TEMPO radically expedites the conversion of sulfides to sulfoxides by pyrene-based metal-organic framework photocatalysis

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64601-7

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

Figures/Tables 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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