ZnCdS纳米球和二苯并噻吩修饰的g-C3N4构成的S型异质结用于增强光催化产氢

doi:10.1016/S1872-2067(22)64201-3

催化学报 ›› 2023, Vol. 46: 167-176.DOI: 10.1016/S1872-2067(22)64201-3

ZnCdS纳米球和二苯并噻吩修饰的g-C₃N₄构成的S型异质结用于增强光催化产氢

李瀚^a, 陶善仁^a, 万思杰^a, 邱国根^a, 龙庆^a, 余家国^a^,^b, 曹少文^a^,^*()

^a武汉理工大学材料复合新技术国家重点实验室, 湖北武汉 430070
^b中国地质大学材料与化学学院, 太阳燃料实验室, 湖北武汉 430074

收稿日期:2022-10-11 接受日期:2022-11-27 出版日期:2023-03-18 发布日期:2023-02-21
通讯作者: *电子信箱: swcao@whut.edu.cn (曹少文)
基金资助:
国家重点研发计划(2022YFE0114800);国家自然科学基金(51922081);国家自然科学基金(51961135303);国家自然科学基金(51932007);大学生创新创业训练计划(S202210497017);中央高校基本科研业务费专项资金资助(武汉理工大学: 2022-CL-A1-01)

S-scheme heterojunction of ZnCdS nanospheres and dibenzothiophene modified graphite carbon nitride for enhanced H₂ production

Han Li^a, Shanren Tao^a, Sijie Wan^a, Guogen Qiu^a, Qing Long^a, Jiaguo Yu^a^,^b, Shaowen Cao^a^,^*()

^aState Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, Hubei, China
^bLaboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, Hubei, China

Received:2022-10-11 Accepted:2022-11-27 Online:2023-03-18 Published:2023-02-21
Contact: *E-mail: swcao@whut.edu.cn (S. Cao)
Supported by:
National Key R&D Program of China(2022YFE0114800);The National Natural Science Foundation of China(51922081);The National Natural Science Foundation of China(51961135303);The National Natural Science Foundation of China(51932007);National Innovation and Entrepreneurship Training Program for College Students(S202210497017);Fundamental Research Funds for the Central Universities(WHUT: 2022-CL-A1-01)

摘要/Abstract

摘要：

光催化分解水产氢被认为是一种具有应用前景的策略来应对能源和环境挑战. 许多种类的光催化剂如CdS和TiO₂等, 已被广泛研究并用于光催化制氢. 在各种半导体中, g-C₃N₄因其能带结构恰当、稳定性好、无毒以及制备容易等优点成为有前途的光催化剂. 然而, 由于g-C₃N₄的可见光吸收较差, 光激发的载流子复合严重等问题导致其光催化活性相对较低. 因此, 研究人员采用了纳米结构设计、掺杂、构建异质结和负载助催化剂等策略来对g-C₃N₄进行改性.

通过引入合适的电子供体(D)或受体(A)单元, 在g-C₃N₄基本构型内创建一个分子内D-A结构, 被确认为一种有效的策略来提高光催化性能. 分子内的D-A结构不仅使g-C₃N₄的带隙变窄以提高其光吸收能力, 还形成了一个内建电场, 加速了激子的解离、体相载流子的分离和传输. 但单组分的光催化剂仍然存在可见光吸收不足和较严重的载流子复合问题. 为了进一步提高光催化产氢的性能, 构建梯型(S型)异质结是解决这些问题的有效方法. S型异质结通过内部电场可以实现有效的空间载流子分离, 同时保留光生电子和空穴的强大的氧化还原能力. 因此, 寻找另外一个能带结构匹配的半导体来与g-C₃N₄构成S型异质结是非常可取的. 另一方面, ZnCdS固溶体已经被广泛用于光催化产氢. 在固溶体晶格中用锌原子替代镉原子, 不仅可以连续调节能带结构, 还可以提高其稳定性.

为了充分利用固溶体和D-A结构的优势, 本文通过自组装方法合成了ZCS(ZnCdS 纳米球)@DBTCN(二苯并噻吩基团修饰的g-C₃N₄) S型异质结光催化剂. 红外光谱、高分辨透射电镜和X射线光电子能谱等结果证明形成了紧密接触的ZCS@DBTCN异质结. 研究了ZCS和DBTCN的能带结构, 通过开尔文探针、莫特肖特基曲线和带隙结果确定了ZCS和DBTCN的功函数, 导带和价带位置. 结果表明, DBTCN的费米能级和导带电位均比ZCS的更负, 揭示了暗态下电子通过紧密接触的界面由DBTCN转移到ZCS, 这与差分电荷密度的计算结果相一致. 暗态下的电子转移可以形成一个界面内建电场, 作为光生载流子迁移的驱动力, 调控光生载流子的定向转移, 实现光生载流子的空间分离. 通过原位X射线光电子能谱和原位开尔文探针力显微镜进一步证明了光照下电子的转移方向, 这种电子转移方向可以保留最大的氧化和还原能力, 并且符合S型异质结电子转移机制. 稳态荧光光谱、瞬态荧光光谱、电化学阻抗谱和光电流曲线结果表明, 分子内电场和S型异质结的协同作用显著加速了光生载流子在分子内和界面的快速转移. 得益于S型异质结和分子内的内建电场的协同作用, 7ZCS@DBTCN显示出了最好的光催化剂产氢活性(8.87 mmol g^-1 h^-1), 分别是单独ZCS和DBTCN的2.55倍和3.46倍. 综上, 本文提供了一种利用给体-受体修饰和S型异质结协同效应来设计高性能光催化剂的思路.

关键词: 光催化, 氮化碳, 锌镉硫, S型异质结, 电子转移

Abstract:

g-C₃N₄-based photocatalysts with an intramolecular donor-acceptor structure still suffer from inadequate visible-light absorption and severe charge recombination. Constructing S-scheme heterojunction is a promising approach to address these issues. Herein, ZCS (ZnCdS nanospheres)@DBTCN (g-C₃N₄ modified by dibenzothiophene groups) S-scheme heterojunction photocatalyst was synthesized through a self-assembly approach. The ZCS@DBTCN material showed a superior photocatalytic H₂ production activity of 8.87 mmol g^-1 h^-1, which is 3.46 and 2.55 times that of pure DBTCN and ZCS, respectively. This enhanced photocatalytic performance could be ascribed to the synergistic effect of intramolecular internal electric field and S-scheme heterojunction, which boosts the separation and transport of photogenerated carriers within the molecular framework and at the interface, and preserves the maximum redox capacity of the spatially separated electrons and holes. Moreover, the S-scheme charge migrate mechanism of ZCS@DBTCN was strongly evidenced by the in-situ irradiated Kelvin probe force microscopy and in-situ irradiated X-ray photoelectron spectroscopy. This study provides a protocol for designing g-C₃N₄-based hybrid photocatalysts with high charge separation efficiency and excellent photocatalytic activity.

Key words: Photocatalysis, Carbon nitride, ZnCdS, S-scheme heterojunction, Charge transfer

李瀚, 陶善仁, 万思杰, 邱国根, 龙庆, 余家国, 曹少文. ZnCdS纳米球和二苯并噻吩修饰的g-C₃N₄构成的S型异质结用于增强光催化产氢[J]. 催化学报, 2023, 46: 167-176.

Han Li, Shanren Tao, Sijie Wan, Guogen Qiu, Qing Long, Jiaguo Yu, Shaowen Cao. S-scheme heterojunction of ZnCdS nanospheres and dibenzothiophene modified graphite carbon nitride for enhanced H₂ production[J]. Chinese Journal of Catalysis, 2023, 46: 167-176.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64201-3

https://www.cjcatal.com/CN/Y2023/V46/I3/167

图/表 9

Fig. 1. (a) Schematic diagram of the fabrication route for ZCS@DBTCN composites. (b) XRD patterns of pristine ZCS, DBTCN and ZCS@DBTCN composites. (c) FT-IR spectra of DBTCN, ZCS, and ZCS@DBTCN composites.

Fig. 2. (a,b) TEM and HRTEM images of 7ZCS@DBTCN. (c) TEM image and corresponding element mapping images of 7ZCS@DBTCN.

Fig. 3. (a) UV-vis DRS of ZCS, DBTCN and ZCS@DBTCN. (b) Plots of (αhv)1/2 versus (hv) for ZCS and DBTCN.

Fig. 4. (a) PL spectra of DBTCN, ZCS, and ZCS@DBTCN. (b) TRPL of DBTCN, ZCS and 7ZCS@DBTCN. EIS plots (c) and photocurrent responses (d) of DBTCN, ZCS and 7ZCS@DBTCN.

Fig. 5. (a) PHE rates of DBTCN, ZCS and ZCS@DBTCN samples. (b) Stability test of PHE over 7ZCS@DBTCN. (c) XRD patterns of 7ZCS@DBTCN before and after reaction. (d) FESEM image of 7ZCS@DBTCN after reaction.

Fig. 6. Mott-Schottky plots (a,b) and Band structures (c) of ZCS and DBTCN. (d) CPD values of DBTCN, ZCS, and 7ZCS@DBTCN.

Fig. 7. (a) XPS survey spectra of ZCS, DBTCN and 7ZCS@DBTCN. High-resolution Zn 2p (b), Cd 3d (c) and C 1s (d) XPS spectra of the samples. In-situ XPS spectra were recorded under light irradiation (λ = 365 nm), where 7ZCS@DBTCN and 7ZCS@DBTCN UV represent under dark and light conditions, respectively.

Fig. 8. AFM image of 7ZCS@DBTCN (a), and corresponding surface potential images of 7ZCS@DBTCN under dark (b) and light-irradiation (c) conditions; The height (d) and surface potential (e) of the line scan from point A to point B. (f) Charge density distribution at the interface of ZCS@DBTCN heterostructure; (g) The planar averaged electron density difference of ZCS@DBTCN. The yellow and cyan areas denote the electron accumulation and loss, respectively.

Fig. 9. Schematic diagram of the S-scheme charge transfer mechanism of the ZCS@DBTCN heterojunction.

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ZnCdS纳米球和二苯并噻吩修饰的g-C₃N₄构成的S型异质结用于增强光催化产氢

S-scheme heterojunction of ZnCdS nanospheres and dibenzothiophene modified graphite carbon nitride for enhanced H₂ production

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