集成二维层状CdS/WO3 S型异质结及金属化Ti3C2 MXene基欧姆结高效光催化产氢

doi:10.1016/S1872-2067(21)63883-4

催化学报 ›› 2022, Vol. 43 ›› Issue (2): 359-369.DOI: 10.1016/S1872-2067(21)63883-4

集成二维层状CdS/WO₃ S型异质结及金属化Ti₃C₂ MXene基欧姆结高效光催化产氢

白浚贤^a^,^†, 沈荣晨^a^,^†, 姜志民^a, 张鹏^b, 李佑稷^c, 李鑫^a^,^*

^a华南农业大学生物质工程研究院, 农业部能源植物资源与利用重点实验室, 广东广州510642
^b郑州大学材料与工程学院, 低碳环保材料智能设计国际联合研究中心, 河南郑州450001
^c吉首大学化学化工学院, 湖南吉首416000

收稿日期:2021-05-08 接受日期:2021-06-26 出版日期:2022-02-18 发布日期:2021-07-08
通讯作者: 白浚贤,沈荣晨,李鑫
基金资助:
国家自然科学基金(21975084);国家自然科学基金(51672089);华南农业大学丁颖人才计划

Integration of 2D layered CdS/WO₃ S-scheme heterojunctions and metallic Ti₃C₂ MXene-based Ohmic junctions for effective photocatalytic H₂ generation

Junxian Bai^a^,^†, Rongchen Shen^a^,^†, Zhimin Jiang^a, Peng Zhang^b, Youji Li^c, Xin Li^a^,^*

^aInstitute of Biomass Engineering, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture and Rural Affairs, South China Agricultural University, Guangzhou 510642, Guangdong, China
^bState Centre for International Cooperation on Designer Low-Carbon & Environmental Materials (CDLCEM), School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^cCollege of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, Hunan, China

Received:2021-05-08 Accepted:2021-06-26 Online:2022-02-18 Published:2021-07-08
Contact: Junxian Bai, Rongchen Shen, Xin Li
Supported by:
This work was supported by the National Natural Science Foundation of China(21975084);This work was supported by the National Natural Science Foundation of China(51672089);the Ding Ying Talent Project of South China Agricultural University.

摘要/Abstract

摘要：

开发低成本的半导体光催化剂以实现可见光下高效、持久的光催化分解水产氢是一个非常具有挑战性的课题. 近年来, 具有高产氢活性的CdS光催化剂引起了人们的研究兴趣. 但是光生电子-空穴对快速复合、反应活性位点不足以及严重的光腐蚀等问题, 严重地制约了CdS在光催化领域的实际应用. 构建S型异质结和负载助催化剂被认为是促进光生电子空穴分离和加速产氢动力学的有效策略. 本文通过在低成本的WO₃和Ti₃C₂ MXene (MX)纳米片上生长CdS纳米片, 设计并构建了具有二维耦合界面的2D/2D/2D层状异质结光催化剂, 以实现高效的可见光光催化分解水产氢. 首先通过水热煅烧和刻蚀的方法分别制备了WO₃和MX纳米片, 然后以乙酸镉和硫脲为原料在乙二胺溶剂中通过水热法合成了MX-CdS/WO₃层状异质结光催化剂. 在可见光下, 以乳酸为牺牲剂测试了光催化剂的产氢活性且经过4次连续的循环反应, MX-CdS/WO₃体系展现出良好的活性及稳定性. 在可见光的照射下, MX-CdS/WO₃层状异质结光催化剂最高的可见光光催化分解水产氢速率达到了27.5 mmol/g/h, 是纯CdS纳米片的11倍. 与此同时, 在450 nm的光照下, 表观量子效率达到了12.0%.
为了深入探讨其高效产氢机理, 通过X射线衍射、X射线光电子能谱、原子力显微镜、透射电镜、高分辨电子显微镜等对MX-CdS/WO₃体系的组成和结构进行分析. 结果表明, 实验成功地合成了CdS, WO₃和MX三种纳米片及其复合材料. 通过紫外-可见漫反射光谱研究了样品材料的光吸收能力. 通过表面光电压、稳态及瞬态荧光光谱等研究了材料的电荷载流子复合和转移行为, 发现MX-CdS/WO₃的光生电子空穴对相比与纯CdS或者二元复合材料具有更高的分离效率. UPS和ESR等表征结果说明, 材料内部电场的方向和在光照条件下光生载流子的迁移方向, 从而证实了S型异质结和欧姆结的成功构建. 综上, 在MX-CdS/WO₃光催化剂体系中, S型异质结形成较强的界面电场能够有效促进CdS纳米片与WO₃纳米片之间光生电子-空穴对的分离. 同时, 二维Ti₃C₂ MXene纳米片作为辅助催化剂, 通过与CdS/WO₃纳米片构建欧姆结, 进而提供大量的电子转移途径和更多的析氢反应活性位点, 使得CdS光催化剂的光催化活性和稳定性得到了很大的提升.
通过构建S型内建电场、欧姆结和2D/2D界面可以协同提高CdS纳米片的光催化性能, 从而加速光生电子在异质结中的分离和利用. 本文所采用基于S型异质结与欧姆结基助催化剂之间的耦合策略可以作为一种通用策略扩展到其它传统半导体光催化剂的改性中, 从而推进高效光催化产氢材料的有效合成.

关键词: 光催化分解水产氢, 2D层状S型异质结, CdS纳米片, WO₃纳米片, Ti₃C₂ MXene基欧姆结, 2D耦合界面

Abstract:

The rapid recombination of photo-generated electron-hole pairs, insufficient active sites, and strong photocorrosion have considerably restricted the practical application of CdS in photocatalytic fields. Herein, we designed and constructed a 2D/2D/2D layered heterojunction photocatalyst with cascaded 2D coupling interfaces. Experiments using electron spin resonance spectroscopy, ultraviolet photoelectron spectroscopy, and in-situ irradiation X-ray photoelectron spectroscopy were conducted to confirm the 2D layered CdS/WO₃ step-scheme (S-scheme) heterojunctions and CdS/MX ohmic junctions. Impressively, it was found that the strong interfacial electric fields in the S-scheme heterojunction photocatalysts could effectively promote spatially directional charge separation and transport between CdS and WO₃ nanosheets. In addition, 2D Ti₃C₂ MXene nanosheets with a smaller work function and excellent metal conductivity when used as a co-catalyst could build ohmic junctions with CdS nanosheets, thus providing a greater number of electron transfer pathways and hydrogen evolution sites. Results showed that the highest visible-light hydrogen evolution rate of the optimized MX-CdS/WO₃ layered multi-heterostructures could reach as high as 27.5 mmol/g/h, which was 11.0 times higher than that of pure CdS nanosheets. Notably, the apparent quantum efficiency reached 12.0% at 450 nm. It is hoped that this study offers a reliable approach for developing multifunctional photocatalysts by integrating S-scheme and ohmic-junction built-in electric fields and rationally designing a 2D/2D interface for efficient light-to-hydrogen fuel production.

Key words: Photocatalytic hydrogen evolution, 2D layered S-scheme heterojunction, CdS nanosheets, WO₃ nanosheets, Ti₃C₂ MXene-based ohmic junctions, Cascade 2D coupling interfaces

白浚贤, 沈荣晨, 姜志民, 张鹏, 李佑稷, 李鑫. 集成二维层状CdS/WO₃ S型异质结及金属化Ti₃C₂ MXene基欧姆结高效光催化产氢[J]. 催化学报, 2022, 43(2): 359-369.

Junxian Bai, Rongchen Shen, Zhimin Jiang, Peng Zhang, Youji Li, Xin Li. Integration of 2D layered CdS/WO₃ S-scheme heterojunctions and metallic Ti₃C₂ MXene-based Ohmic junctions for effective photocatalytic H₂ generation[J]. Chinese Journal of Catalysis, 2022, 43(2): 359-369.

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图/表 11

Scheme 1. Schematic of the fabrication of MX-CdS/WO3 composites.

Fig. 1. (a) The XRD patterns of CdS, CdS/WO3, MX-CdS, and MX-CdS/WO3; (b) XRD patterns of MX and WO3.

Fig. 2. TEM images of CdS (a), WO3 (b), MX (c), MX-CdS/WO3 (d,f); (e) HRTEM image of MX-CdS/WO3; Elemental mapping (g-m) and EDX spectrum (n) of MX-CdS/WO3.

Fig. 3. XPS scan of Cd 3d (a), S 2p (b), W4f (c), and Ti 2p (d).

Fig. 4. UV-vis absorption spectra (a) and hydrogen evolution (b) of CdS, MX-CdS, CdS/WO3, and MX-CdS/WO3; (c) Recycled photocatalytic H2 evolution experiments of MX-CdS/WO3 and CdS; (d) Apparent quantum efficiency of MX-CdS/WO3.

Fig. 5. (a) PL spectra; (b) EIS Nyquist plots, with inset showing the electrical equivalent circuit of the Nyquist plots; (c) Polarization curves; (d) Photocurrent profiles.

Fig. 6. (a) Fluorescence lifetime spectra of CdS, MX-CdS, CdS/WO3, and MX-CdS/WO3 composites; (b) SPV spectra of CdS, CdS/WO3, and MX- CdS/WO3.

Fig. 7. (a,b) Mott-Schottky plots of CdS and WO3 under dark and light conditions; (c,d) VB XPS profiles of CdS and WO3.

Fig. 8. (a) (αhv)1/2 vs. hν plots of CdS and WO3 from UV-visible DRS analysis; (b) UPS spectra of CdS, WO3, and Ti3C2; (c) Energy level position schematics of CdS and WO3 from the Mott-Schottky plot under dark and light conditions; (d) Band structures of CdS and WO3.

Fig. 9. (a) High-resolution XPS for Cd 3d of CdS/WO3 under 420-nm visible-light irradiation or in the dark; (b) ESR spectra of CdS, WO3, and CdS/WO3 in the dark; (c,d) ESR spectra of CdS, WO3, and CdS/WO3 (DMPO-•O2- and DMPO-•OH-).

Fig. 10. S-scheme heterojunction of MX-CdS/WO3: (a) before contact interaction, (b) after contact interaction, and (c) after contact interaction under irradiation, photogenerated carrier migration and separation, and photocatalytic hydrogen evolution.

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集成二维层状CdS/WO₃ S型异质结及金属化Ti₃C₂ MXene基欧姆结高效光催化产氢

Integration of 2D layered CdS/WO₃ S-scheme heterojunctions and metallic Ti₃C₂ MXene-based Ohmic junctions for effective photocatalytic H₂ generation

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