Mn掺杂的铁电半导体BiFeO3本征光催化氧化水活性的研究

doi:10.1016/S1872-2067(20)63713-5

催化学报 ›› 2021, Vol. 42 ›› Issue (6): 945-952.DOI: 10.1016/S1872-2067(20)63713-5

Mn掺杂的铁电半导体BiFeO₃本征光催化氧化水活性的研究

Jafar Hussain Shah^a^,^b, Anum Shahid Malik^a^,^b, Ahmed Mahmoud Idris^a^,^b, Saadia Rasheed^a^,^b, 韩洪宪^a^,^*(), 李灿^a

^a中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 催化基础国家重点实验室太阳能部, 辽宁大连116023
^b中国科学院大学, 北京100049

收稿日期:2020-07-21 接受日期:2020-09-21 出版日期:2021-06-18 发布日期:2021-01-30
通讯作者: 韩洪宪
基金资助:
国家自然科学基金中韩国际合作项目(2017YFA0204804);科技部重点研发计划项目课题(21761142018);科技部重点研发计划项目课题(21473189)

Intrinsic photocatalytic water oxidation activity of Mn-doped ferroelectric BiFeO₃

Jafar Hussain Shah^a^,^b, Anum Shahid Malik^a^,^b, Ahmed Mahmoud Idris^a^,^b, Saadia Rasheed^a^,^b, Hongxian Han^a^,^*(), Can Li^a

^aState Key Laboratory of Catalysis & Division of Solar Energy, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-07-21 Accepted:2020-09-21 Online:2021-06-18 Published:2021-01-30
Contact: Hongxian Han
About author:^*Tel: +86-411-84379760; Fax: +86-0411-84694447; E-mail: hxhan@dicp.ac.cn
Supported by:
National Key R&D Program of China(2017YFA0204804);National Natural Science Foundation of China(21761142018);National Natural Science Foundation of China(21473189)

摘要/Abstract

摘要：

开发稳定高效的可见光吸收的氧化物半导体光催化剂是太阳能光催化分解水的一个重要研究方向. 最近我们提出(J. Mater. Chem. A, 2020, 8, 6863-6873), 具有室温铁电性质的BiFeO₃(BFO)薄膜体系表现出低光电流密度响应是由于铁电畴壁/界面处的电荷复合, 而该作用在纳米粒子催化剂体系中应该会大大减少. 为了证明这一观点, 我们通过溶胶-凝胶法合成了BFO纳米粒子, 并进行了Mn掺杂获得了Mn-BFO. 光催化水氧化反应表明, 纯BFO具有光催化氧化水的活性, 析氧数率达到70 μmol h^-1 g^-1; 而Mn掺杂量优化(0.05%)后的Mn-BFO在可见光(λ ≥ 420 nm)照射下的析氧活性大大提高, 达到255 μmol h^-1 g^-1. 带隙研究表明, 通过改变Mn的掺杂量, 可以将Mn-BFO的带隙从2.1 eV调整为1.36 eV. DFT计算表明, 表面的Fe物种是水氧化的活性位点, 而不是Mn物种, 因为Mn掺杂后Fe物种的水氧化过电势0.51 V, 是所考察的表面Fe和Mn物种中过电势中最低的. 因此, Mn-BFO光催化水氧化活性的增强可归因于半导体带隙变窄后吸收更多的可见光、降低了的水氧化过电势以及抑制光生电荷复合这几项的协同效应. 这项工作表明, 锰掺杂是提高纳米粒子铁电BFO光催化剂固有光催化水氧化活性的有效策略.
本文采用溶胶-凝胶法成功制备了锰掺杂的BFO样品, 并使用XRD, DRS, Mott-Schottky, XPS和PL等进行了表征. XRD分析结果表明, Mn掺杂后, BFO的(110)和(104)衍射峰向高位衍射角方向位移合并产生一个更宽的峰, 表明Mn的掺杂引起BFO晶格结构变形. DRS光谱分析表明, Mn的掺杂可以拓展可见光的吸收, 从纯BFO的550 nm吸收边(对应于2.1 eV的带隙)扩展到BFO-2的800 nm(对应于1.46 eV的带隙)吸收带边. 这些结果与用DFT计算DOS分析得到的BFO和BFO-2理论带隙值2.05和1.53 eV一致. Mott-Schottky分析表明, BFO和BFO-2是p型半导体, 其平带(Vfb)电势分别为1.7和1.6 V vs NHE, VB位置估计分别为2.0和1.9 V vs NHE, 而CB位置估计分别为-0.11和0.44 V vs NHE. 因此, Mn-BFO在热力学有利于光催化OER但不利于HER. 从Mn-BFO的XPS光谱可以看出除了Bi, Fe和O光谱外, 也可以在641.20和652.7 eV处观察到出Mn 2p_3/2和2p_1/2, 表明Mn是以Mn ³⁺的形式均匀地掺入BFO的晶格中. 对一系列不同含量Mn掺杂的Mn-BFO的光催化OER活性表明研究表明, 0.05% Mn掺杂的BFO-2的光催化OER活性最优, 其析氧活性达到255 μmol h ^-1 g^-1, 这是迄今为止未加载任何助催化剂的BFO的最高固有光催化OER活性值. PL光谱(290 nm激发)显示, 与纯BFO相比, BFO-2的荧光强度弱得多, 表明Mn的掺杂可以抑制光生电荷的复合. DFT计算显示, BFO的表面Fe活性中心的OER过电势为0.93 V; 而对于Mn掺杂的BFO-2, 理论计算得到表面Fe中心和Mn中心的析氧过电位分别为0.51和0.60 V. 由此可见, Mn掺杂不改变BFO的析氧活性中心, 但是可大大降低Fe活性中心OER过电位, 这与锰掺杂的BFO-2表现出比BFO更高光催化氧化水的催化活性实验结果相一致.
综上所述, 在纳米粒子光催化体系中, Mn掺杂的BFO可以促进可见光的吸收, 促进光生电荷有效分离, 降低表面Fe基活性中心氧化水的过电位, 从而显著提高光催化氧化水的活性. Mn的掺杂对于铁电性质的影响及其光催化活性的关系, 有待进一步探索.

关键词: 光催化水氧化, 带隙工程, 铁酸铋, 铁电材料, 阳离子掺杂

Abstract:

The development of stable and efficient visible light-absorbing oxide-based semiconductor photocatalysts is a desirable task for solar water splitting applications. Recently, we proposed that the low photocurrent density in film-based BiFeO₃ (BFO) is due to charge recombination at the interface of the domain walls, which could be largely reduced in particulate photocatalyst systems. To demonstrate this hypothesis, in this work we synthesized particulate BFO and Mn-doped BiFeO₃ (Mn-BFO) by the sol-gel method. Photocatalytic water oxidation tests showed that pure BFO had an intrinsic photocatalytic oxygen evolution reaction (OER) activity of 70 μmol h^-1g^-1, while BFO-2, with an optimum amount of Mn doping (0.05%), showed an OER activity of 255 μmol h ^-1g^-1under visible light (λ ≥ 420 nm) irradiation. The bandgap of Mn-doped BFO could be reduced from 2.1 to 1.36 eV by varying the amount of Mn doping. Density functional theory (DFT) calculations suggested that surface Fe (rather than Mn) species serve as the active sites for water oxidation, because the overpotential for water oxidation on Fe species after Mn doping is 0.51 V, which is the lowest value measured for the different Fe and Mn species examined in this study. The improved photocatalytic water oxidation activity of Mn-BFO is ascribed to the synergistic effect of the bandgap narrowing, which increases the absorption of visible light, reduces the activation energy of water oxidation, and inhibits the recombination of photogenerated charges. This work demonstrates that Mn doping is an effective strategy to enhance the intrinsic photocatalytic water oxidation activity of particulate ferroelectric BFO photocatalysts.

Key words: Photocatalytic water oxidation, Bandgap engineering, Bismuth ferrite, Ferroelectric materials, Cation doping

Jafar Hussain Shah, Anum Shahid Malik, Ahmed Mahmoud Idris, Saadia Rasheed, 韩洪宪, 李灿. Mn掺杂的铁电半导体BiFeO₃本征光催化氧化水活性的研究[J]. 催化学报, 2021, 42(6): 945-952.

Jafar Hussain Shah, Anum Shahid Malik, Ahmed Mahmoud Idris, Saadia Rasheed, Hongxian Han, Can Li. Intrinsic photocatalytic water oxidation activity of Mn-doped ferroelectric BiFeO₃[J]. Chinese Journal of Catalysis, 2021, 42(6): 945-952.

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图/表 8

Fig. 1. (a) XRD patterns of the BFO, BFO-1, BFO-2, BFO-3 and BFO-4; (b) Enlarged patterns of (104) and (110) peaks for BFO, BFO-1, BFO-2, BFO-3 and BFO-4.

Fig. 2. (a) DRS of the BFO, BFO-1, BFO-2, BFO-3 and BFO-4; (b) Tauc’s plot for bandgap calculations of the BFO, BFO-1, BFO-2, BFO-3 and BFO-4. Partial and total DOS calculations using DFT for BFO (c) and BFO-2 (d); (e) Mott-Schottky plots of BFO and BFO-2; (f) Energy band diagram showing the band edges of BFO and BFO-2.

Table 1 Particle sizes and bandgap energies of all samples.

Sample	Particle Size (nm)	Bandgap (eV)
BFO	130	2.1
BFO-1	50	1.52
BFO-2	40	1.46
BFO-3	38	1.4
BFO-4	34	1.36

Fig. 3. HR-SEM images of BFO (a,b), BFO-1 (c), BFO-2 (d), BFO-3 (e), and BFO-3 (f). (Scale bar 1 μm). Insets in (a-f) show the distribution of particle size of all the samples, respectively.

Fig. 4. EDS elemental mapping for BFO-2. (a) Bi; (b) Fe; (c) Mn; (d) O. (scale bar 3 μm). (e) EDS analysis graph indicating the presence of Bi, Fe, O and Mn.

Fig. 5. XPS analysis of BFO-2. (a) Bi 4f; (b) Fe 2p3/2 and 2p1/2; (c) O 1s; (f) Mn 2p.

Fig. 6. (a) Photocatalytic water oxidation activity results of BFO, BFO-1, BFO-2, BFO-3 and BFO-4; (b) Time course of water oxidation activity test for BFO and BFO-2. (Reaction conditions: 0.1 g photocatalyst + 0.04 M Na2S2O8 + 150 mL H2O under visible light irradiation ≥ 420 nm at pH~13.5). PL studies of BFO and BFO-2: (c) PLE spectra for BFO using 290 nm excitation wavelength; (d) PL spectrum for BFO and BFO-2.

Fig. 7. (a) Free energy diagram for BFO; (b) BFO-2 with Mn as the metal active site; (c) BFO-2 with Fe as metal active site.

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Mn掺杂的铁电半导体BiFeO₃本征光催化氧化水活性的研究

Intrinsic photocatalytic water oxidation activity of Mn-doped ferroelectric BiFeO₃

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