超薄ZnTi-LDH纳米片作为一种具有路易斯酸和布朗斯特酸的双功能光催化剂用于串联反应合成N-亚苄基苯胺

doi:10.1016/S1872-2067(23)64449-3

催化学报 ›› 2023, Vol. 49: 102-112.DOI: 10.1016/S1872-2067(23)64449-3

超薄ZnTi-LDH纳米片作为一种具有路易斯酸和布朗斯特酸的双功能光催化剂用于串联反应合成N-亚苄基苯胺

刘成^a, 陈梦宁^a, 时应章^a, 王志文^a, 郭韦^a, 林森^a^,^*(), 毕进红^a^,^b^,^*(), 吴棱^a^,^*()

^a福州大学能源与环境光催化国家重点实验室, 福建福州 350116
^b福州大学环境科学与工程学院, 福建福州 350108

收稿日期:2023-02-08 接受日期:2023-04-30 出版日期:2023-06-18 发布日期:2023-06-05
通讯作者: ^*电子信箱: slin@fzu.edu.cn (林森),wuling@fzu.edu.cn (吴棱),bijinhong@fzu.edu.cn (毕进红).
基金资助:
国家自然科学基金(22272026);国家自然科学基金(22272028);国家自然科学基金(21973013);福建省青年人才支持下项目(00387077)

Ultrathin ZnTi-LDH nanosheet: A bifunctional Lewis and Brönsted acid photocatalyst for synthesis of N-benzylideneanilline via a tandem reaction

Cheng Liu^a, Mengning Chen^a, Yingzhang Shi^a, Zhiwen Wang^a, Wei Guo^a, Sen Lin^a^,^*(), Jinhong Bi^a^,^b^,^*(), Ling Wu^a^,^*()

^aState Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350116, Fujian, China
^bDepartment of Environmental Science and Engineering, Fuzhou University, Fujian 350108, Fujian, China

Received:2023-02-08 Accepted:2023-04-30 Online:2023-06-18 Published:2023-06-05
Contact: ^*E-mail: slin@fzu.edu.cn (S. Lin), wuling@fzu.edu.cn (L. Wu),bijinhong@fzu.edu.cn (J. Bi).
Supported by:
National Natural Science Foundation of China(22272026);National Natural Science Foundation of China(22272028);National Natural Science Foundation of China(21973013);Youth Talent Support Program of Fujian Province(00387077)

摘要/Abstract

摘要：

半导体光催化作为一种绿色可持续方法受到研究者的广泛关注. 由于理论模型与实际催化剂存在较大差异, 探究活性位点与光催化性能之间的关系一直是一个悬而未决的问题, 需要寻找一种合适的材料深入了解该关系. 超薄二维纳米材料因其活性位点占比较高, 且活性位点种类相对简单而被认为是一种理想的模型. 串联催化反应可以在单一体系中进行多步反应, 避免了相对复杂的中间体分离和纯化, 具有较大的经济和环保效益. 在该过程中, 独立的活性位点在不同的催化反应中起着重要的作用. 目前已有一些关于光催化串联反应的研究报道, 基于光催化过程, 一般通过电子空穴分离效率或基于半导体价带理论来揭示, 而活性位点与光催化性能之间的相互作用仍有待进一步研究.

本文制备了两种不同厚度(1.4和4.0 nm)的超薄ZnTi-LDH纳米片用于光催化串联反应合成N-亚苄基苯胺, 研究了该体系中的活性位点-催化性能的相互关系. X射线光电子能谱、红外光谱(FTIR)和电子自旋共振结果表明, 减小ZnTi-LDH纳米片的厚度, 可以暴露出更多的表面羟基和氧空位缺陷, 形成配位不饱和Ti位点. 紫外-可见光漫反射光谱和原位吸附FTIR光谱结果表明, 在ZnTi-LDH纳米片上两种反应物(苯甲醇和硝基苯)能有效地化学吸附并活化. 其中苯甲醇分子通过C‒O···Ti的配位方式吸附并活化在配位不饱和Ti位点(L酸位点)上, 而硝基苯分子以N‒O···H‒O的配位方式吸附并活化表面羟基的氢位点(B酸位点)上. 在该体系中, 光生空穴和光生电子能被有效利用, 分别促进了苯甲醇选择性氧化为苯甲醛和硝基苯选择性还原为苯胺. 阻抗和光电流实验结果表明, ZnTi-LDH纳米片厚度越薄, 越有利于提高光生电子-空穴对的分离效率. 由于其厚度的减小形成了氧空位, 而氧空位作为电子的捕获中心, 促进了光生电子-空穴对的分离. 更薄的ZnTi-LDH纳米片具有更多的活性位点, 不仅有利于反应物的活化, 也有利于光生载流子的分离. 因此, 较薄的ZnTi-LDH纳米片实现了100%的高转化率和96%的高选择性. 从分子水平上提出了该串联反应体系中分子活化协同光催化的机理. 本文不仅为串联反应开发了具有独立活性位点的双功能催化剂, 而且通过从分子水平上研究活性位点与催化性能之间的相互作用, 对光催化机理提供了深入的认识.

关键词: 超薄纳米片, 分子活化, 串联反应, 锌钛水滑石, 半导体光催化

Abstract:

Two ultrathin ZnTi-LDH nanosheets with different thickness (1.4 and 4.0 nm) were prepared to study the interplay between the active site and catalytic performance in photocatalytic synthesis of N-benzylideneanilline via a tandem reaction. ZnTi-LDH nanosheet possesses dual isolated active sites including the coordinatively unsaturated Ti atoms (Lewis acid sites) and the H atoms of OH groups (Brönsted acid sites), achieving the activation of benzyl alcohol and nitrobenzene via C-O···Ti species and N-O···H-O species, respectively. Photogenerated holes and electrons facilitate the oxidation of benzyl alcohol to benzaldehyde and the reduction of nitrobenzene to aniline, respectively. The thinner sample possesses more active sites, facilitating not only the activation of reactants but also the separation of photogenerated carriers. Therefore, a thinner ZnTi-LDH nanosheet shows the high conversion (100%) and the high selectivity (96%). Finally, a synergetic photocatalytic mechanism connected to the molecular activation is illustrated at the molecule level.

Key words: Ultrathin nanosheet, Molecular activation, Tandem reaction, ZnTi-LDH, Semiconductor photocatalysis

刘成, 陈梦宁, 时应章, 王志文, 郭韦, 林森, 毕进红, 吴棱. 超薄ZnTi-LDH纳米片作为一种具有路易斯酸和布朗斯特酸的双功能光催化剂用于串联反应合成N-亚苄基苯胺[J]. 催化学报, 2023, 49: 102-112.

Cheng Liu, Mengning Chen, Yingzhang Shi, Zhiwen Wang, Wei Guo, Sen Lin, Jinhong Bi, Ling Wu. Ultrathin ZnTi-LDH nanosheet: A bifunctional Lewis and Brönsted acid photocatalyst for synthesis of N-benzylideneanilline via a tandem reaction[J]. Chinese Journal of Catalysis, 2023, 49: 102-112.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64449-3

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图/表 11

Scheme 1. Schematic illustration of photocatalytic synthesis of N-benzylideneanilline via a tandem reaction.

Fig. 1. Powder XRD patterns (a), N2 sorption isotherm and pore size distribution (ZT-1: (b), ZT-2: (c)) for the samples.

Fig. 2. SEM (a), TEM (b), HRTEM (c) images with the corresponding intensity profiles, AFM image (d) with the corresponding height profiles for ZT-1.

Fig. 3. (a) UV-vis DRS spectra and corresponding Tauc plots of the samples; The Zn 2p (b), Ti 2p (c) and O 1s (d) XPS spectra of the samples; FTIR (e) and ESR (f) spectra of the samples.

Scheme 2. Band positions of the samples and redox potentials of nitrobenzene (NB), benzyl alcohol (BA) and benzaldehyde (BAD).

Table 1 The proportion of different types of O atoms in the samples.

Type	Binding energy (eV)	ZT-1 (%)	ZT-2 (%)
O-lattice	529.6	18.90	29.70
O-vacancy	530.2	6.30	2.60
O-OH group	531.4	39.40	25.50
O-H₂O	532.1	25.20	34.00
O-CO₃^2-	532.9	10.20	8.20

Fig. 4. Nyquist impedance plots (a) and photocurrent measurements (b) of the samples. (c) In situ FT-IR spectra of pyridine absorption on ZT-1: (1) Degassing stage; (2) Physical and chemical adsorption stage; (3) Chemical adsorption stage. (d) The acid sites in ZT-1 structure. (e) On-off light experiments for the tandem reaction over ZT-1. (f) The experiments about the effect of the molar ratio of benzyl alchol and nitrobenzene to reaction activity.

Table 2 Photocatalytic activity tests for the tandem reaction.

Entry	Catalyst	Temperature (°C)	Atmosphere	hv (λ ≥ 320 nm)	Conversion (%)	Selectivity (%)
1	ZT-1	25	Ar	+	100	96
2	ZT-2	25	Ar	+	76	58
3	ZT-1	25	Ar	λ ≥ 400 nm	18	37
4	ZT-1	25	Air	+	—	—
5	None	25	Ar	+	—	—
6	ZT-1	25	Ar	—	—	—
7	ZT-1	80	Ar	—	—	—

Table 3 Photocatalytic activity tests using various nitroarenes.

Entry	Group (R)	t (h)	Conversion (%)	Selectivity (%)
1	-H	4.0	100	96
2	-Cl	3.0	98	97
3	-Br	3.5	100	95
4	-CH₃	5.0	93	96
5	-OCH₃	5.5	95	97

Fig. 5. UV-vis DRS spectra of ZT-1 after the adsorption of benzyl alcohol (a) and nitrobenzene (b). (c) ESR spectra of the samples. In situ FTIR spectra of benzyl alcohol (d) and nitrobenzene (e) absorbed on ZT-1: (1) FTIR spectrum of free benzyl alcohol or nitrobenzene; (2) Degassing stage; (3) Physical and chemical adsorption stage; (4) Chemical adsorption stage. (f) Simulated in situ ESR spectra of the samples in the mixed solution (1.5 mL of BTF and 0.100 mmol of BA) in Ar atmosphere using DMPO as spin trapping agent.

Scheme 3. Possible mechanism for photocatalytic synthesis of NBA via a tandem reaction.

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超薄ZnTi-LDH纳米片作为一种具有路易斯酸和布朗斯特酸的双功能光催化剂用于串联反应合成N-亚苄基苯胺

Ultrathin ZnTi-LDH nanosheet: A bifunctional Lewis and Brönsted acid photocatalyst for synthesis of N-benzylideneanilline via a tandem reaction

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