具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO<sub>2</sub>微米球及其高效全光谱光催化产氧

引用本文: 赵行, 梁嫜倩, 刘香, 邱鹏源, 崔洪芝, 田健. 具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO₂微米球及其高效全光谱光催化产氧[J]. 催化学报, 2020, 41(2): 333-340. doi: S1872-2067(19)63428-5 shu

Citation: Hang Zhao, Zhangqian Liang, Xiang Liu, Pengyuan Qiu, Hongzhi Cui, Jian Tian. Noble metal-like behavior of plasmonic Bi particles deposited on reduced TiO₂ microspheres for efficient full solar spectrum photocatalytic oxygen evolution[J]. Chinese Journal of Catalysis, 2020, 41(2): 333-340. doi: S1872-2067(19)63428-5 shu

具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO₂微米球及其高效全光谱光催化产氧

山东科技大学材料科学与工程学院, 山东青岛 266590
基金项目:
国家自然科学基金（51872173，51772176）；山东省泰山学者青年专家（tsqn201812068）；山东省省属高校优秀青年人才联合基金（ZR2017JL020）；山东省泰山学者攀登计划（tspd20161006）；山东省重点研发计划（2018GGX102028）.

摘要: 化石燃料的快速消耗导致了严重的环境问题，特别是全球变暖和雾霾.寻找替代传统化石能源的清洁能源是当务之急.光催化水分解技术被认为是将太阳能转化为绿色可再生能源的一种很有前景的方法.作为一种用于光催化的半导体材料，需要满足三个条件：（1）带隙要高于水分解的电压（1.23eV）；（2）带边缘位置应跨越氢还原电位和氧氧化电位；（3）在光催化过程中，光催化材料应具有抗光腐蚀的稳定性.然而，水氧化的半反应是非常困难的，主要是涉及到复杂的四电子氧化过程和O-O键形成的高激活能量.TiO₂是光催化剂中最重要的材料之一，因为它具有成本低，无毒，光稳定性好等优点。但TiO₂的可见光利用率低，载流子复合率高，光催化效率受到严重限制.通过H₂还原可以引入Ti³⁺，还原得到的TiO₂带隙变窄，具有较好的可见光催化产氧活性.
由于贵金属纳米粒子具有表面等离子体共振（SPR）效应，将贵金属（如金或者银）与TiO₂结合是将光催化剂的光吸收边扩展到更长的波长一种有效途径.然而，贵金属的价格限制了它们的商业化，因此需要低成本的金属作为替代品.最近，金属铋（Bi）被证明是贵金属的理想替代品，具有明显的SPR效应，在可见光甚至近红外范围具有优异的光吸收性能.通过光还原，化学还原，水热还原等还原方法，可以方便地获得金属Bi.然而，通过原位沉积的方法将金属Bi纳米粒子直接沉积到半导体表面仍然是一个很大的挑战.
本文采用双金属有机骨架衍生的合成策略，通过调节合成温度，将金属Bi原位沉积到还原TiO₂微球表面（Bi@R-TiO₂）.采用X射线衍射，扫描电镜，透射电镜，X射线光电子能谱，漫反射光谱，光致发光光谱，阻抗，光电流响应等表征技术对制备样品的结构和光学性能进行了研究.结果表明，通过乙二醇可以将Ti⁴⁺还原为Ti³⁺得到还原的TiO_x，Bi³⁺同时也被还原为金属Bi.当退火温度控制在300℃时，相应的Bi@R-TiO₂-300表现出最高的全光谱光催化产氧活性（4728.709μmol h^-1 g^-1），分别是的纯TiO₂和Bi-Ti双金属有机框架的5.9和9.5倍.这可归因于以下三点：（1）金属Bi作为“电子受体”，加速了TiO₂向Bi的载流子转移；（2）负载到还原TiO₂表面的金属Bi具有SPR效应可以增强可见光和近红外光的吸收能力；（3） Ti³⁺的产生进一步减小TiO₂的禁带宽度.

关键词:

English

Noble metal-like behavior of plasmonic Bi particles deposited on reduced TiO₂ microspheres for efficient full solar spectrum photocatalytic oxygen evolution

School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, Shangdong, China
Received Date: 20 April 2019
Revised Date: 16 May 2019
Fund Project:
The authors are thankful for fundings from the National Natural Science Foundation of China (51872173 and 51772176), Taishan Scholarship of Young Scholars (tsqn201812068), Natural Science Foundation of Shandong Province (ZR2017JL020), Taishan Scholarship of Climbing Plan (tspd20161006), and Key Research and Development Program of Shandong Province (2018GGX102028).

Abstract: Herein, novel plasmonic Bi metal in situ deposited in reduced TiO₂ microspheres (Bi@R-TiO₂) are fabricated via a bimetallic MOF-derived synthesized strategy by adjusting the synthesizing temperature. Different characterization techniques, including XRD, SEM, TEM, XPS, DRS, PL, EIS, and photocurrent generation, are performed to investigate the structural and optical properties of the as-prepared samples. The results indicate that the Bi particles are generated inside and outside of reduced TiO₂ microspheres via the reduction of Ti⁴⁺ and Bi³⁺ by ethylene glycol. When the annealing temperature is controlled at 300 ℃, the corresponding Bi@R-TiO₂-300 sample with an appropriate amount of Bi nanoparticles exhibits the highest full solar spectrum photocatalytic oxygen evolution activity (4728.709 μmol h^-1 g^-1), which is 5.9 and 9.5 times higher than that of pure TiO₂ and Bi-Ti bimetal organic frameworks (Bi-Ti-MOFs). Several reasons are suggested for the above results:(1) Bi metal behaves as an "electron acceptor" to accelerate the charge carrier transfer from TiO₂ to Bi; (2) The surface plasmon resonance effect of loaded metallic Bi particles can enhance the visible and NIR light absorption capacity; (3) The generation of Ti³⁺ further narrows the band gap of TiO₂.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO₂微米球及其高效全光谱光催化产氧

English

Noble metal-like behavior of plasmonic Bi particles deposited on reduced TiO₂ microspheres for efficient full solar spectrum photocatalytic oxygen evolution

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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中国化学会秘书处

具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO2微米球及其高效全光谱光催化产氧

English

Noble metal-like behavior of plasmonic Bi particles deposited on reduced TiO2 microspheres for efficient full solar spectrum photocatalytic oxygen evolution

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

具有贵金属行为的等离子Bi纳米颗粒负载到还原TiO₂微米球及其高效全光谱光催化产氧

Noble metal-like behavior of plasmonic Bi particles deposited on reduced TiO₂ microspheres for efficient full solar spectrum photocatalytic oxygen evolution

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs