阳离子镍基MOF自组装CdS/PFC-8催化剂用于可见光光催化选择性苯甲醇氧化耦合产氢

doi:10.3866/PKU.WHXB202205039

物理化学学报 >> 2023, Vol. 39 >> Issue (4): 2205039.doi: 10.3866/PKU.WHXB202205039

所属专题：庆祝谢有畅教授九十华诞专刊

阳离子镍基MOF自组装CdS/PFC-8催化剂用于可见光光催化选择性苯甲醇氧化耦合产氢

项景超¹^,²^,³^,⁴, 李静君²^,³^,⁴, 杨雪²^,³^,⁴, 高水英²^,³^,⁴^,*(), 曹荣²^,³^,⁴^,*()

¹ 福建师范大学化学与材料学院, 福州 350007
² 中国科学院福建物质结构研究所结构化学国家重点实验室, 福州 350002
³ 中国科学院大学, 北京 100049
⁴ 中国福建光电信息科学技术创新实验室, 福州 350108

收稿日期:2022-05-16 录用日期:2022-07-07 发布日期:2022-07-14
通讯作者: 高水英,曹荣 E-mail:gaosy@fjirsm.ac.cn;rcao@fjirsm.ac.cn
基金资助:
国家重点研究开发计划(2021YFA1501500);国家重点研究开发计划(2017YFA0700102);国家自然科学基金(22033008);国家自然科学基金(21871263);国家自然科学基金(22071245);国家自然科学基金(22171265);中国福建光电信息科学与技术创新实验室(2021ZZ103)

Cationic Ni-MOF-Assembled CdS/PFC-8 Catalyst for Photocatalytic Hydrogen Production with Selective Benzyl Alcohol Oxidation under Visible Light

Jingchao Xiang¹^,²^,³^,⁴, Jingjun Li²^,³^,⁴, Xue Yang²^,³^,⁴, Shuiying Gao²^,³^,⁴^,*(), Rong Cao²^,³^,⁴^,*()

¹ College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China
² State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
³ University of the Chinese Academy of Sciences, Beijing 100049, China
⁴ Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, China

Received:2022-05-16 Accepted:2022-07-07 Published:2022-07-14
Contact: Shuiying Gao, Rong Cao E-mail:gaosy@fjirsm.ac.cn;rcao@fjirsm.ac.cn
Supported by:
the National Key Research and Development Program of China(2021YFA1501500);the National Key Research and Development Program of China(2017YFA0700102);the National Natural Science Foundation of China(22033008);the National Natural Science Foundation of China(21871263);the National Natural Science Foundation of China(22071245);the National Natural Science Foundation of China(22171265);Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ103)

摘要/Abstract

摘要：

可见光驱动的光催化制氢与有机氧化合成相结合由于其环境友好性和可持续性而极具吸引力，它可以在温和的条件下同时产生清洁的氢气燃料和高价值化学品，而无需牺牲剂。半导体材料和金属有机骨架(MOFs)材料由于其性能和优势，在光催化领域得到了广泛的应用。在这项工作中，我们通过静电自组装成功合成了一种名为CdS/PFC-8的新型有效催化剂。其中，PFC-8作为镍基金属有机骨架，CdS/PFC-8复合材料作为无贵金属催化剂，在可见光下具有优异的光催化制氢和苯甲醇氧化性能。对CdS/PFC-8复合材料进行了一系列催化表征。X射线衍射(XRD)和扫描电子显微镜(SEM)结果表明了CdS/PFC-8复合材料的成功合成。X射线光电子能谱(XPS)表明了CdS纳米棒与PFC-8之间存在一定的界面相互作用。通过紫外-可见漫反射光谱(DRS)、光致发光光谱(PL)和电化学测试对光电性能进行了表征，表明CdS/PFC-8复合材料的可见光响应和光催化可行性。对不同催化剂的光催化实验结果进行比较，在可见光下，CdS/PFC-8复合材料将H₂的产生与苯甲醇的选择性氧化耦合, 表现出显著的H₂产率3376 μmol∙g^-1∙h^-1和苯甲醛产率4120 μmol∙g^-1∙h^-1，大大高于单一CdS。对反应前后催化剂的变化进行分析，推测出PFC-8中的镍可能作为催化活性位点来提高催化活性。此外，讨论了可能的光催化反应机理。这项工作突出了结合半导体和MOF功能以增强光催化活性的优势。

关键词: 光催化, 金属有机框架, 硫化镉, 氢气, 苯甲醇

Abstract:

Visible-light-driven photocatalytic H₂ evolution coupled with oxidative organic synthesis is attracting extensive attention owing to the environmental friendliness and sustainability of these processes, which can coproduce clean H₂ fuel and high-value chemicals under mild conditions without requiring sacrificial agents. Semiconductor materials and metal-organic framework (MOF) materials have been widely used in photocatalys owing to their properties and advantages. In this work, we successfully synthesized a novel effective catalyst (named CdS/PFC-8) by electrostatic self-assembly. Among the components of the CdS/PFC-8 composite, PFC-8 was a nickel-based MOF. The CdS/PFC-8 composite, as a noble metal-free catalyst, enabled excellent photocatalytic H₂ evolution and benzyl alcohol oxidation under visible light. A series of catalytic characterizations were performed with the CdS/PFC-8 composite. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results demonstrated the successful synthesis of the CdS/PFC-8 composite. X-ray photoelectron spectroscopy (XPS) results demonstrated the existence of an interfacial interaction between CdS nanorods and PFC-8. The optoelectronic performance was characterized by ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), photoluminescence (PL) spectroscopy, and electrochemical tests, and the results demonstrated the visible-light response and photocatalytic feasibility of the CdS/PFC-8 composite. The photocatalytic results obtained with different catalysts were compared. Under visible light, the CdS/PFC-8 composite enabled the generation of H₂ with the selective oxidation of benzyl alcohol in a single reaction. It exhibited a remarkable H₂ production rate of 3376 μmol∙g^-1∙h^-1; further, the benzaldehyde yield was 4120 μmol∙g^-1∙h^-1, which is higher than that of CdS alone. Photocatalytic cycling reactions were carried out to verify the activity and stability of the catalysts. The changes in the catalysts before and after the reaction were analyzed, and the results suggested that the nickel in PFC-8 could be used as a catalytically active site to improve the catalytic activity. In addition, the possible photocatalytic reaction mechanism was discussed. This work highlights the advantages of combining the functionalities of semiconductors and MOFs to enhance the photocatalytic activity.

Key words: Photocatalytic, Metal-organic frameworks, Cadmium sulfide, Hydrogen, Benzyl alcohol

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项景超, 李静君, 杨雪, 高水英, 曹荣. 阳离子镍基MOF自组装CdS/PFC-8催化剂用于可见光光催化选择性苯甲醇氧化耦合产氢[J]. 物理化学学报, 2023, 39(4), 2205039. doi: 10.3866/PKU.WHXB202205039

Jingchao Xiang, Jingjun Li, Xue Yang, Shuiying Gao, Rong Cao. Cationic Ni-MOF-Assembled CdS/PFC-8 Catalyst for Photocatalytic Hydrogen Production with Selective Benzyl Alcohol Oxidation under Visible Light[J]. Acta Phys. -Chim. Sin. 2023, 39(4), 2205039. doi: 10.3866/PKU.WHXB202205039

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202205039

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I4/2205039

图/表 9

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Cat.	Light source	Solvent	H₂/(μmol∙g⁻¹∙h⁻¹)	Benzalydehyde/(μmol∙g⁻¹∙h⁻¹)	Sel. (%)	Ref.
CdS/PFC-8	300 W Xe lamp, λ > 420 nm	CH₃CN	3376	4120	99	This work
g-C₃N₄(W)	300 W Xe lamp, λ > 420 nm	CH₃CN	298.7	305.1	–	9
CdS@MoS₂	300 W Xe lamp, λ > 420 nm	CH₃CN	4233	5800	99	10
CdS/MIL-53(Fe)	300 W Xe lamp, λ > 420 nm	CH₃CN	2334	2825	99	19
Ni/CdS/TiO₂@MIL-101	50 W LED blue, λ = 470 nm	CH₃CN	–	18250	–	30
Pt-g-C₃N₄	300 W Xe lamp, λ > 400 nm	H₂O	255	200	90	31
Pt/Zn₃ln₂S₆	300 W Xe lamp, λ > 420 nm	BTF	878.3	921.3	> 93	32
Co-CdS	300 W Xe lamp, λ > 420 nm	CH₃CN	2310	2054.5	86.3	33
Mn_0.25Cd_0.75S/WO₃	300 W Xe lamp, λ > 420 nm	BTF	4680	4700	91	34
CdS/TiO₂/MoS₂	300 W Xe lamp, λ > 420 nm	CH₃CN	21400	22800	> 99	35
TiO₂/Ti₃C₂	300 W Xe lamp, λ > 200 nm	H₂O	3650	3167	90.5	36

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阳离子镍基MOF自组装CdS/PFC-8催化剂用于可见光光催化选择性苯甲醇氧化耦合产氢

Cationic Ni-MOF-Assembled CdS/PFC-8 Catalyst for Photocatalytic Hydrogen Production with Selective Benzyl Alcohol Oxidation under Visible Light

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