CdS/WO3复合材料用于光催化选择性芳香醇氧化及析氢反应

doi:10.1016/S1872-2067(21)63989-X

催化学报 ›› 2022, Vol. 43 ›› Issue (7): 1851-1859.DOI: 10.1016/S1872-2067(21)63989-X

CdS/WO₃复合材料用于光催化选择性芳香醇氧化及析氢反应

吴玉兰, 祁明雨, 谭昌龙, 唐紫蓉(), 徐艺军()

福州大学化学学院, 能源与环境光催化国家重点实验室, 福建福州350116

收稿日期:2021-10-08 接受日期:2021-12-06 出版日期:2022-07-18 发布日期:2022-05-20
通讯作者: 唐紫蓉,徐艺军
基金资助:
国家自然科学基金(22172030);国家自然科学基金(22072023);国家自然科学基金(21872029);国家自然科学基金(U1463204);国家万人计划科技创新领军人才(00387072);闽江学者特聘教授奖励计划;福建省自然科学基金(2017J07002);福建省自然科学基金(2019J01631)

Photocatalytic selective oxidation of aromatic alcohols coupled with hydrogen evolution over CdS/WO₃ composites

Yu-Lan Wu, Ming-Yu Qi, Chang-Long Tan, Zi-Rong Tang(), Yi-Jun Xu()

College of Chemistry, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350116, Fujian, China

Received:2021-10-08 Accepted:2021-12-06 Online:2022-07-18 Published:2022-05-20
Contact: Zi-Rong Tang, Yi-Jun Xu
Supported by:
Natural Science Foundation of China(22172030);Natural Science Foundation of China(22072023);Natural Science Foundation of China(21872029);Natural Science Foundation of China(U1463204);Program for National Science and Technology Innovation Leading Talents(00387072);1st Program of Fujian Province for Top Creative Young Talents, the Program for Leading Talents of Fujian Universities, the Award Program for Minjiang Scholar Professorship;Natural Science Foundation of Fujian Province(2017J07002);Natural Science Foundation of Fujian Province(2019J01631)

摘要/Abstract

摘要：

使用可再生太阳能将水转化为清洁的氢燃料被认为是解决当前化石能源枯竭和环境污染问题的有效策略之一. 然而在传统的光催化分解水反应体系中, 由于缓慢的水氧化半反应, 整体的析氢效率较低. 引入光生空穴牺牲试剂虽然可以在一定程度上提高体系的光催化析氢效率, 但同时也造成了光生空穴氧化能力的浪费. 近年来, 生物质及其衍生物平台分子的光催化选择性氧化引起了人们的广泛关注. 其中苯甲醇选择性氧化为苯甲醛是重要的化学反应, 产物苯甲醛是一种高附加值的关键中间体, 被广泛应用于食品、医药和化妆品行业. 基于此, 用生物质及其衍生物平台分子代替光生空穴牺牲剂构建一个产氢和有机合成耦合的双功能光催化氧化还原体系, 以充分利用光生电子和空穴, 同时获得清洁的氢燃料和高附加价值的化学品, 为解决上述问题提供了一条理想途径.

作为典型的窄带隙(E_g = 2.4 eV)硫化物半导体, CdS具有合适的带边位置, 是一种理想的光催化产氢半导体材料. 但CdS由于自身光腐蚀现象严重、光生电子和空穴容易复合等缺点限制了其在光催化产氢领域的应用. WO₃因其成本低、稳定性良好和氧化能力优异而被广泛关注. 通过构建Z型异质结CdS/WO₃复合光催化剂, 既有利于分离光生电子和空穴, 又能减缓CdS的光腐蚀现象, 从而实现高效的光催化析氢和选择性将芳香醇氧化成芳香醛的耦合催化反应.

本文采用溶剂热法将CdS纳米颗粒原位生长于WO₃纳米片表面, 制备了一种新型的直接Z型异质结CdS/WO₃复合光催化剂, 用于双功能耦合光催化氧化还原体系, 同时实现光催化还原析氢和氧化合成芳香醛. 结果表明, 引入WO₃后明显抑制CdS的光腐蚀现象, 从而改善了CdS的光催化性能. 此外, WO₃与CdS之间形成直接Z型异质结构, 有效提高光生电子和空穴的分离效率, 并保留了光生载流子较强的氧化还原能力. 优化后的CdS/WO₃复合材料对产氢和芳香醇选择性氧化表现出较好的光催化活性. 循环活性实验以及反应前后催化剂的表征结果证明, CdS/WO₃复合材料具有良好的光催化稳定性. 另外, 电子自旋共振光谱技术对反应过程中的自由基中间体进行原位监测, 发现以碳为中心的自由基是光催化氧化苯甲醇生成苯甲醛过程中关键的自由基中间体.

本文为进一步设计新型高效的双功能光催化氧化还原体系, 同时合成清洁太阳能燃料和高附加值的化学品提供启发.

关键词: 光催化剂, 芳香醇, Z型异质结, 复合光催化剂, 析氢

Abstract:

Simultaneously utilizing photogenerated electrons and holes to convert renewable biomass and its derivatives into corresponding value-added products and hydrogen (H₂) is a promising strategy to deal with the energy and environmental crisis. Herein, we report a facile hydrothermal method to construct a direct Z-scheme CdS/WO₃ binary composite for photocatalytic coupling redox reaction, simultaneously producing H₂ and selectively converting aromatic alcohols into aromatic aldehydes in one pot. Compared with bare CdS and WO₃, the CdS/WO₃ binary composite exhibits significantly enhanced performance for this photocatalytic coupled redox reaction, which is ascribed to the extended light harvesting range, efficient charge carrier separation rate and optimized redox capability of CdS/WO₃ composite. Furthermore, the feasibility of converting various aromatic alcohols to corresponding aldehydes coupled with H₂ evolution on the CdS/WO₃ photocatalyst is proved and a reasonable reaction mechanism is proposed. It is hoped that this work can provide a new insight into the construction of direct Z-scheme photocatalysts to effectively utilize the photogenerated electrons and holes for photocatalytic coupled redox reaction.

Key words: Photocatalyst, Aromatic alcohols, Z-scheme, Composite photocatalyst, Hydrogen evolution

吴玉兰, 祁明雨, 谭昌龙, 唐紫蓉, 徐艺军. CdS/WO₃复合材料用于光催化选择性芳香醇氧化及析氢反应[J]. 催化学报, 2022, 43(7): 1851-1859.

Yu-Lan Wu, Ming-Yu Qi, Chang-Long Tan, Zi-Rong Tang, Yi-Jun Xu. Photocatalytic selective oxidation of aromatic alcohols coupled with hydrogen evolution over CdS/WO₃ composites[J]. Chinese Journal of Catalysis, 2022, 43(7): 1851-1859.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63989-X

https://www.cjcatal.com/CN/Y2022/V43/I7/1851

图/表 6

Fig. 1. (a) Schematic diagram of the preparation process of CdS/WO3 composites. FESEM (b) and HRTEM (c) images of CdS/WO3-20 composite. (d) The magnification image of the selected area in the red circle of panel c. EDS spectrum (e) and Element mapping (f) of Cd, S, W, and O of CdS/WO3-20 composite.

Fig. 2. (a) XRD patterns of WO3, CdS and CdS/WO3; XPS spectra of Cd 3d (b), S 2p (c), W 4f (d) and O 1s (e) of the pure CdS (bottom), the pure WO3 (bottom) and CdS/WO3-20 composite(top). (f) DRS spectra of the WO3, CdS and CdS/WO3-x composites.

Fig. 3. (a) The results of photocatalytic performance tests of H2 evolution integrated with selective BA oxidation into BAD over bare WO3, bare CdS and CdS/WO3-x composites. (b) Photocatalytic cyclic tests over CdS/WO3-20 composite. Reaction conditions: 5 mg catalysts, 100 μmol BA, 10 mL H2O, full spectrum, irradiation for 2 h.

Table 1 Photocatalytic H2 evolution integrated with a series of biomass-derived alcohols oxidation.

Entry	Alcohol substrate	Yield of oxidation product (μmol)		Yield of H₂(μmol)
1	1-phenylethanol	Acetophenone	79.9	103.1
2	p-methoxybenzyl alcohol	Anisaldehyde	76.3	102.3
3	p-methylbenzyl alcohol	p-methyl benzaldehyde	67.9	95.2
4	p-fluorobenzyl alcohol	p-fluorobenzaldehyde	60.6	91.6
5	Furfuryl alcohol	Furfural	78.0	82.3
6	p-chlorobenzyl alcohol	p-chlorobenzaldehyde	43.5	87.2

Fig. 4. (a) Polarization curves of bare CdS, bare WO3 and CdS/WO3-20 composite. (b) Photocurrent density under full spectrum. (c) The EIS Nyquist plots of bare CdS, bare WO3 and CdS/WO3-20 composite. EPR spectra of DMPO-•O2- (d), DMPO-•OH (e) and EPR spectra (f) of DMPO-CH(OH)Ph over bare CdS, bare WO3 and CdS/WO3-20 composite with light irradiation.

Fig. 5. The schematic diagram of the charge transfers in CdS/WO3-20 heterojunction (left) and proposed reaction mechanism for photocatalytic BA oxidation integrated with H2 evolution over CdS/WO3 composite (right).

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CdS/WO₃复合材料用于光催化选择性芳香醇氧化及析氢反应

Photocatalytic selective oxidation of aromatic alcohols coupled with hydrogen evolution over CdS/WO₃ composites

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