S-型分级多孔CdS/UiO-66光催化剂的构建实现4-硝基苯胺的高效还原

doi:10.1016/S1872-2067(20)63661-0

催化学报 ›› 2021, Vol. 42 ›› Issue (1): 78-86.DOI: 10.1016/S1872-2067(20)63661-0

S-型分级多孔CdS/UiO-66光催化剂的构建实现4-硝基苯胺的高效还原

魏晋欣^a^,^b, 陈雅文^a^,^b, 张鸿洋^a^,^b, 庄赞勇^a^,^b^,^*(), 于岩^a^,^b^,^#()

^a福州大学新校区材料科学与工程学院, 福建福州350108
^b福州大学生态材料先进技术重点实验室, 福建福州350108

收稿日期:2020-03-11 接受日期:2020-04-25 出版日期:2021-01-18 发布日期:2021-01-18
通讯作者: 庄赞勇,于岩
基金资助:
国家自然科学基金(U1905215);国家自然科学基金(51772053);国家自然科学基金(51672046)

Hierarchically porous S-scheme CdS/UiO-66 photocatalyst for efficient 4-nitroaniline reduction

Jinxin Wei^a^,^b, Yawen Chen^a^,^b, Hongyang Zhang^a^,^b, Zanyong Zhuang^a^,^b^,^*(), Yan Yu^a^,^b^,^#()

^aCollege of Materials Science and Engineering, Fuzhou University, New Campus, Fuzhou 350108, Fujian, China
^bKey Laboratory of Eco-Materials Advanced Technology, Fuzhou University, Fuzhou 350108, Fujian, China

Received:2020-03-11 Accepted:2020-04-25 Online:2021-01-18 Published:2021-01-18
Contact: Zanyong Zhuang,Yan Yu
About author:^#E-mail: yuyan_1972@126.com
^*E-mail: zyzhuang@fzu.edu.cn;
Supported by:
National Natural Science Foundation of China(U1905215);National Natural Science Foundation of China(51772053);National Natural Science Foundation of China(51672046)

摘要/Abstract

摘要：

金属有机框架(MOFs)材料因其高孔隙率特性在气体吸附分离、药物传递、催化等领域具有广泛应用. 近年来, 将功能化纳米颗粒(NPs)封装在MOFs中的研究在催化领域引起了科学家的兴趣. 其中, 较大比表面积的MOFs可以为NPs的分散和固定提供理想的平台, 而NPs反过来可以为催化反应引入更多的活性位点, 提高催化效率. 然而, MOFs本身的孔隙常局限于微孔(< 2 nm), 这极大地限制了NPs在MOFs孔隙中的有效封装. 因此, 设计并制备含有介孔(2-50 nm)或大孔(> 50 nm)的多级孔MOFs, 揭示其孔径大小对复杂NPs/MOFs复合催化剂催化性能的影响具有重要意义. 然而, 具有不同孔径MOFs的可控制备具有巨大挑战性, MOFs孔径如何影响和调控NPs/MOFs复合材料催化活性是一个悬而未决的科学问题.
本文结合金属离子刻蚀法和调控配体法设计了两种具有不同孔径(大孔和介孔)的UiO-66, 并系统研究了孔径大小对CdS NPs的分布以及所形成的复合催化剂CdS/UiO-66的催化性能的影响及机制. 我们首先阐明了UiO-66调控孔径后影响和修饰CdS NPs的空间分布: 对于具有开放大孔结构的UiO-66纳米笼, CdS NPs倾向于自发沉积在UiO-66纳米笼内壁上. 相比之下, CdS NPs则主要附着于介孔UiO-66的外表面. 据此, 具有大孔和介孔结构的CdS/UiO-66表现出不同的光催化性能. 以光还原4-硝基苯胺反应为例, 大孔CdS/UiO-66的反应速率常数是介孔和实心样品的3-13倍, 且优于许多文献报道的CdS复合材料催化剂, 表明大孔结构在制备高效复合催化材料上的潜在优势. 通过光吸收能力、能级结构等计算表征, 该催化剂的电子空穴对传输遵循S-型异质结光催化机制; 大孔CdS/UiO-66具有较高光催化活性可归因于纳米笼对NPs的限域效应, 即CdS被限制在UiO-66纳米笼内, 缩短了催化剂与底物之间的电子传输距离; 空心纳米笼结构则保护其内部的CdS NPs免受光腐蚀的影响, 进而获得较高的催化效率和循环稳定性. 可见, 本文提出了一种结合离子刻蚀法和调控配体法获得具有不同孔径MOFs的有效策略, 阐明了调控MOFs的孔径尺寸可以影响NPs的空间分布, 是制约其性能的关键因素, 有望为高效催化剂的设计及催化机制的研究提供新的依据.

关键词: 孔尺寸效应, 纳米限域, 多级孔金属有机框架材料, 纳米粒子/金属有机框架复合材料, 纳米笼

Abstract:

Unveiling the pore-size performance of metal organic frameworks (MOFs) is imperative for controllable design of sophisticated catalysts. Herein, UiO-66 with distinct macropores and mesopores were intentionally created and served as substrates to create advanced CdS/UiO-66 catalysts. The pore size impacted the spatial distribution of CdS nanoparticles (NPs): CdS tended to deposit on the external surface of mesoporous UiO-66, but spontaneously penetrated into the large cavity of macroporous UiO-66 nanocage. Normalized to unit amount of CdS, the photocatalytic reaction constant of macroporous CdS/UiO-66 over 4-nitroaniline reduction was ~3 folds of that of mesoporous counterpart, and outperformed many other reported state-of-art CdS-based catalysts. A confinement effect of CdS NPs within UiO-66 cage could respond for its high activity, which could shorten the electron-transport distance of NPs-MOFs-reactant, and protect the active CdS NPs from photocorrosion. The finding here provides a straightforward paradigm and mechanism to rationally fabricate advance NPs/ MOFs for diverse applications.

Key words: Pore-size Effect, Nanoconfinement, Hierarchically porous MOFs, NPs/MOFs, Nanocage

魏晋欣, 陈雅文, 张鸿洋, 庄赞勇, 于岩. S-型分级多孔CdS/UiO-66光催化剂的构建实现4-硝基苯胺的高效还原[J]. 催化学报, 2021, 42(1): 78-86.

Jinxin Wei, Yawen Chen, Hongyang Zhang, Zanyong Zhuang, Yan Yu. Hierarchically porous S-scheme CdS/UiO-66 photocatalyst for efficient 4-nitroaniline reduction[J]. Chinese Journal of Catalysis, 2021, 42(1): 78-86.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63661-0

https://www.cjcatal.com/CN/Y2021/V42/I1/78

图/表 6

Scheme 1. Scheme illustrating the preparation of CdS/UiO-66 hybrids with distinct macro- and meso-pores following similar procedure.

Fig. 1. TEM (a) and elemental mapping (b) of Mac-UiO; TEM (c), elemental mapping (d) and HRTEM (e) of Mac-Cd/UiO; N2 adsorption-desorption isotherms and pore size distribution of Mac-UiO (f); TEM (g) and elemental mapping (h) of Meso-UiO(N); TEM (i), elemental mapping (j) and HRTEM (k) of Mes-Cd/UiO(N); N2 adsorption-desorption isotherms and pore size distribution of Mes-UiO(N) (l).

Fig. 2. The photocatalytic reduction of 4-nitroaniline (a); the photocatalytic efficiency (b) and corresponding rate constant (c) of 4-nitroaniline reduction with different catalysts (k); normalized catalytic performance with k/Cd% as the benchmark (d); DRS of tested samples (e); TPR of tested samples (f); EIS curves of tested samples (g), the inset of (g) show the zoomed-in EIS for ZRe = 0-5000 Ohm.

Scheme 2. Schematic illustration of the S-scheme dominated photocatalytic mechanism over CdS/UiO-66.

Fig. 3. SEM (a), TEM images (b), and Linear EDS results (c) of Mac-UiO; SEM (d), TEM images (e), and Linear EDS results (f) of Mac/Cd-UiO; Elemental mapping images of Zr, W and Cd in a single crystal of Mac/Cd-UiO (g-j).

Fig. 4. Circulating experiments of Mac-Cd/UiO (a), Mes-Cd/UiO(N) (b), S-Cd/UiO (c) and S-Cd/UiO(N) (d), respectively; catalytic efficiency in 1st cycle and after 5th cycles of four samples (e); schematic diagram of macro-, meso-, solid samples with different CdS location (f).

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S-型分级多孔CdS/UiO-66光催化剂的构建实现4-硝基苯胺的高效还原

Hierarchically porous S-scheme CdS/UiO-66 photocatalyst for efficient 4-nitroaniline reduction

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