H₂ evolution activity of lanthanide-doped TiO₂ nanosheets with coexposed {001}/{101} facets.

Key words: Photocatalysis, H₂ evolution, Lanthanide ion doping, TiO₂, Coexposed facets, {001} facets, Nanosheets

朱永安, 张振翼, 吕娜, 华瑞年, 董斌. 利用镧系离子掺杂延长{001}/{101}晶面共暴露的TiO₂纳米片电荷分离态以增强其光催化产氢性能[J]. 催化学报, 2019, 40(3): 413-423.

Yongan Zhu, Zhenyi Zhang, Na Lu, Ruinian Hua, Bin Dong. Prolonging charge-separation states by doping lanthanide-ions into {001}/{101} facets-coexposed TiO₂ nanosheets for enhancing photocatalytic H₂ evolution[J]. Chinese Journal of Catalysis, 2019, 40(3): 413-423.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(18)63182-1

https://www.cjcatal.com/CN/Y2019/V40/I3/413

参考文献

[1] H. Ahmad, S. K. Kamarudin, L. J. Minggu, M. Kassim, Renew. Sust. Energy Rev., 2015, 43, 599-610.
[2] E. Pulido Melián, O. Gonzalez Díaz, A. Ortega Méndez, C. R. López, M. Nereida Suárez, J. M. Doña Rodríguez, J. A. Navío, D. Fernan-dez Hevia, J. Perez Peña, Int. J. Hydrogen Energy, 2013, 38, 2144-2155.
[3] K. Z. Qi, B. Cheng, J. G. Yu, W. K. Ho, Chin. J. Catal., 2017, 38, 1936-1955.
[4] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[5] K. Hirano, E. Suzuki, A. Ishikawa, T. Moroi, H. Shiroishi, M. Kaneko, J. Photochem. Photobiol. A, 2000, 136, 157-161.
[6] X. W. Wang, L. C. Yin, G. Liu, Chem. Commun., 2014, 50, 3460-3463.
[7] S. Ma, J. Xie, J. Q. Wen, K. L. He, X. Li, W. Liu, X. C. Zhang, Appl. Surf. Sci., 2017, 391, 580-591.
[8] J. Jiang, S. W. Cao, C. L. Hu, C. H. Chen, Chin. J. Catal., 2017, 38, 1981-1989.
[9] G. Liu, Y. N. Zhao, C. H. Sun, F. Li, G. Q. Lu, H. M. Cheng, Angew. Chem. Int. Ed., 2008, 47, 4516-4520.
[10] H. F. Moafi, A. F. Shojaie, M. A. Zanjanchi, Chem. Eng. J., 2011, 166, 413-419
[11] Y. Xu, Y. A. Li, P. Wang, X. F. Wang, H. G. Yu, Appl. Surf. Sci., 2018, 430, 176-183.
[12] Z. Y. Huang, Z. G. Gao, S. M. Gao, Q. Y. Wang, Z. Y. Wang, B. B. Huang, Y. Dai, Chin. J. Catal., 2017, 38, 821-830.
[13] S. G. Kumar, K. S. R. Koteswara, Appl. Surf. Sci., 2017, 391, 124-148.
[14] D. Dvoranová, V. Brezová, M. Mazúr, M. A. Malati, Appl. Catal. B, 2002, 37, 91-105.
[15] Z. F. Bian, T. Tachikawa, P. Zhang, M. Fujitsuka, T. Majima, J. Am. Chem. Soc., 2014, 1361, 458-465.
[16] Y. H. Chen, Z. H. Zeng, C. Li, W. B. Wang, X. S. Wang, B. W. Zhang, New J. Chem., 2005, 29, 773-776.
[17] J. Li, M. Zhang, Q. Y. Li, J. J. Yang, Appl. Surf. Sci., 2017, 391, 184-193.
[18] M. C. Wu, K. C. Hsiao, Y. H. Chang, S. H. Chan, Appl. Surf. Sci., 2018, 430, 407-414.
[19] J. H Chen, T. Ding, J. M. Cai, Y. T. Wang, M. Q. Wu, H. Zhang, W. Y. Zhao, Y. Tian, X. T. Wang, X. G. Li, Appl. Surf. Sci., 2018, 453, 101-109.
[20] S. H. Wei, S. Ni, X. X. Xu, Chin. J. Catal., 2018, 39, 510-516.
[21] Q. F. Liu, Q. Zhang, B. R. Liu, S. Y. Li, J. J. Ma, Chin. J. Catal., 2018, 395, 42-548.
[22] M. Lazzeri, A. Vittadini, A. Selloni, Phys. Rev. B., 2001, 63, 155409/1-155409/9.
[23] X. Q. Gong, A. Selloni, J. Phys. Chem. B, 2005, 109, 19560-19562.
[24] C. P. Sajan, S.Wageh, A. A. Al-Ghamdi, J. G. Yu, S. W. Cao, Nano Res., 2016, 9, 3-27.
[25] H. G.Yang, G. Liu, S. Z. Qiao, C. H. Sun, Y. G. Jin, S. C. Smith, J. Zou, H. M. Cheng, G. Q. Lu, J. Am. Chem. Soc., 2009, 131, 4078-4083.
[26] Q. J. Xiang, J. G. Yu, Chin. J. Catal., 2011, 32, 525-531.
[27] M. S. Akple, J. X. Low, Z. Y. Qin, S. Wageh, A. A. Al-Ghamidi, J. G. Yu, S. W. Liu, Chin. J. Catal., 2015, 36, 2127-2134.
[28] A. Y. Meng, J. Zhang, D. F. Xu, B. Cheng, J. G. Yu, Appl. Catal. B, 2016, 198, 286-294.
[29] N. Roy, Y. Sohn, D. Pradhan, ACS Nano, 2013, 7, 2532-2540.
[30] Y. R.Yang, K. Ye, D. X. Cao, P. Gao, M. Qiu, L. Liu, P. P. Yang, ACS Appl. Mater. Interfaces., 2018, 10, 19633-19638.
[31] Y. Liu, L. Yu, Z. G. Wei, Z. C. Pan, Y. D. Zou, Y. H. Xie, Chem. J. Chin. U., 2013, 34, 434-440.
[32] M. F. Hou, F. B. Li, R. F. Li, H. F. Wan, G. Y. Zhou, K. C. Xie, J. Rare Earths, 2004, 22, 542-546.
[33] D. W. Hwang, J. S. Lee, W. Li, S. H. Oh, J. Phys. Chem. B, 2003, 107, 4963-4970.
[34] Y. C. Jiao, M. F. Zhu, F. Chen, J. L. Zhang, Chin. J. Catal., 2013, 34, 585-592.
[35] G. H. Chen, Y. Wang, J. H. Zhang, C. L. Wu, H. D. Liang, H. Yang, J. Nanosci. Nanotechnol., 2012, 12, 3799-3805.
[36] L. Matějová, K. Kocí, M. Reli, L. Capek, A. Hospodková, P. Peiker-tová, Z. Matěj, L. Obalova, A. Wach. P. Kustrowski, A. Kotarba, Appl. Catal. B, 2014, 152-153, 172-183.
[37] J. Reszczynska, T. Grzyb, J. W. Sobczak, W. Lisowski, M. Gazda, B. Ohtani, A. Zaleska, Appl. Surf. Sci., 2014, 307, 333-345.
[38] Z. Q. He, L. N. Wen, D. Wang, Y. J. Xue, Q. W. Lu, C. W. Wu, J. M. Chen, S. Song, Energy Fuels, 2014, 28, 3982-3993.
[39] J. Zhang, L. L. Zhang, Y. X. Shi, G. L. Xu, E. P. Zhang, H. B. Wang, Z. Kong, J. H. Xi, Z. G. Ji, Appl. Surf. Sci., 2017, 420, 839-848.
[40] M. A. Butler, J. Appl. Phys., 1977, 48, 1914-1920.
[41] Z. Y. Zhang, B. Dong, M. Y. Zhang, J. D. Huang, F. Lin, C. L. Shao, Int. J. Hydrogen Energy, 2014, 39, 19434-19443.
[42] Y. H. Cao, Q. Y. Li, C. Li, J. L. Li, J. J. Yang, Appl. Catal. B, 2016, 198, 378-388.
[43] J. L. Wu, Z. Y. Zhang, B. K. Liu, Y. R. Fang, L. Wang, B. Dong, Sol. RRL, 2018, 2, 1800039.
[44] S. C. Sun, P. Gao, Y. R. Yang, P. P. Yang, Y. J. Chen, Y. B. Wang, ACS Appl. Mater. Interfaces., 2016, 8, 18126-18131.
[45] X. H. Yang, Z. Li, G. Liu, J. Xing, C. H. Sun, H. G. Yang, C. Z. Li, CrystEngComm, 2011, 13, 1378-1383.
[46] Y. C. Chen, Y. C. Pu, Y. J. Hsu, J. Phys. Chem. C, 2012, 116, 2967-2975.
[47] X. T. Wang, C. H. Liow, A. Bisht, X. F. Liu, T. C. Sum, X. D. Chen, S. Z. Li, Adv. Mater., 2015, 27, 2207-2214.
[48] K. Das, S. K. De, J. Phys. Chem. C, 2009, 113, 3494-3501.
[49] Z. Y. Zhang, Y. Z. Huang, K. C. Liu, L. J. Guo, Q. Yuan, B. Dong, Adv. Mater., 2015, 27, 5906-5914.
[50] Z.Y. Zhang, X. Y. Jiang, B. K. Liu, L. J. Guo, N. Lu, L. Wang, J. D. Huang, K. C. Liu, B. Dong, Adv. Mater., 2018, 30, 1705221.
[51] N. Tian, H. W. Huang, C. Y. Liu, F. Dong, T. R. Zhang, X. Du, S. X. Yu, Y. H. Zhang, J. Mater. Chem. A, 2015, 3, 17120-17129.

利用镧系离子掺杂延长{001}/{101}晶面共暴露的TiO₂纳米片电荷分离态以增强其光催化产氢性能

Prolonging charge-separation states by doping lanthanide-ions into {001}/{101} facets-coexposed TiO₂ nanosheets for enhancing photocatalytic H₂ evolution

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵彬彬, 钟威, 陈峰, 王苹, 别传彪, 余火根. 高晶化g-C₃N₄光催化剂: 合成、结构调控和光催化产氢[J]. 催化学报, 2023, 52(9): 127-143.
[2]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[3]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[4]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[5]	江梓聪, 程蓓, 张留洋, 张振翼, 别传彪. 氧化锌基梯型异质结光催化剂[J]. 催化学报, 2023, 52(9): 32-49.
[6]	刘博文, 蔡家杰, 张建军, 谭海燕, 程蓓, 许景三. MOF/CdS梯型光催化剂同时进行苯甲醇氧化和析氢反应及其机理研究[J]. 催化学报, 2023, 51(8): 204-215.
[7]	宋明明, 宋相海, 刘鑫, 周伟强, 霍鹏伟. ZnIn₂S₄/MOF-808微球结构S型异质结光催化剂的制备及其光还原CO₂性能研究[J]. 催化学报, 2023, 51(8): 180-192.
[8]	邵秀丽, 李可, 李静萍, 程强, 王国宏, 王楷. 揭示NiS@Ta₂O₅纳米纤维中梯型电荷转移路径及光催化CO₂转化性能[J]. 催化学报, 2023, 51(8): 193-203.
[9]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[10]	阎菲, 张由子, 刘思碧, 邹睿卿, Jahan B Ghasemi, 李炫华. 供体-受体型卟啉基金属有机框架实现有效电荷分离高效光催化析氢[J]. 催化学报, 2023, 51(8): 124-134.
[11]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[12]	刘海峰, 黄祥, 陈加藏. 电子态调控促进氢气无损耗纯化中CO的光致富集和氧化[J]. 催化学报, 2023, 51(8): 49-54.
[13]	乔秀清, 李晨, 王紫昭, 侯东芳, 李东升. TiO_2-_x@C/MoO₂肖特基结: 合理设计及高效电荷分离提升光催化性能[J]. 催化学报, 2023, 51(8): 66-79.
[14]	袁鑫, 范海滨, 刘杰, 覃龙州, 王剑, 段秀, 邱江凯, 郭凯. 连续流技术在光氧化还原催化转化的最新进展[J]. 催化学报, 2023, 50(7): 175-194.
[15]	余治晗, 关晨, 岳晓阳, 向全军. 碳环渗入的结晶氮化碳S型同质结及其光催化析氢[J]. 催化学报, 2023, 50(7): 361-371.