g-C3N4/CoTiO3梯型异质结及其增强的可见光催化分解纯水制氢性能

doi:10.1016/S1872-2067(22)64111-1

催化学报 ›› 2022, Vol. 43 ›› Issue (10): 2548-2557.DOI: 10.1016/S1872-2067(22)64111-1

g-C₃N₄/CoTiO₃梯型异质结及其增强的可见光催化分解纯水制氢性能

孟爱云^,^†, 周双^,^†, 温达, 韩培刚(), 苏耀荣()

深圳技术大学新材料与新能源学院, 广东深圳 518118

收稿日期:2022-03-13 接受日期:2022-04-17 出版日期:2022-10-18 发布日期:2022-09-30
通讯作者: 韩培刚,苏耀荣
作者简介:^†共同第一作者.
基金资助:
国家自然科学基金(22002091);国家自然科学基金(22178224);深圳技术大学基本科研业务费专项资金;广东省基础与应用基础研究项目(2020A1515110873);广东省晶体生长与应用工程技术研究中心项目(2020GCZX005);上海鸿之微Prop计划;深圳市基础研究面上项目(JCYJ20190813113408912);深圳技术大学高端人才研究经费(2019211);广东省创新专项(2020KTSCX125);深圳市稳定支持项目(SZWD2021015)

g-C₃N₄/CoTiO₃ S-scheme heterojunction for enhanced visible light hydrogen production through photocatalytic pure water splitting

Aiyun Meng^,^†, Shuang Zhou^,^†, Da Wen, Peigang Han(), Yaorong Su()

College of New Materials and New Energies, Shenzhen Technology University, Shenzhen 518118, Guangdong, China

Received:2022-03-13 Accepted:2022-04-17 Online:2022-10-18 Published:2022-09-30
Contact: Peigang Han, Yaorong Su
About author:^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22002091);National Natural Science Foundation of China(22178224);Fundamental Research Funds for Shenzhen Technology University;Guangdong Basic and Applied Basic Research Foundation(2020A1515110873);University Engineering Research Center of Crystal Growth and Applications of Guangdong Province(2020GCZX005);Prop project of Hongzhiwei Technology (Shanghai) Co., LTD;Shenzhen Fundamental Research Program(JCYJ20190813113408912);Natural Science Foundation of Top Talent of SZTU(2019211);Special Innovative Projects of Guangdong Province(2020KTSCX125);Shenzhen Stable Supporting Program(SZWD2021015)

摘要/Abstract

摘要：

光催化分解纯水制氢在利用太阳能制备清洁能源方面极具潜力, 寻找高效的光催化剂是实现其实际应用的关键因素. 高效的光催化剂需同时具备宽光谱吸收、低载流子复合率以及足够强的氧化还原能力等条件. 然而, 具有强氧化还原能力的光催化剂通常具有较高的导带和较低的价带位置, 导致其带隙较宽, 光吸收范围缩窄, 因此, 单一的光催化剂难以同时满足宽光谱吸收和强氧化还原能力也难以实现高效的光催化纯水分解制氢. 相比之下, 梯型异质结可以将两种带隙适宜、能带结构匹配的光催化剂集成在一起, 在保持原本光催化剂的强氧化还原能力的同时也能充分地利用太阳光, 因此梯型异质结的研究受到广泛关注. 目前报道的梯型异质结光催化剂的可见光催化分解纯水制氢效率仍然很低, 并且大部分的材料都是在全光谱条件下进行测试的, 因此有必要开发在可见光下具有高活性的梯型异质结复合光催化剂.

本文报道了一种具有可见光响应的新型g-C₃N₄/CoTiO₃复合梯型异质结光催化剂, 在不添加牺牲剂的情况下, 成功实现了可见光催化分解纯水制氢气. 光催化测试结果表明, 在可见光(λ > 400 nm)照射下, 当CoTiO₃的含量为1.5 wt%时, 复合光催化剂的产氢速率达到最大值(118 μmol∙h^‒1∙g^‒1). 较好的光催化性能可归因于以下几个方面: (1) g-C₃N₄纳米片和CoTiO₃多面体之间形成梯型异质结, 不仅增强了光生电荷的分离和迁移, 也保留了较强的氧化还原能力; (2) CoTiO₃的添加拓展了g-C₃N₄/CoTiO₃异质结在500‒800 nm波长范围内的可见光吸收. 透射电镜和X射线光电子能谱结果表明, g-C₃N₄纳米片将CoTiO₃多面体均匀地包裹在一起, 形成接触紧密的界面, 这为梯型异质结的形成提供了必要条件. 原位XPS结果显示, 在可见光照射下, g-C₃N₄/CoTiO₃异质结中C 1s和N 1s的结合能负移, 而Co 2p和Ti 2p的结合能正移, 表明光生电子从CoTiO₃迁移至C₃N₄. 电子自旋共振结果表明, 相比纯g-C₃N₄和CoTiO₃, g-C₃N₄/CoTiO₃异质结在光照条件下能产生更多的羟基自由基和超氧自由基, 表明具有较强氧化能力的CoTiO₃价带空穴和具有较强还原能力的g-C₃N₄导带电子被保留下来, 进一步验证了g-C₃N₄/CoTiO₃的梯型异质结电荷传输机制. 综上, 本文通过系统地研究g-C₃N₄/CoTiO₃梯型异质结的制备、光催化纯水分解制氢性能以及电荷传输机理, 为构建具有可见光响应的高效光催化纯水分解制氢光催化剂提供了借鉴.

关键词: g-C₃N₄, CoTiO₃, 梯型异质结, 光催化, 产氢, 纯水分解

Abstract:

Photocatalytic hydrogen (H₂) production via water splitting in the absence of sacrificial agents is a promising strategy for producing clean and sustainable hydrogen energy from solar energy. However, the realization of a photocatalytic pure water splitting system with desirable efficiency is still a huge challenge. Herein, visible light photocatalytic H₂ production from pure water splitting was successfully achieved using a g-C₃N₄/CoTiO₃ S-scheme heterojunction photocatalyst in the absence of sacrificial agents. An optimum hydrogen evolution rate of 118 μmol∙h^-1∙g^-1 was reached with the addition of 1.5 wt% CoTiO₃. The remarkably promoted hydrogen evolution rate was attributed to the intensified light absorption coupled with the synergistic effect of visible light responsive CoTiO₃, the promoted efficiency in charge separation, and the reserved strong redox capacity induced by the S-scheme charge transfer mechanism. This work provides an alternative to visible light-responding oxidation photocatalysts for the construction of S-scheme heterojunctions and high-efficiency photocatalytic systems for pure water splitting.

Key words: CoTiO₃, g-C₃N₄, Photocatalytic hydrogen evolution, Pure water splitting, S-scheme heterojunction

孟爱云, 周双, 温达, 韩培刚, 苏耀荣. g-C₃N₄/CoTiO₃梯型异质结及其增强的可见光催化分解纯水制氢性能[J]. 催化学报, 2022, 43(10): 2548-2557.

Aiyun Meng, Shuang Zhou, Da Wen, Peigang Han, Yaorong Su. g-C₃N₄/CoTiO₃ S-scheme heterojunction for enhanced visible light hydrogen production through photocatalytic pure water splitting[J]. Chinese Journal of Catalysis, 2022, 43(10): 2548-2557.

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https://www.cjcatal.com/CN/Y2022/V43/I10/2548

图/表 10

Fig. 1. XRD patterns of the CN, CoTiO3 (a) and CCT-x (x = 0.5, 1.5, 2, 3) (b) samples.

Fig. 2. FESEM images of CN (a), CoTiO3 (b), and CCT-1.5 (c). TEM image (d) and high-resolution transmission electron microscopy (HRTEM) image (e) of CCT-1.5; FESEM image (f) and corresponding EDS mapping images (g-k) of CCT-1.5. Scale bar of (g-k) is 10 μm.

Fig. 3. UV-Vis diffuse reflectance spectroscopy of the CN, CoTiO3, and CCT-x (x = 0.5, 1.5, 2, 3) samples.

Fig. 4. Survey (a) and high-resolution XPS spectra of C 1s (b), N 1s (c), and O 1s (d) for CN, CoTiO3, CCT-1.5, and CCT-1.5-light (CCT-1.5 under light irradiation). High-resolution XPS spectra of Ti 2p (e) and Co 2p (f) for CCT-15 and CCT-15-light.

Fig. 5. Electrostatic potentials of C3N4 (a) and CoTiO3 (110) planes (b). The blue, gray, red, light gray, and purple spheres represent N, C, O, Ti, and Co atoms, respectively. The red and blue dashed lines represent the Fermi potential and vacuum energy potential, respectively.

Fig. 6. (a) Photocatalytic H2 production rates over the CN, CoTiO3, and CCT-x (x = 0.5, 1.5, 2, 3) samples under visible light illumination (λ > 400 nm). (b) Time-dependent H2 production yields on the CN, CoTiO3, and CCT-x samples under visible light illumination (λ > 400 nm). (c) Photocatalytic H2 production rates of CCT-1.5 under different light sources (λ = 365, 400, and 475 nm, visible light with λ > 400 nm, UV-Vis light without filter). (d) Absorption intensity of H2O2 over CN, CoTiO3, and CCT-1.5 suspensions after 3 h of pure water splitting. The amount of H2O2 was measured using iodometry via UV-Vis absorption spectroscopy. Detailed measurements are shown in experimental part.

Fig. 7. (a,b) M-S curves of CN, CoTiO3, and CCT-1.5. (c) Band structure illustrations for CN and CoTiO3.

Fig. 8. EPR spectra of DMPO-•O2- in methanol (a) and DMPO-•OH in the aqueous dispersion (b) in the presence of CN, CoTiO3, and CCT-1.5.

Fig. 9. PL spectra (a) and transient photocurrent response curves (b) of the samples under visible light irradiation (λ > 400 nm).

Fig. 10. Schematic of the energy levels of CN and CoTiO3 without contact (a), with contact (b), and under irradiation (c) and the photocatalytic S-scheme reaction mechanism of CCT-1.5 under irradiation.

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g-C₃N₄/CoTiO₃梯型异质结及其增强的可见光催化分解纯水制氢性能

g-C₃N₄/CoTiO₃ S-scheme heterojunction for enhanced visible light hydrogen production through photocatalytic pure water splitting

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