构建K3PW12O40/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应

doi:10.1016/S1872-2067(23)64507-3

摘要/Abstract

摘要：

太阳能向化学能转化是能源催化研究领域中一项意义重大且具有挑战性的课题, 实现由半导体光催化剂产生的电子和空穴同步高效利用是该领域的研究目标. 在众多催化剂中, S型异质结具有高氧化还原能力和快速电荷分离能力, 非常适合用于完成同步的光解水反应和有机氧化反应, 使电子和空穴得到同步高效利用. 苯甲醇(BA)氧化是一种典型的有机氧化反应, BA可被选择性氧化为苯甲醛(BAD), 其在合成药物、维生素、香料和其他有价值的化学品等方面具有重要作用.

本文采用水热法合成了keggin型多金属氧化物H₃PW₁₂O₄₀空心十二面体(KPW), 将15 nm的CdS纳米颗粒原位集成在KPW壳体上, 形成KPW@CdS S型核-壳异质结. 由于CdS和KPW之间的紧密界面和费米能级差异, 形成了一个巨大的内部电场(IEF), 促使载流子形成S型电荷转移机制. 采用能带结构分析(原位辐照X射线光电子能谱(ISI-XPS)、价带X射线光电子能谱(VB-XPS)和电子自旋共振(ESR))等方法确定了S型异质结界面上的有效电子转移途径. 光照条件下原位辐照的XPS结果表明Cd、S和W元素的结合能发生了变化. 与普通XPS光谱相比, Cd和S向低结合能方向移动, K, P, O和W向高结合能方向运动. 原位辐照XPS结果表明, KPW@CdS所含各元素的结合能偏移, 这为光催化剂中的载流子迁移和IEF的形成提供有力的证据. 此外, VB-XPS和ESR结果证实电荷转移途径遵循S型机制. 在光照射下, IEF作为驱动力可以促进光生载流子的分离和迁移. 优化后的复合材料的析氢速率为18.7 mmol g^‒1 h^‒1, 增值产物(BAD)的产率为17.5 mmol g^‒1 h^‒1, 远高于CdS. 光电实验结果表明, S型异质结界面处存在强内电场效应, 且复合材料的IEF强度是纯CdS的27.2倍. 优化后的样品在连续照射30 h后, 光催化活性没有明显下降, 说明KPW@CdS异质结可以作为一种潜在的光催化剂同时生成BAD和H₂. 此外, 中空结构有利于提高光的吸收和利用, 核壳结构提供了双重还原和氧化位点, 空心核壳结构与S型机制的协同作用提高了光催化活性. 综上, 本文为设计空心S型异质结实现光催化氧化还原反应来提升太阳能的转化利用提供参考.

关键词: S型异质结, 内建电场, 空心核壳结构, 多金属氧酸盐, 苯甲醇氧化

Abstract:

Simultaneous generation of clean energy, H₂, and organic products holds immense potential in the realm of photocatalysis. The S-scheme heterojunction stands out for these dual-function applications due to its robust redox capacity, facilitating both the water reduction reaction and organic oxidation reactions. In this study, a Keggin-type polymetallic oxide, H₃PW₁₂O₄₀ hollow dodecahedron (KPW), was synthesized using a hydrothermal approach. Subsequently, cadmium sulfide (CdS) nanoparticles averaging 15 nm in size were integrated in situ onto the KPW shell, resulting in the creation of a core-shell KPW@CdS S-scheme heterojunction. This optimized composite showcased a hydrogen evolution rate of 18.7 mmol g^-1 h^-1, alongside a value-added product, benzaldehyde, with a yield of 17.5 mmol g^-1 h^-1 substantially surpassing the performance of standalone CdS. This S-scheme junction, featuring a pronounced internal electronic field, emerges between the KPW and CdS. It significantly enhances the segregation of photogenerated carriers while preserving formidable redox capability. Furthermore, the hollow structure augments light absorption and utility, and the core-shell architecture delivers dual reduction and oxidation sites. As a result, the interplay between the hollow core-shell configuration and the S-scheme mode intensifies the photocatalytic activity. This research provides an innovative approach to crafting hollow S-scheme heterojunctions, aiming to optimize photocatalytic redox reactions for effective solar energy utilization.

Key words: S-scheme heterojunction, Internal electric field, Hollow core-shell structure, Polyoxometalate, Benzyl alcohol oxidation

孙丽娟, 于晓慧, 唐丽永, 王伟康, 刘芹芹. 构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应[J]. 催化学报, 2023, 52: 164-175.

Lijuan Sun, Xiaohui Yu, Liyong Tang, Weikang Wang, Qinqin Liu. Hollow dodecahedron K₃PW₁₂O₄₀/CdS core-shell S-scheme heterojunction for photocatalytic synergistic H₂ evolution and benzyl alcohol oxidation[J]. Chinese Journal of Catalysis, 2023, 52: 164-175.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64507-3

https://www.cjcatal.com/CN/Y2023/V52/I9/164

图/表 9

Scheme 1. Schematic of the S-scheme heterojunction for photocatalytic synergistic HER and BA oxidation reaction under ambient conditions.

Fig. 1. (a) Schematic of CSK heterojunctions preparation process. TEM images of CdS (b), KPW (c), and CSK-3 (d). HRTEM images (e) and elemental mapping (f) of CSK-3.

Fig. 2. XRD patterns (a) and FT-IR spectra (b) of CdS, KPW, and CSK-x heterojunctions. (c) XPS full spectra of different samples. XPS high-resolution spectra of Cd 3d (d), S 2p (e), K 2p (f), P 2p (g), W 4f (h), and O 1s (i) of different samples.

Fig. 3. (a) Time-caused photocatalytic H2 production activity. H2 and BAD production rates of different samples (b) and under different light wavelengths (c-f). Long-term light irradiation experiments (g) and comparison of photocatalytic HER coupled with BA oxidation reaction activity over various photocatalysts (h).

Fig. 4. Photocurrent density with and without addition of H2O2 for CdS (a), CSK-3 (b), and KPW (c). Surface charge densities (d), SPV spectra (e) and IEF intensities (f) of CdS, CSK-3, and KPW.

Fig. 5. Photocurrent (a), photocurrent decay (b), EIS curves (c), PL spectra (d), TR-PL spectra (e), and TPV spectra (f) of CdS, CSK-3, and KPW samples.

Fig. 6. DRS (a) and colors (b) of different samples. (c) Tauc plots of KPW and CdS. (d-f) VB-XPS spectra of CdS, CSK-3, and KPW samples. (g) Possible band structure over CSK-3.

Fig. 7. (a,b) In-situ XPS spectra of Cd 3d and W 4f of different samples. DMPO-·O2- (c) and DMPO-·OH (d) of different samples.

Fig. 8. Possible mechanism of the CSK-3 S-scheme heterojunction for photocatalytic synergistic H2 evolution and BA oxidation.

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构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应

Hollow dodecahedron K₃PW₁₂O₄₀/CdS core-shell S-scheme heterojunction for photocatalytic synergistic H₂ evolution and benzyl alcohol oxidation

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