ZrO2修饰均匀氮掺杂氧化物MgTa2O6-xNx以提升其光催化分解水性能

doi:10.1016/S1872-2067(23)64534-6

催化学报 ›› 2023, Vol. 54: 220-228.DOI: 10.1016/S1872-2067(23)64534-6

ZrO₂修饰均匀氮掺杂氧化物MgTa₂O_6-_xN_x以提升其光催化分解水性能

王宁宁^a, 王硕^a, 李灿^a, 李晨阳^a, 刘春江^a, 陈闪山^a^,^*(), 章福祥^b^,^*()

^a南开大学材料科学与工程学院, 国家新材料研究院, 天津300350
^b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, 洁净能源国家实验室, 能源材料化学协同创新中心, 辽宁大连116023

收稿日期:2023-08-26 接受日期:2023-10-09 出版日期:2023-11-18 发布日期:2023-11-15
通讯作者: *电子邮箱: sschen@nankai.edu.cn (陈闪山), fxzhang@dicp.ac.cn (章福祥).
基金资助:
国家自然科学基金(22272082);国家自然科学基金(21925206);中央高校基本科研业务费, 南开大学(63213098);河北省科学技术厅基金(226Z4307G)

ZrO₂ modification of homogeneous nitrogen-doped oxide MgTa₂O_6-_xN_x for promoted photocatalytic water splitting

Ningning Wang^a, Shuo Wang^a, Can Li^a, Chenyang Li^a, Chunjiang Liu^a, Shanshan Chen^a^,^*(), Fuxiang Zhang^b^,^*()

^aSchool of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin 300350, China
^bState Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian 116023, Liaoning, China

Received:2023-08-26 Accepted:2023-10-09 Online:2023-11-18 Published:2023-11-15
Contact: *E-mail: sschen@nankai.edu.cn (S. Chen); fxzhang@dicp.ac.cn (F. Zhang).
Supported by:
National Natural Science Foundation of China(22272082);National Natural Science Foundation of China(21925206);Fundamental Research Funds for the Central Universities, Nankai University(63213098);Hebei Provincial Department of Science and Technology(226Z4307G)

摘要/Abstract

摘要：

光催化分解水被认为是非常有前景的制氢技术之一, 该技术不依赖传统化石燃料, 且避免了温室气体CO₂的排放. 提升太阳能光催化分解水效率的一个重要前提是开发高效的窄带隙半导体光催化材料. 近年来, 多种窄带隙半导体, 如掺杂氧化物、氮(氧)化物、硫(氧)化物、卤氧化物和卤氮化物等, 被开发并应用于可见光光催化分解水反应体系. 其中, 均匀氮掺杂氧化物是一类典型的窄带隙半导体, 主要包含氮掺杂层状或者隧道状氧化物. 前期本课题组开发了一系列均匀氮掺杂氧化物并用于可见光光催化分解水体系. 通过将MgTa₂O_6-_xN_x和TaON构筑异质结后, 最终组装出的Z机制全分解水体系的表观量子效率可达12.3% (420 nm). 与异质结相比, 氮掺杂氧化物本身仍存在电荷分离较差的问题, 如何改善该类材料的电荷分离是当前面临的重要挑战之一. 表面修饰被认为是一种可以通过减少表面复合中心从而提升电荷分离效率的策略. 例如, 通过在TaON和Ta₃N₅半导体表面分别修饰ZrO₂和MgO可以显著减少材料本身的表面缺陷从而提高光催化分解水性能.

考虑到氮掺杂氧化物和氮(氧)化物具有相似的组成和性质, 本文以氮掺杂隧道状氧化物MgTa₂O_6-_xN_x为模型材料, 验证了ZrO₂修饰策略也可有效改善均匀氮掺杂氧化物类半导体材料的电荷分离, 提升光催化分解水性能. 首先, 对MgTa₂O₆进行表面修饰, 得到ZrO₂/MgTa₂O₆前驱体, 再经过掺氮处理后制得ZrO₂/MgTa₂O_6-_xN_x. 结果表明, Zr物种以粒径为20 nm左右的ZrO₂纳米颗粒形式存在, 对MgTa₂O_6-_xN_x晶体结构和形貌等几乎无影响. 紫外可见漫反射光谱和X射线光电子能谱结果表明, ZrO₂修饰能在一定程度上抑制MgTa₂O_6-_xN_x材料在氮掺杂过程中低价钽物种的生成. 将系列样品分别担载产氢或产氧助催化剂后, ZrO₂/MgTa₂O_6-_xN_x样品的光催化水还原或水氧化活性均比MgTa₂O_6-_xN_x样品有明显提升. 其中, Pt-ZrO₂/MgTa₂O_6-_xN_x (Zr/Ta = 0.10)光催化剂的产氢活性约是Pt-MgTa₂O_6-_xN_x活性的4.5倍, 相应的表观量子效率高于大多数已报道的其它均匀氮掺杂光催化剂的结果, 证明了ZrO₂修饰策略在改善电荷分离和提高光催化分解水性能方面的有效性. 这可能是因为, ZrO₂修饰后MgTa₂O_6-_xN_x表面会产生Zr-O-Ta键, 在一定程度上抑制了低价钽物种(光生载流子复合中心)的生成, 进而提升了MgTa₂O_6-_xN_x电荷分离效率.

综上, 本文拓展了ZrO₂修饰策略在宽光谱响应的均匀氮掺杂氧化物类材料方面的应用范围, 为开发高效太阳能光催化转化体系提供了一种新思路.

关键词: MgTa₂O_6-_xN_x, 氮掺杂, 光催化剂, 水分解, ZrO₂修饰

Abstract:

Homogeneous nitrogen-doped oxides are of wide visible light utilization for promising photocatalytic water splitting to produce hydrogen, but currently the poor charge separation severely limits their photocatalytic performances. In this work, a homogeneous nitrogen-doped tunneled oxide of MgTa₂O_6-_xN_x with an absorption edge of 570 nm was selected as a prototype to investigate the influence of ZrO₂ modification on the charge separation as well as photocatalytic performance. It is interesting to observe that the formation of the reduced tantalum species, regarded as recombination centers, in the MgTa₂O_6-_xN_x sample could be effectively inhibited via the surface passivation with ZrO₂ nanoparticles, based on which the photocatalytic water reduction and oxidation half-reaction activities could be remarkably promoted. Together with modification of the deposited Pt cocatalyst, the optimized H₂ evolution rate over Pt-ZrO₂/MgTa₂O_6-_xN_x (Zr/Ta = 0.10) photocatalyst was almost 4.5 times as high as that of the pristine Pt-MgTa₂O_6-_xN_x sample free of ZrO₂ modification, whose apparent quantum yield at 420 nm (± 15 nm) achieved herein was superior to those of other reported homogeneous nitrogen-doped photocatalysts. The improved charge separation probably attributes to the introduction of Zr-O-Ta bond after ZrO₂ modification, which is helpful to stabilize the tantalum species at more cationic state and inhibit the formation of the reduced tantalum species. This work extends the application territory of ZrO₂ modification to the homogeneous nitrogen-doped oxide photocatalysts, and demonstrates its feasibility and effectiveness for remarkably enhanced photocatalytic water splitting performance.

Key words: MgTa₂O_6-_xN_x, Nitrogen doping, Photocatalyst, Water splitting, ZrO₂ modification

王宁宁, 王硕, 李灿, 李晨阳, 刘春江, 陈闪山, 章福祥. ZrO₂修饰均匀氮掺杂氧化物MgTa₂O_6-_xN_x以提升其光催化分解水性能[J]. 催化学报, 2023, 54: 220-228.

Ningning Wang, Shuo Wang, Can Li, Chenyang Li, Chunjiang Liu, Shanshan Chen, Fuxiang Zhang. ZrO₂ modification of homogeneous nitrogen-doped oxide MgTa₂O_6-_xN_x for promoted photocatalytic water splitting[J]. Chinese Journal of Catalysis, 2023, 54: 220-228.

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图/表 5

Fig. 1. Structural characterizations of ZrO2/MgTa2O6-xNx samples with different molar ratios of Zr/Ta. (a) Crystalline structure of MgTa2O6. (b) XRD patterns. (c) Enlarged XRD patterns.

Fig. 2. (a) UV-vis DRS of ZrO2/MgTa2O6-xNx samples with different molar ratios of Zr/Ta. (b) Ta 4f XPS of MgTa2O6-xNx (i) and ZrO2/MgTa2O6-xNx (ii) samples. Herein, the molar ratio of Zr/Ta was 0.10 for the ZrO2/MgTa2O6-xNx sample.

Fig. 3. Microscopy characterization of ZrO2/MgTa2O6-xNx sample with a Zr/Ta molar ratio of 0.10. (a,b) SEM images. (c) STEM image. (d-f) EDS elemental mapping images. (g,h) HRTEM images. Herein, elements of Ta (d), Zr (e), and a superimposition of both elements (f) were showed in the EDS elemental mapping images.

Fig. 4. Photocatalytic H2 (a) and O2 (b) evolution rates of ZrO2/MgTa2O6-xNx samples with different molar ratios of Zr/Ta. Reaction conditions: photocatalyst (0.1 g); ascorbic acid aqueous solution (10 mmol/L, 100 mL); 300 W Xe lamp with a cutoff filter (λ ≥ 420 nm) for (a). Photocatalyst (0.1 g); AgNO3 aqueous solution (50 mmol/L, 100 mL); La2O3 (0.1 g); 300 W Xe lamp with a cutoff filter (λ ≥ 420 nm) for (b). Herein, 0.2 wt% Pt or 1.0 wt% CoOx was loaded on the photocatalyst for H2 or O2 evolution reaction, respectively.

Fig. 5. Analysis of the roles of ZrO2 modification on the MgTa2O6-xNx sample. (a) PL emission spectra. (b,c) Schematic illustration. Herein, 0.2 wt% Pt was deposited, and the molar ratio of Zr/Ta was 0.10 for the ZrO2/MgTa2O6-xNx sample.

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ZrO₂修饰均匀氮掺杂氧化物MgTa₂O_6-_xN_x以提升其光催化分解水性能

ZrO₂ modification of homogeneous nitrogen-doped oxide MgTa₂O_6-_xN_x for promoted photocatalytic water splitting

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