TEMPO显著加速芘基金属有机框架光催化硫化物到亚砜的转化

doi:10.1016/S1872-2067(23)64601-7

摘要/Abstract

摘要：

随着全球对可再生能源的需求持续上升, 太阳能因其无限、清洁和可持续的特点被视为最理想的能源之一. 在太阳能转化为化学能的过程中, 半导体光催化技术因能够有效利用太阳能驱动化学反应而受到广泛关注. 金属有机框架(MOF)因具有类似半导体的性质而广泛应用于光催化领域. 然而, MOF在光催化选择性催化上仍存在活性低或选择性差等问题. 为解决上述问题, 加入氧化还原介质成为一个潜在的解决方案. 通过深入研究氧化还原介质与MOF之间的协同作用, 有望提升光催化选择性氧化的效率, 从而推动MOF在光催化领域的应用发展.

本文将炔基整合到芘基配体中, 进一步调节金属有机框架的可见光吸收性质. 具体来说, 以4-苯基苯甲酸作为调节剂, 由4,4',4'',4'''-(芘-1,3,6,8-四基四(乙炔-2,1-二基))四苯甲酸和Zr₆O₄(OH)₄¹²⁺团簇合成了芘基MOF, 即NU-1100, 并采用粉末晶体衍射、氮气吸附-脱附、扫描电镜与透射电镜对结构进行表征. 结果表明, 由于拓宽配体的共轭结构, 与NU-1000相比, NU-1100的可见光吸收带红移. 实验结果表明, 在光催化体系中加入氧化还原介质2,2,6,6-四甲基哌啶-N-氧化物(TEMPO)可以显著加速有机硫化物到亚砜的转化. 在绿光照射下, 体系中加入催化量(3 mol%)氧化还原介质TEMPO和4-羧基TEMPO后, 转化率分别是单独使用NU-1100的2.7倍和5.2倍. 而NU-1000由于不吸收绿光无法驱动硫化物的氧化. 动力学研究结果表明, 4-羧基TEMPO可以加速硫化物转化为亚砜的反应进程. 光电化学测试结果表明, 4-羧基TEMPO可以促进NU-1100光生电子和空穴的分离以及转移. 利用密度泛函理论计算和一系列结构表征手段, 研究了加入4-羧基TEMPO提高NU-1100光催化活性的原因. 结果表明, 4-羧基TEMPO吸附在NU-1100的Zr₆O₄(OH)₄¹²⁺团簇外表面, 介导了空穴的转移, 实现了更高的电荷转移效率. 通过猝灭实验和原位电子顺磁共振测试研究了4-羧基TEMPO和NU-1100对硫化物氧化为亚砜的反应机理. 加入对苯醌作为超氧阴离子捕获剂后反应彻底停止, 而将溶剂甲醇替换为氘代甲醇后反应的转化率基本不变, 这说明单线态氧对反应不起作用, 超氧阴离子是该反应关键活性氧物种. 原位电子顺磁共振测试结果表明, 4-羧基TEMPO信号强度在开灯后迅速降低, 关灯后信号恢复, 说明其在硫化物氧化反应中存在循环. 底物拓展实验结果表明, 在NU-1100光催化和4-羧基TEMPO的协同作用下, 一系列有机硫化物可以被分子氧氧化转化为相应的亚砜产物.

利用光催化技术将丰富的太阳能转化为可利用的化学能具有广阔的应用前景和实际价值. 综上, 本文为设计和构筑可见光光催化提供了新思路, 并展示了氧化还原介质与金属有机框架协同作用在提升体系性能方面的优势, 进而为太阳能的转化和利用提供了一定的参考.

关键词: 金属有机框架, 氧化还原介质, 绿光, 选择性氧化, 光催化

Abstract:

Metal-organic frameworks (MOFs) are well-documented for visible light photocatalysis because of their tailorable structures and tunable absorptions through organic linkers. By employing a highly conjugated linker, 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid, the optical absorption of the MOF NU-1100 is effectively tuned to visible light below 600 nm region. Under green light irradiation, NU-1100 triggers charge separation and modulates electron transfer from the linkers to the Zr₆O₄(OH)₄¹²⁺ clusters, driving the oxidation of sulfides to sulfoxides. Notably, adding a redox mediator radically expedites the oxidation of sulfides by NU-1100 photocatalysis, TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) and 4-carboxy-TEMPO. At least 2.7 and 5.2 times of conversions of phenyl methyl sulfide are achieved by NU-1100 photocatalysis with TEMPO and 4-carboxy-TEMPO, respectively. A series of characterizations illustrate that 4-carboxy-TEMPO is adsorbed onto the exterior surface of Zr₆O₄(OH)₄¹²⁺ clusters of NU-1100 to mediate hole transfer and achieve higher charge transfer efficiency. Mechanistic studies indicate that superoxide is the essential reactive oxygen species and that the oxidation of sulfides is driven by an electron transfer pathway. This study demonstrates the integration of redox mediators with MOFs can drive more efficient visible light photocatalytic reactions.

Key words: Metal-organic framework, Redox mediator, Green light, Selective oxidation, Photocatalysis

曾冰, 黄凤伟, 王月欣, 熊康慧, 郎贤军. TEMPO显著加速芘基金属有机框架光催化硫化物到亚砜的转化[J]. 催化学报, 2024, 58: 226-236.

Bing Zeng, Fengwei Huang, Yuexin Wang, Kanghui Xiong, Xianjun Lang. TEMPO radically expedites the conversion of sulfides to sulfoxides by pyrene-based metal-organic framework photocatalysis[J]. Chinese Journal of Catalysis, 2024, 58: 226-236.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64601-7

https://www.cjcatal.com/CN/Y2024/V58/I3/226

图/表 12

Fig. 1. Schematic of a pyrene-based MOF NU-1100.

Fig. 2. (a) PXRD patterns of NU-1100. (b) FTIR spectra of NU-1100 and PTBA.

Fig. 3. N2 adsorption and desorption isotherms (a), pore size distribution (b), SEM image (c), and HRTEM image (d) of NU-1100.

Fig. 4. (a) UV-vis DRS of NU-1100 and light spectrum emitted by the green LEDs. (b) Tauc plot of NU-1100. (c) Mott-Schottky plots for NU-1100 in 0.1 mol L?1 Na2SO4. (d) Band structure of NU-1100.

Fig. 5. Impact of TEMPO and 4-carboxy-TEMPO on the conversions of organic sulfides by NU-1100 photocatalysis. Reaction conditions: NU-1100 (5 mg), TEMPO or 4-carboxy-TEMPO (9 μmol, 3 mol%), sulfide (0.3 mmol), CH3OH (1 mL), green LEDs, air (1 atm), 40 min.

Fig. 6. (a) Kinetic curves of the photocatalytic oxidation of phenyl methyl sulfide. (b) Recycling experiments. Reaction conditions: NU-1100 (5 mg), TEMPO or 4-carboxy-TEMPO (9 μmol, 3 mol%), phenyl methyl sulfide (0.3 mmol), CH3OH (1 mL), green LEDs, air (1 atm), 50 min.

Fig. 7. (a) Photocurrent densities. (b) EIS Nyquist plots. (c) The LSV curves. (d) Time-resolved PL spectra.

Fig. 8. XPS spectrum (a) and EPR spectra (b) of the addition of 4-carboxy-TEMPO to NU-1100.

Table 1 ROS quenching results for the photocatalytic oxidation of phenyl methyl sulfide. a

Entry	Quencher	Equiv.	Role	Conv.^b (%)	Sel.^b (%)
1	—	—	standard	66	97
2	N₂	—	O₂ replacement	0	—
3	p-BQ	0.2	O₂^•- scavenger	0	—
4	AgNO₃	1	e^- scavenger	15	97
5	HCOOH	3	h⁺ scavenger	22	99
6	CD₃OD	—	¹O₂ maintainer	64	97

Fig. 9. EPR spectra of e- (a), h+ (b), DMPO trapped O2?- (c), and 4-carboxy-TEMPO (d) on the oxidation of phenyl methyl sulfide with O2 during NU-1100 photocatalysis. (e) The spatial charge distribution of HOMO and LUMO for simplified fragments NU-1100.

Fig. 10. A tentative mechanism of the conversion of organic sulfide to sulfoxide by NU-1100 photocatalysis with 4-carboxy-TEMPO.

Table 2 Green light-driven oxidation of organic sulfides to sulfoxides by NU-1100 photocatalysis with 4-carboxy-TEMPO.a

Entry	t (min)	Conv.^b (%)	Sel.^b (%)
1	50	91	94
2	40	93	95
3	40	98	96
4	50	91	94
5	50	95	98
6	50	91	94
7	60	87	91
8	60	87	91
9	60	89	91
10	100	93	85
11	150	90	94
12	50	91	92
13	18	95	99
14	20	99	98

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