Cr2O3-Rh/Ga2O3光催化分解水的时间分辨红外光谱研究

doi:10.1016/S1872-2067(20)63688-9

催化学报 ›› 2021, Vol. 42 ›› Issue (5): 808-816.DOI: 10.1016/S1872-2067(20)63688-9

Cr₂O₃-Rh/Ga₂O₃光催化分解水的时间分辨红外光谱研究

丁倩^a^,^b, 陈涛^a^,^c, 政^a, 冯兆池^a, 王秀丽^a^,^*()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连116023
^b中国科学院大学, 北京100049
^c大连海洋大学, 海洋科技与环境学院, 辽宁大连116023

收稿日期:2020-05-01 接受日期:2020-05-01 出版日期:2021-05-18 发布日期:2021-01-29
通讯作者: 王秀丽
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家自然科学基金(21633015);国家自然科学基金(21872143);国家自然科学基金(21761142018);国家重点基础研究发展计划(973)项目(2014CB239400);辽宁省自然科学基金指导项目(201602097)

Time-resolved infrared spectroscopic investigation of Ga₂O₃ photocatalysts loaded with Cr₂O₃-Rh cocatalysts for photocatalytic water splitting

Qian Ding^a^,^b, Tao Chen^a^,^c, Zheng Li^a, Zhaochi Feng^a, Xiuli Wang^a^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cSchool of Marine Science and Environment Engineering, Dalian Ocean University, Dalian 116023, Liaoning, China

Received:2020-05-01 Accepted:2020-05-01 Online:2021-05-18 Published:2021-01-29
Contact: Xiuli Wang
About author:^* Tel: +86-411-84379027; Fax: +86-411-84694447; E-mail: xiuliwang@dicp.ac.cn
First author contact:
^† These authors equally contributed to the work.
Supported by:
National Natural Science Foundation of China(21633015);National Natural Science Foundation of China(21872143);National Natural Science Foundation of China(21761142018);973 National Basic Research Program of the Ministry of Science and Technology of China(2014CB239400);Guidance Program of Natural Science Foundation of Liaoning Province(201602097)

摘要/Abstract

摘要：

研究半导体光催化分解水反应中光生电荷动力学和助催化剂的作用对理解其反应机理至关重要. 一般来说,助催化剂不仅可以促进半导体/助催化剂界面处的光生电荷高效分离, 而且可以作为反应活性中心来直接催化表面氧化或还原反应. Cr₂O₃-Rh是一种重要的产氢助催化剂, 通过担载Cr₂O₃-Rh助催化剂来提高光催化分解水的策略被应用到许多光催化分解水体系中. 已有研究发现, Rh/Cr₂O₃核壳结构助催化剂的产氢活性位仍然在Rh纳米粒子表面, 而Cr₂O₃壳层阻止O₂到达Rh核从而抑制生成水的逆反应. 此外, 在(Rh_2-_yCr_yO₃)/(Ga_1-_xZn_x)(N_1-_xO_x)光催化剂中, CrO_x促进了从半导体光催化剂到活性位RhO_x的电子转移. 然而, Cr₂O₃-Rh助催化剂的作用本质(包括Cr₂O₃所起的作用)仍然是一个悬而未决的问题, 特别是Cr₂O₃-Rh助催化剂的担载对半导体催化剂中光生电荷动力学影响的研究还非常少.

本文采用原位光沉积的方法制备了Ga₂O₃、Rh/Ga₂O₃、Cr₂O₃/Ga₂O₃和Cr₂O₃-Rh/Ga₂O₃等一系列光催化剂; 采用紫外可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、CO吸附红外光谱和高分辨透射电镜(HRTEM)等表征手段研究了Cr₂O₃-Rh助催化剂的结构和形貌; 采用时间分辨红外光谱(TR-MIR)研究了这些光催化剂在真空或者反应物(水汽或者氧气)存在条件下的光生电子的衰减动力学过程.

UV-Vis DRS结果表明, Ga₂O₃的带隙基本上不受Rh或者Cr₂O₃-Rh助催化剂担载的影响. XPS结果表明, Cr₂O₃和Rh成功地担载在Ga₂O₃表面上. CO吸附红外和HRTEM结果表明, 在Cr₂O₃-Rh助催化剂中Rh纳米粒子被Cr₂O₃部分覆盖. 光生电子的衰减动力学研究结果显示, Ga₂O₃中光生电子很难直接参与质子还原反应, 只有被Rh捕获后的电子才能高效地参与产氢反应; 在水汽存在条件下Ga₂O₃、Rh/Ga₂O₃和Cr₂O₃-Rh/Ga₂O₃中光生电子的衰减速率随着它们光催化产氢活性的升高而增加; 与Cr₂O₃/Ga₂O₃和Rh/Ga₂O₃相比, Cr₂O₃-Rh/Ga₂O₃中光生电子的初始吸光度和寿命均减小, 说明Cr₂O₃对Rh/Ga₂O₃的结构修饰促进了电子从Ga₂O₃向Rh的转移过程, 从而加速了质子还原反应. 最后, 基于这些结果提出了Cr₂O₃-Rh/Ga₂O₃光催化剂上的光催化分解水机理. 本文的研究结果有利于更加深入地认识半导体光催化分解水反应机理, 并为高效半导体光催化剂的合成提供一定的理论支持和指导.

关键词: 光催化, 时间分辨红外光谱, 光生电荷动力学, 全分解水, 助催化剂, 氧化镓

Abstract:

Investigation of the charge dynamics and roles of cocatalysts is crucial for understanding the reaction of photocatalytic water splitting on semiconductor photocatalysts. In this work, the dynamics of photogenerated electrons in Ga₂O₃ loaded with Cr₂O₃-Rh cocatalysts was studied using time-resolved mid-infrared spectroscopy. The structure of these Cr₂O₃-Rh cocatalysts was identified with high-resolution transmission electron microscopy and CO adsorption Fourier-transform infrared spectroscopy, as Rh particles partly covered with Cr₂O₃. The decay dynamics of photogenerated electrons reveals that only the electrons trapped by the Rh particles efficiently participate in the H₂ evolution reaction. The loaded Cr₂O₃ promotes electron transfer from Ga₂O₃ to Rh, which accelerates the electron-consuming reaction for H₂ evolution. Based on these observations, a photocatalytic water-splitting mechanism for Cr₂O₃-Rh/Ga₂O₃ photocatalysts has been proposed. The elucidation of the roles of the Cr₂O₃-Rh cocatalysts aids in further understanding the reaction mechanisms of photocatalytic water splitting and guiding the development of improved photocatalysts.

Key words: Time-resolved mid-infrared spectroscopy, Carrier dynamics, Overall water splitting, Cocatalyst, Gallium oxide, Photocatalysis, Time-resolved mid-infrared spectroscopy, Carrier dynamics, Overall water splitting, Cocatalyst, Gallium oxide

丁倩, 陈涛, 政, 冯兆池, 王秀丽. Cr₂O₃-Rh/Ga₂O₃光催化分解水的时间分辨红外光谱研究[J]. 催化学报, 2021, 42(5): 808-816.

Qian Ding, Tao Chen, Zheng Li, Zhaochi Feng, Xiuli Wang. Time-resolved infrared spectroscopic investigation of Ga₂O₃ photocatalysts loaded with Cr₂O₃-Rh cocatalysts for photocatalytic water splitting[J]. Chinese Journal of Catalysis, 2021, 42(5): 808-816.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63688-9

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图/表 19

Fig. 1. Photocatalytic activities of the photocatalysts. 0.1 g photocatalyst was dispersed into 500 mL deionized water and irradiated with a 450 W mercury lamp.

Fig. 2. HRTEM images of Cr2O3-Rh/Ga2O3 photocatalysts. (a) lattice fringes corresponding to Ga2O3; (b) lattice fringes corresponding to Rh.

Fig. 3. FT-IR spectra of CO adsorbed on Rh/Ga2O3 (1) and Cr2O3-Rh/Ga2O3 (2) photocatalysts.

Fig. 4. Time-resolved IR absorption spectra of Rh/Ga2O3 in air recorded in the step-scan measurement mode. A 1 Hz, 266 nm laser was used to excite the sample. The inset shows the normalized decay curves at 1480, 1300, and 900 cm-1.

Fig. 5. Transient MIR absorption decays of Ga2O3 in vacuum (1), water vapor (2), and oxygen (3) excited by a 1 Hz, 266 nm laser pulse. The inset shows the normalized transient MIR absorption profiles.

Table 1 Lifetimes (τ50%) of Ga2O3-based photocatalysts in vacuum, water vapor, and O2.

τ_50%/μs	in vacuum	in H₂O	in O₂
Ga₂O₃	31	31	31
Cr₂O₃/Ga₂O₃	31	53	31
Rh/Ga₂O₃	21	12	21
Cr₂O₃-Rh/Ga₂O₃	12	10	12

Table 1 Lifetimes (τ50%) of Ga2O3-based photocatalysts in vacuum, water vapor, and O2.

τ_50%/μs	in vacuum	in H₂O	in O₂
Ga₂O₃	31	31	31
Cr₂O₃/Ga₂O₃	31	53	31
Rh/Ga₂O₃	21	12	21
Cr₂O₃-Rh/Ga₂O₃	12	10	12

Fig. 6. Transient MIR absorption decays of Cr2O3/Ga2O3 in vacuum (1), water vapor (2), and oxygen (3) excited by a 1 Hz, 266 nm laser pulse. The inset shows the normalized transient MIR absorption profiles.

Fig. 7. Transient MIR absorption decays of Rh/Ga2O3 in vacuum (1), water vapor (2), and oxygen (3) excited by a 1 Hz, 266 nm laser pulse. The inset shows the normalized transient MIR absorption profiles.

Fig. 8. Transient MIR absorption decays of Cr2O3-Rh/Ga2O3 in vacuum (1), water vapor (2), and oxygen (3) excited by a 1 Hz, 266 nm laser pulse. The inset shows the normalized transient MIR absorption profiles.

Scheme 1. Schematic model of working mechanisms of Rh or Rh-Cr2O3 in photocatalytic water splitting on Rh/Ga2O3 or Cr2O3-Rh/Ga2O3. Blue arrows indicate the photocatalytic redox reactions. Black arrows indicate the photogenerated charge transfer processes. The thickness of the black solid arrow lines indicates the relative contents of the transfer path, where thicker arrow lines represent higher content than the thinner ones. The dashed lines indicate the possible charge transfer.

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Cr₂O₃-Rh/Ga₂O₃光催化分解水的时间分辨红外光谱研究

Time-resolved infrared spectroscopic investigation of Ga₂O₃ photocatalysts loaded with Cr₂O₃-Rh cocatalysts for photocatalytic water splitting

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