具有光控氧空缺的钼掺杂Bi5O7Br纳米片用于光催化氮气合成氨

doi:10.1016/S1872-2067(21)63837-8

催化学报 ›› 2021, Vol. 42 ›› Issue (11): 2020-2026.DOI: 10.1016/S1872-2067(21)63837-8

具有光控氧空缺的钼掺杂Bi₅O₇Br纳米片用于光催化氮气合成氨

陈雪, 祁明雨, 李月华, 唐紫蓉, 徐艺军^*()

福州大学化学学院, 能源与环境光催化国家重点实验室, 福建福州350116

收稿日期:2021-03-28 修回日期:2021-03-28 接受日期:2021-04-28 出版日期:2021-11-18 发布日期:2021-05-18
通讯作者: 徐艺军
基金资助:
国家自然科学基金(21872029);国家自然科学基金(22072023);国家自然科学基金(U1463204);国家万人计划科技创新领军人才(00387072);福建省首批青年拔尖创新人才;福建省高校领军人才;闽江学者特聘教授奖励计划;福建省自然科学基金(2017J07002);福建省自然科学基金(2019J0106)

Enhanced ambient ammonia photosynthesis by Mo-doped Bi₅O₇Br nanosheets with light-switchable oxygen vacancies

Xue Chen, Ming-Yu Qi, Yue-Hua Li, Zi-Rong Tang, Yi-Jun Xu^*()

College of Chemistry, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350116, Fujian, China

Received:2021-03-28 Revised:2021-03-28 Accepted:2021-04-28 Online:2021-11-18 Published:2021-05-18
Contact: Yi-Jun Xu
About author:^*Tel/Fax: +86-591-22865836; E-mail: yjxu@fzu.edu.cn
Supported by:
Natural Science Foundation of China(21872029);Natural Science Foundation of China(22072023);Natural Science Foundation of China(U1463204);Program for National Science and Technology Innovation Leading Talents(00387072);1st Program of Fujian Province for Top Creative Young Talents;Program for Leading Talents of Fujian Universities;Award Program for Minjiang Scholar Professorship;Natural Science Foundation of Fujian Province(2017J07002);Natural Science Foundation of Fujian Province(2019J0106)

摘要/Abstract

摘要：

氨(NH₃)作为合成燃料、化肥和潜在能源载体的重要前体, 是现代化学工业中最重要的化学品之一. 工业中主要通过高能耗的Haber-Bosch工艺在高温高压下将氮气和氢气转化为NH₃, 而原料氢气由天然气蒸汽获得, 因而不仅消耗大量能源, 而且导致温室气体二氧化碳的大量排放, 对环境造成危害. 光催化固氮以光能为驱动力, 以水为质子源, 为合成NH₃提供了一种温和、绿色和可持续的方法. 然而, 传统固氮催化剂具有与N₂结合弱、成键难以及电子转移效率低的缺点. 为了克服上述问题, 在催化剂中引入氧空缺和过渡金属作为给电子中心和活性位点的策略被广泛研究.
本文以半导体Bi₅O₇Br纳米片作为研究对象, 通过在水热合成过程中添加Na₂MoO₄前驱盐在Bi₅O₇Br中掺杂钼元素, 合成了不同摩尔含量的钼掺杂Bi₅O₇Br (Mo-Bi₅O₇Br)纳米片, 并将其应用于光催化N₂还原反应, 发现Mo-Bi₅O₇Br的光催化固氮性能显著优于空白Bi₅O₇Br的催化性能. 扫描电镜、透射电镜、能量色散X射线元素映射以及X射线光电子能谱的结果表明, 掺杂过程不会影响Bi₅O₇Br纳米片的晶相和形貌, 掺杂后钼元素均匀地分布在Bi₅O₇Br纳米片晶格中. 采用紫外可见漫反射光谱、电子自旋共振光谱、氮气程序升温脱附谱以及光电化学测试等方法研究了Mo-Bi₅O₇Br相较于空白Bi₅O₇Br纳米片在光催化N₂还原反应中催化性能提升的原因. UV-vis DRS结果表明, 钼掺杂对Bi₅O₇Br可见光吸收能力具有增强作用. 以催化NH₃产率最高的Mo-Bi₅O₇Br-1(Mo摩尔百分含量为1%)为研究样本, EPR结果表明, 在黑暗条件下, 只有Mo-Bi₅O₇Br-1样品可以检测到明显的表面氧空位(OVs)信号; 在光照条件下, Bi₅O₇Br和Mo-Bi₅O₇Br-1两种样品都出现OVs的信号峰, 但同等光照时间下的Mo-Bi₅O₇Br-1具有更高的信号强度. 此外, OVs信号会随着光照时间的延长逐渐增强; 当移除光源后, 信号强度逐渐降低. 这表明Mo-Bi₅O₇Br-1在光照下会产生更高浓度的表面光控OVs. N₂-TPD结果表明, 光控OVs作为活性位点促进催化剂对N₂的吸附. 关闭光源后, OVs被环境中的水或氧气中的氧原子重新填充, 避免了OVs易被氧化而导致反应失活的缺点, 有助于保持Mo-Bi₅O₇Br-1催化N₂还原反应的活性和稳定性. 光电化学表征结果表明, Mo-Bi₅O₇Br-1中的光生载流子的分离和迁移效率明显提高. 以上结果表明, 掺杂过渡金属钼有助于Bi₅O₇Br纳米片表面光控OVs的生成, 光控OVs作为活性位点提升了Bi₅O₇Br吸附和活化N₂的能力, 钼掺杂和光控OVs协同提高Bi₅O₇Br内部光生载流子的分离迁移效率, 增强Bi₅O₇Br光催化固氮合成氨的反应性能.

关键词: 光催化剂, 钼掺杂, Bi₅O₇Br纳米片, 光控氧空缺, 光催化固氮

Abstract:

The fabrication of efficient catalysts to reduce nitrogen (N₂) to ammonia (NH₃) is a significant challenge for artificial N₂ fixation under mild conditions. In this work, we demonstrated that the simultaneous introduction of oxygen vacancies (OVs) and Mo dopants into Bi₅O₇Br nanosheets can significantly increase the activity for photocatalytic N₂ fixation. The 1 mol% Mo-doped Bi₅O₇Br nanosheets exhibited an optimal NH₃ generation rate of 122.9 μmol g^-1 h^-1 and durable stability, which is attributed to their optimized conduction band position, suitable absorption edge, large number of light-switchable OVs, and improved charge carrier separation. This work provides a promising approach to design photocatalysts with light-switchable OVs for N₂ reduction to NH₃ under mild conditions, highlighting the wide application scope of nanostructured BiOBr-based photocatalysts as effective N₂ fixation systems.

Key words: Photocatalyst, Mo-doped, Bi₅O₇Br nanosheets, Light-switchable oxygen vacancies, N₂ photoreduction to NH₃

陈雪, 祁明雨, 李月华, 唐紫蓉, 徐艺军. 具有光控氧空缺的钼掺杂Bi₅O₇Br纳米片用于光催化氮气合成氨[J]. 催化学报, 2021, 42(11): 2020-2026.

Xue Chen, Ming-Yu Qi, Yue-Hua Li, Zi-Rong Tang, Yi-Jun Xu. Enhanced ambient ammonia photosynthesis by Mo-doped Bi₅O₇Br nanosheets with light-switchable oxygen vacancies[J]. Chinese Journal of Catalysis, 2021, 42(11): 2020-2026.

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图/表 4

Fig. 1. (a) Schematic diagram of the fabrication of Mo-Bi5O7Br; (b) SEM, (c) TEM, and (d) HRTEM images of Mo-Bi5O7Br-1 nanosheets; (e) HAADF-STEM image with corresponding elemental mappings and (f) EDX spectrum of Mo-Bi5O7Br-1 nanosheets.

Fig. 2. (a) UV-vis absorption spectra and corresponding Tauc plots (inset) of the as-prepared blank Bi5O7Br and Mo-Bi5O7Br-1 nanosheets; (b) Valence band XPS profile of Mo-Bi5O7Br-1 nanosheets. The inset shows the electronic energy level diagram; XPS profiles of Mo 3d (c), Bi 4f (d), Br 3d (e), and O 1s (f) levels of blank Bi5O7Br and Mo-Bi5O7Br-1 nanosheets.

Fig. 3. (a) EPR spectra of blank Bi5O7Br and Mo-Bi5O7Br-1 nanosheets before and after irradiation at 77 K; (b) Time-dependent EPR spectra of Mo-Bi5O7Br-1 nanosheets at 77 K; (c) Photocatalytic NH3 production rate over Mo-Bi5O7Br-x samples; (d) Photocatalytic cycling tests for Mo-Bi5O7Br-1 nanosheets.

Fig. 4. (a) N2 TPD profiles of blank Bi5O7Br and Mo-Bi5O7Br-1 nanosheets; (b) Cyclic voltammetry and (c) EIS plots of blank Bi5O7Br and Mo-Bi5O7Br-1 nanosheets; (d) Steady-state PL emission spectra of blank Bi5O7Br and Mo-Bi5O7Br-1 nanosheets with an excitation wavelength of 375 nm; (e) Schematic illustration of ph

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具有光控氧空缺的钼掺杂Bi₅O₇Br纳米片用于光催化氮气合成氨

Enhanced ambient ammonia photosynthesis by Mo-doped Bi₅O₇Br nanosheets with light-switchable oxygen vacancies

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