三元复合材料Ni2P@UiO-66-NH2/Zn0.5Cd0.5S的合成及其显著提升光催化产氢性能

doi:10.1016/S1872-2067(21)63912-8

催化学报 ›› 2022, Vol. 43 ›› Issue (5): 1295-1305.DOI: 10.1016/S1872-2067(21)63912-8

三元复合材料Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S的合成及其显著提升光催化产氢性能

王爱霞^a, 张临河^a, 李旭力^a, 高旸钦^a, 李宁^a, 卢贵武^b, 戈磊^a^,^*()

^a中国石油大学(北京)新能源与材料学院, 重质油加工国家重点实验室, 北京102249
^b中国石油大学(北京)理学院, 物理系, 北京102249

收稿日期:2021-07-01 接受日期:2021-07-19 出版日期:2022-05-18 发布日期:2022-03-23
通讯作者: 戈磊
基金资助:
国家重点研发计划(2019YFC1907602);中国石油勘探开发研究院(2018YCQ05);国家自然科学基金(51572295);国家自然科学基金(21273285);国家自然科学基金(21003157)

Synthesis of ternary Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S composite materials with significantly improved photocatalytic H₂ production performance

Aixia Wang^a, Linhe Zhang^a, Xuli Li^a, Yangqin Gao^a, Ning Li^a, Guiwu Lu^b, Lei Ge^a^,^*()

^aState Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China
^bCollege of Science, China University of Petroleum Beijing, Beijing 102249, China

Received:2021-07-01 Accepted:2021-07-19 Online:2022-05-18 Published:2022-03-23
Contact: Lei Ge
Supported by:
National Key R&D Program of China(2019YFC1907602);National Natural Science Foundation of China(51572295);National Natural Science Foundation of China(21273285);National Natural Science Foundation of China(21003157)

摘要/Abstract

摘要：

低成本、高性能的光催化制氢反应杂化材料的设计与构建, 对于氢能的大规模应用具有极其重要的意义. Zn_0.5Cd_0.5S固溶体具有如稳定性较高、合成简单、性能优异等许多优点, 但是存在比表面积低、电荷复合速度快等缺陷, 影响了Zn_0.5Cd_0.5S的开发利用. 金属有机骨架(MOF)是一种新兴材料, 与无机半导体相比, MOF具有表面积大、多孔结构可调节和结构多样等优点. 因此, 研究者致力于将纳米颗粒包裹进MOF材料中, 来改善其催化活性. UiO-66-NH₂是一种典型的由锆氧羰基团簇和对苯二甲酸盐组成的MOF, 具有多孔性、优异的高温高压稳定性和半导体性能. 过渡金属磷化物由于具有独特的结构和电子性质, 近年来被认为是有望能够替代贵金属的产氢助催化剂, 其中磷化镍(Ni₂P)纳米颗粒助催化剂就表现出优异的催化性能.

本文采用原位溶剂热法将单分散、小尺寸、非贵过渡金属磷化物Ni₂P包裹在MOF(UiO-66-NH₂)中, 构建了核壳助催化剂材料Ni₂P@UiO-66-NH₂, 然后将其修饰到Zn_0.5Cd_0.5S硫化物上, 从而设计和制备了Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S三元复合材料. 对得到的复合光催化材料进行了X射线衍射测试, 结果表明, 各衍射峰的位置都与标准卡片对应, 说明成功合成了Zn_0.5Cd_0.5S和UiO-66-NH₂材料. 采用扫描电子显微镜和透射电子显微镜对Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S三元体系进行分析, 结果表明, Zn_0.5Cd_0.5S呈纳米棒状, 测量得到Ni₂P磷化物的(111)晶面条纹间距为0.22 nm, 说明成功合成了三元复合体系. XPS测试结果表明, Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S三元复合体系中的元素结合能与文献报道一致, 说明该三元体系中的元素化学结合环境与预期相符.

通过光电和化学表征, 证实了三元复合材料具有良好的动力学制氢性能. 10% Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S三元复合体系的光催化产氢性能率为40.91 mmol·g^‒1·h^‒1, 420 nm可见光照射下的表观量子效率达到13.57%. 负载核壳助催化材料Ni₂P@UiO-66-NH₂增加了三元材料的比表面积, 提供了丰富的反应位点, 在三元复合体系内形成了有效的电荷转移通道, 有利于催化剂的高效产氢. 本文证明了三元复合体系的形成有利于高效催化反应的发生, 为高性能光催化剂材料的制备提供了新的视角.

关键词: 磷化镍, UiO-66-NH₂, Zn_0.5Cd_0.5S纳米棒, 产氢, 三元光催化剂

Abstract:

abstract The design and construction of low-cost and high-performance hybrid materials for the photocatalytic hydrogen production reaction (HER) are extremely important for the large-scale application of hydrogen energy. Metal-organic frameworks (MOFs) are considered to be potential photocatalytic materials. Herein, monodisperse, small size, non-precious metal transition metal phosphide Ni₂P is encapsulated into a typical MOF (UiO-66-NH₂) as a hybrid core-shell cocatalyst to modify Zn_0.5Cd_0.5S for photocatalytic hydrogen production. Ni₂P is wrapped in UiO-66-NH₂ via an in situ solvothermal method, and Zn_0.5Cd_0.5S sulfide is decorated with a core-shell Ni₂P@UiO-66-NH₂cocatalyst to obtain ternary Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S composite materials. Photoelectric and chemical characterization confirms that the ternary composites have good kinetic hydrogen production performance. The hydrogen production rate of 10% 10 mg Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S reaches 40.91 mmol·g^-1·h^-1 with an apparent quantum efficiency at 420 nm of 13.57%. The addition of 10 mg Ni₂P@UiO-66-NH₂ increases the surface area of the ternary material, providing abundant reaction sites and forming an efficient charge transfer channel, which is conducive to efficient hydrogen production by the ternary photocatalysts. It is shown that the formation of a ternary composite system is beneficial to the occurrence of an efficient catalytic reaction. This study provides a new perspective for the construction of high-performance photocatalytic materials.

Key words: Ni₂P, UiO-66-NH₂, Zn_0.5Cd_0.5S, Hydrogen evolution, Ternary photocatalyst

王爱霞, 张临河, 李旭力, 高旸钦, 李宁, 卢贵武, 戈磊. 三元复合材料Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S的合成及其显著提升光催化产氢性能[J]. 催化学报, 2022, 43(5): 1295-1305.

Aixia Wang, Linhe Zhang, Xuli Li, Yangqin Gao, Ning Li, Guiwu Lu, Lei Ge. Synthesis of ternary Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S composite materials with significantly improved photocatalytic H₂ production performance[J]. Chinese Journal of Catalysis, 2022, 43(5): 1295-1305.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63912-8

https://www.cjcatal.com/CN/Y2022/V43/I5/1295

图/表 12

Fig. 1. XRD patterns of different samples. (a) Pure UiO-66-NH2 (U), 10 mg Ni2P@UiO-66-NH2 (10 N@U) and pure Ni2P (N); (b) Zn0.5Cd0.5S (ZCS), 10% 10mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (10% 10 N@U/ZCS) and 20% 10mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (20% 10 N@U/ZCS).

Fig. 2. (a) SEM result for UiO-66-NH2 (U); (b) SEM result for 10 mg Ni2P@UiO-66-NH2 (10 N@U); (c) TEM result for UiO-66-NH2 (U); TEM (d), HRTEM (e) results, and EDX mapping (f) of the 10mg Ni2P@UiO-66-NH2 (10 N@U) sample.

Fig. 3. (a) TEM result for Zn0.5Cd0.5S (ZCS) (HRTEM image in illustration); TEM (b) and HRTEM (c) images for 20% 10mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (20% 10 N@U/ZCS).

Fig. 4. XPS spectra of the 10% 10mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S photocatalyst (10% 10 N@U/ZCS). (a) Zn 2p; (b) Cd 3d; (c) S 2p; (d) Zr 3d; (e) C 1s; (f) Ni 2p; (g) P 2p; (h) survey.

Fig. 5. Diffuse reflectance spectra of pure Zn0.5Cd0.5S (ZCS) and 10% 10 mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (10% 10 N@U/ZCS). Inset: spectra of pure UiO-66-NH2 (U) and 10 mg Ni2P@UiO-66-NH2 (10 N@U).

Fig. 6. MS curves of pure Zn0.5Cd0.5S (ZCS) (a) and pure UiO-66-NH2 (U) (b).

Fig. 7. (a) Transient photocurrent diagrams for Zn0.5Cd0.5S (ZCS), 10% 10mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (10% 10 N@U/ZCS) (with, inset, the transient photocurrent diagrams of UiO-66-NH2 (U), and 10mg Ni2P@UiO-66-NH2 (10 N@U)); (b) Electrochemical impedance diagrams for UiO-66-NH2 (U), 10mg Ni2P@UiO-66-NH2 (10 N@U), pure Zn0.5Cd0.5S (ZCS) and 10% 10mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (10% 10 N@U/ZCS).

Fig. 8. SPV spectra of Zn0.5Cd0.5S (ZCS) and 10% 10mg Ni2P@UiO-66-NH2/ Zn0.5Cd0.5S (10% 10 N@U/ZCS).

Fig. 9. Hydrogen production rates under visible-light illumination. (a) With different contents of x mg Ni2P@UiO-66-NH2 (x N@U) catalysts; (b) x% 10mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (x% 10 N@U/ZCS) with different contents of 10 N@U cocatalyst.

Fig. 10. Hydrogen production cycles (a) and quantum efficiency (b) at 420 nm for 10% 10mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (10% 10 N@U/ZCS).

Fig. 11. ESR spectra of e- and h+ signals of pure Zn0.5Cd0.5S (ZCS) and 10% 10 mg Ni2P@UiO-66-NH2/Zn0.5Cd0.5S (10% 10 N@U/ZCS) ternary photocatalysts at room temperature: e- signal with light irradiation time of 0 min (a), 5 min (b) and 10 min (c); h+ signal with light irradiation time of 0 min (d), 5 min (e) and 10 min (f).

Fig. 12. Electron transfer and hydrogen production mechanism of N@U/ZCS under visible light irradiation.

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三元复合材料Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S的合成及其显著提升光催化产氢性能

Synthesis of ternary Ni₂P@UiO-66-NH₂/Zn_0.5Cd_0.5S composite materials with significantly improved photocatalytic H₂ production performance

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