可调控且稳定的SrMoO4等离激元共振用于增强的可见光驱动的氮还原

doi:10.1016/S1872-2067(21)63799-3

催化学报 ›› 2021, Vol. 42 ›› Issue (10): 1763-1771.DOI: 10.1016/S1872-2067(21)63799-3

可调控且稳定的SrMoO₄等离激元共振用于增强的可见光驱动的氮还原

李强^a, 赵振环^a(), 白晓霞^a, 童鑫^b, 岳帅^c, 罗晶莹^a, 于欣^d, 王珍妮^a, 王政^a(), 李沛沛^a, 梁燕萍^a, 王志明^b()

^a西安电子科技大学先进材料与纳米科技学院, 应用化学系, 陕西西安710126
^b电子科技大学基础与前沿研究院, 四川成都610054
^c中国科学院国家纳米科学中心, 北京100190
^d济南大学前沿交叉科学研究院, 山东济南250022

收稿日期:2021-01-23 接受日期:2021-03-05 出版日期:2021-10-18 发布日期:2021-06-20
通讯作者: 赵振环,王政,王志明
作者简介:$电子信箱:zhmwang@uestc.edu.cn
*电子信箱:zhzhao@xidian.edu.cn;
基金资助:
国家重点研发计划政府间国际科技创新合作/港澳台科技创新合作重点专项(2019YFE0121600);陕西省自然科学基金(2019JM-298);西安电子科技大学研究生创新基金(YJS2113)

Tunable and stable localized surface plasmon resonance in SrMoO₄ for enhanced visible light driven nitrogen reduction

Qiang Li^a, Zhenhuan Zhao^a(), Xiaoxia Bai^a, Xin Tong^b, Shuai Yue^c, Jingying Luo^a, Xin Yu^d, Zhenni Wang^a, Zheng Wang^a(), Peipei Li^a, Yanping Liang^a, Zhiming Wang^b()

^aDepartment of Applied Chemistry, School of Advanced Materials and Nanotechnology, Xidian University, Xi’an 710126, Shaanxi, China
^bInstitute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
^cNational Center for Nanoscience and Technology, Chinese Academy of Sciences, Beijing 100190, China
^dInstitute for Advanced Interdisciplinary Research, University of Jinan, Jinan 250022, Shandong, China

Received:2021-01-23 Accepted:2021-03-05 Online:2021-10-18 Published:2021-06-20
Contact: Zhenhuan Zhao,Zheng Wang,Zhiming Wang
About author:$E-mail: zhmwang@uestc.edu.cn
Supported by:
National Key Research and Development Program of China(2019YFE0121600);Natural Science Foundation of Shaanxi province(2019JM-298);Innovation Fund of Xidian University for Graduate Students(YJS2113)

摘要/Abstract

摘要：

光催化固氮是最具潜力的人工光合过程之一, 也是有望取代工业Haber-Bosch方法实现氨的绿色合成的清洁能源技术之一. 由于氮气分子还原为氨需要较高的还原电位, 导致大部分常规的半导体材料的导带能级不能满足固氮反应的热力学要求. 同时, 固氮光催化剂普遍存在光响应波段窄、表面催化活性低、太阳光向氨的转化效率低等问题. 缺陷工程是目前制备高效固氮光催化剂的最有效的途径之一. 在催化剂中引入缺陷可以带来两个方面的好处: (1)促进氮气分子在缺陷位点上的化学吸附和活化, 从而降低反应能垒; (2)拓宽催化剂的太阳光响应波段, 提高对太阳光的利用效率. 等离激元效应来自于自由载流子的集体振荡, 广泛存在于金属纳米结构中. 尽管金属等离激元纳米材料在光催化中也有广泛的应用, 可以通过等离激元增强的光吸收和散射、热载流子传输以及等离激元共振能量传递等机理提高太阳能转化效率, 但其能量转化效率仍有限, 多用于弥补半导体材料的弱点. 研究发现, 一些半导体纳米材料在可见光和近红外光范围表现出优异的等离激元共振吸收. 相比等离激元金属纳米材料, 这些半导体的等离激元共振效应的调控手段更加丰富. 等离激元半导体材料普遍具有较高的缺陷浓度、非常宽的光响应波段, 因而是理想的固氮光催化剂.
本文利用具有还原性的气氛处理溶剂热法制备的SrMoO₄, 通过引入高浓度的氧空位, 实现了可调控的稳定的等离激元共振吸收. 制备的SrMoO₄在可见光和近红外光范围具有强的等离激元吸收, 其共振吸收峰的中心位置可从520调到815 nm, 显著拓宽了SrMoO₄的光响应波段, 而样品的本征吸收边仍然位于310 nm. 研究发现, 氢气还原没有改变Sr的氧化态, 而是将Mo⁶⁺还原成Mo⁵⁺. 紫外光电子能谱分析结果表明, 高温氢气处理没有改变SrMoO₄样品的导带和价带能级. 电子顺磁共振研究结果表明, 氢气处理在SrMoO₄中形成了大量的氧空位. Mott-Schottky测试结果发现, 氢气处理后的样品的载流子浓度高达~2.0 × 10²⁰ cm^‒3. 具有等离激元效应的SrMoO₄表现出优异的可见光固氮性能, 相比不具有等离激元效应的SrMoO₄, 在入射光波长大于420 nm的可见光照射下, 在氢气气氛中处理10 min, 3, 6和8 h的SrMoO₄样品的氨的产率分别为41.2, 36.3, 24.5和20.8 μg g_cat^‒1 h^‒1. 其增强光催化活性主要来源于更宽的太阳光吸收波段、等离激元激发产生的热载流子和丰富的缺陷活性位点. 一方面, SrMoO₄具有较高的导带能级, 本征激发形成的导带电子能在热力学上将氮气分子还原为氨; 另一方面, 等离激元激发产生的热载流子具有较高的能量, 能够越过固液界面的肖特基能垒, 将吸附在催化剂表面缺陷处的氮气分子还原为氨. 但是, 尽管缺陷在光催化固氮中展现出多方面的优点, 其在半导体中的浓度仍需进一步的优化.

关键词: SrMoO₄, 等离激元半导体, 局域表面等离激元共振, 氧空位, 光催化氮还原

Abstract:

Photocatalytic nitrogen reduction for the green synthesis of ammonia at ambient conditions has been slowed by the narrow light harvesting range, low activity and high charge recombination of photocatalysts. Plasmonic semiconducting nanomaterials are becoming the promising candidates for nitrogen photofixation because of the broad absorption spectrum, rich defects and hot carriers. In the present study, plasmonic SrMoO₄ is developed by regulating the concentration of oxygen vacancies that are accompanied in the reduction process from Mo⁶⁺ to Mo⁵⁺. The stable and tunable localized surface plasmon resonance (LSPR) absorption in visible and near infrared light range makes the wide bandgap SrMoO₄ utilize the solar energy more efficiently. Energetic electrons from both the intrinsic band excitation and the LSPR excitation enable the reduction of dinitrogen molecules thermodynamically in ultrapure water to ammonia. This work provides a unique clue to design efficient photocatalysts for nitrogen fixation.

Key words: SrMoO₄, Plasmonic semiconductor, Localized surface plasmon resonance, Oxygen vacancy, Photocatalytic nitrogen reduction

李强, 赵振环, 白晓霞, 童鑫, 岳帅, 罗晶莹, 于欣, 王珍妮, 王政, 李沛沛, 梁燕萍, 王志明. 可调控且稳定的SrMoO₄等离激元共振用于增强的可见光驱动的氮还原[J]. 催化学报, 2021, 42(10): 1763-1771.

Qiang Li, Zhenhuan Zhao, Xiaoxia Bai, Xin Tong, Shuai Yue, Jingying Luo, Xin Yu, Zhenni Wang, Zheng Wang, Peipei Li, Yanping Liang, Zhiming Wang. Tunable and stable localized surface plasmon resonance in SrMoO₄ for enhanced visible light driven nitrogen reduction[J]. Chinese Journal of Catalysis, 2021, 42(10): 1763-1771.

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图/表 5

Fig. 1. XRD patterns (a) and Raman spectra (b) of SrMoO4, SMO-10 min, SMO-3 h, SMO-6 h and SMO-8 h; (c) HRTEM image of SMO-10 min, the insert in (c) is the FFT pattern; (d) EDX elemental mapping images of SMO-10 min showing the homogeneous distribution of Sr, Mo, and O.

Fig. 2. (a) The UV-vis spectra of the SrMoO4 samples annealed in H2/Ar for different time, the inset shows the photographs of SrMoO4 (white powder) and SMO-10 min (black powder); (b) The UV-vis spectra of the SMO-10 min sample stored for different time; (c) The ammonia production rate of the samples under full spectrum and visible light irradiation (λ > 420 nm); (d) The AQE of photocatalytic nitrogen reduction for ammonia over SrMoO4 and SMO-10 min under monochromatic light irradiation; (e) The ammonia production rate of the SMO-10 min sample and the sample exposed to air for four months under full spectrum irradiation; (f) The ammonia production rate of the SMO-10 min sample with five repeated cycles of photocatalytic experiments.

Fig. 3. Chemical states characterization. XPS core level spectra for Mo 3d (a), O 1s (b), and Sr 3d (c) for the pristine SrMoO4 and the SMO-10 min sample; (d) EPR spectra at 77 K of the pristine SrMoO4 and the annealed samples.

Fig. 4. (a) Ultraviolet photoelectron spectroscopy (UPS) of SrMoO4 and SMO-10 min; (b) Mott-Schottky plots of the pristine SrMoO4, the annealed samples in hydrogen (SMO-10 min, SMO-3 h, SMO-6 h, and SMO-8 h); (c) The transient photocurrent density of the pristine SrMoO4 and the annealed samples under the full spectrum and visible light (λ > 420 nm) irradiation, respectively; (d) The transient photocurrent density of the pristine SrMoO4 and the SMO-10 min sample under irradiation of monochromatic light (450, 500, 600, and 650 nm).

Fig. 5. (a) Ultrafast TA spectra of SMO-10 min after 360 nm excitation; (b) TA kinetics curves of the SMO-10 min sample with the probe wavelength of 505 nm; (c) The schematic illustration of the crystalline structure of the oxygen vacancy rich SrMoO4 and the proposed nitrogen fixation mechanism by LSPR excitation.

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可调控且稳定的SrMoO₄等离激元共振用于增强的可见光驱动的氮还原

Tunable and stable localized surface plasmon resonance in SrMoO₄ for enhanced visible light driven nitrogen reduction

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