Photocatalytic Dehydrogenation of Primary Alcohols: Selectivity Goes Against Adsorptivity

Overview

Journal ACS Omega

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Aug 29

PMID 31457713

Citations 3

Authors

Dongge Ma

Anan Liu

Chichong Lu

Chuncheng Chen

Affiliations

Soon will be listed here.

Abstract

Solid/liquid heterogeneous photocatalysis was often considered to occur on the active sites of a solid catalyst surface. Herein, we report that the selectivity of photocatalytic dehydrogenative oxidations of aliphatic primary alcohols in acetonitrile solution into corresponding aldehydes exhibits an anomalous relationship with adsorption behavior of the alcohols. By using Pt-loaded TiO photocatalyst in an inert atmosphere under UV light illumination, primary short-chain alcohols (SCAs) with strong adsorption were dehydrogenated into aldehydes in very poor selectivity, whereas weak-adsorbable long-chain alcohols (LCAs) were transformed into corresponding aldehydes with much higher selectivity. More than 20 examples of primary LCAs (C-C) were successfully transformed into their corresponding aldehydes with satisfactory selectivity and yield. Both solid-state magic-angle-spinning C NMR and attenuated total reflectance-Fourier transform infrared spectroscopy studies provided concrete differences in adsorption behaviors on the Pt-TiO photocatalyst surface between SCA ethanol and LCA -octanol. To further uncover the mechanism for different selectivities of SCAs and LCAs in photodehydrogenation, in situ electron paramagnetic resonance (EPR) experiments (at 8 K temperature) were employed to observe the oxidation features of photogenerated hole in the valance band of Pt-TiO (h ). The EPR experimental studies exhibited that unlike ethanol, either -octanol or solvent acetonitrile alone all could not scavenge photogenerated h on Pt-P25 photocatalyst and only -octanol dissolved in acetonitrile solvent could smoothly react with photoinduced hole. This indicated that selective oxidations of LCAs were achieved by solvent-delivered oxidation rather than directly destructive oxidation of photogenerated h . Our results may open an alternative way in selective dehydrogenative oxidation of various substrates sensitive to both dioxygen and high-temperature treatments.

Citing Articles

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References

Chen X, Mao S . Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chem Rev. 2007; 107(7):2891-959. DOI: 10.1021/cr0500535. View

Yurdakal S, Palmisano G, Loddo V, Augugliaro V, Palmisano L . Nanostructured rutile TiO2 for selective photocatalytic oxidation of aromatic alcohols to aldehydes in water. J Am Chem Soc. 2008; 130(5):1568-9. DOI: 10.1021/ja709989e. View

Augugliaro V, Caronna T, Loddo V, Marci G, Palmisano G, Palmisano L . Oxidation of aromatic alcohols in irradiated aqueous suspensions of commercial and home-prepared rutile TiO(2): a selectivity study. Chemistry. 2008; 14(15):4640-6. DOI: 10.1002/chem.200702044. View

Parrino F, Ramakrishnan A, Kisch H . Semiconductor-photocatalyzed sulfoxidation of alkanes. Angew Chem Int Ed Engl. 2008; 47(37):7107-9. DOI: 10.1002/anie.200800326. View

Zhang M, Chen C, Ma W, Zhao J . Visible-light-induced aerobic oxidation of alcohols in a coupled photocatalytic system of dye-sensitized TiO2 and TEMPO. Angew Chem Int Ed Engl. 2008; 47(50):9730-3. DOI: 10.1002/anie.200803630. View

Zhang M, Wang Q, Chen C, Zang L, Ma W, Zhao J . Oxygen atom transfer in the photocatalytic oxidation of alcohols by TiO2: oxygen isotope studies. Angew Chem Int Ed Engl. 2009; 48(33):6081-4. DOI: 10.1002/anie.200900322. View

Augugliaro V, Loddo V, Lopez-Munoz M, Marquez-Alvarez C, Palmisano G, Palmisano L . Home-prepared anatase, rutile, and brookite TiO(2) for selective photocatalytic oxidation of 4-methoxybenzyl alcohol in water: reactivity and ATR-FTIR study. Photochem Photobiol Sci. 2009; 8(5):663-9. DOI: 10.1039/b818353h. View

Wang Q, Zhang M, Chen C, Ma W, Zhao J . Photocatalytic aerobic oxidation of alcohols on TiO2: the acceleration effect of a Brønsted acid. Angew Chem Int Ed Engl. 2010; 49(43):7976-9. DOI: 10.1002/anie.201001533. View

Chen C, Ma W, Zhao J . Semiconductor-mediated photodegradation of pollutants under visible-light irradiation. Chem Soc Rev. 2010; 39(11):4206-19. DOI: 10.1039/b921692h. View

10.

Zhu H, Ke X, Yang X, Sarina S, Liu H . Reduction of nitroaromatic compounds on supported gold nanoparticles by visible and ultraviolet light. Angew Chem Int Ed Engl. 2010; 49(50):9657-61. DOI: 10.1002/anie.201003908. View

11.

Lang X, Ji H, Chen C, Ma W, Zhao J . Selective formation of imines by aerobic photocatalytic oxidation of amines on TiO2. Angew Chem Int Ed Engl. 2011; 50(17):3934-7. DOI: 10.1002/anie.201007056. View

12.

Lang X, Ma W, Zhao Y, Chen C, Ji H, Zhao J . Visible-light-induced selective photocatalytic aerobic oxidation of amines into imines on TiO2. Chemistry. 2012; 18(9):2624-31. DOI: 10.1002/chem.201102779. View

13.

Rueping M, Zoller J, Fabry D, Poscharny K, Koenigs R, Weirich T . Light-mediated heterogeneous cross dehydrogenative coupling reactions: metal oxides as efficient, recyclable, photoredox catalysts in C-C bond-forming reactions. Chemistry. 2012; 18(12):3478-81. DOI: 10.1002/chem.201103242. View

14.

Manley D, McBurney R, Miller P, Howe R, Rhydderch S, Walton J . Unconventional titania photocatalysis: direct deployment of carboxylic acids in alkylations and annulations. J Am Chem Soc. 2012; 134(33):13580-3. DOI: 10.1021/ja306168h. View

15.

Qu Y, Duan X . Progress, challenge and perspective of heterogeneous photocatalysts. Chem Soc Rev. 2012; 42(7):2568-80. DOI: 10.1039/c2cs35355e. View

16.

Kisch H . Semiconductor photocatalysis--mechanistic and synthetic aspects. Angew Chem Int Ed Engl. 2012; 52(3):812-47. DOI: 10.1002/anie.201201200. View

17.

Li N, Lang X, Ma W, Ji H, Chen C, Zhao J . Selective aerobic oxidation of amines to imines by TiO2 photocatalysis in water. Chem Commun (Camb). 2013; 49(44):5034-6. DOI: 10.1039/c3cc41407h. View

18.

Steves J, Stahl S . Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: alleviating steric and electronic constraints of Cu/TEMPO catalyst systems. J Am Chem Soc. 2013; 135(42):15742-5. PMC: 6346749. DOI: 10.1021/ja409241h. View

19.

Lang X, Chen X, Zhao J . Heterogeneous visible light photocatalysis for selective organic transformations. Chem Soc Rev. 2013; 43(1):473-86. DOI: 10.1039/c3cs60188a. View

20.

Manley D, McBurney R, Miller P, Walton J, Mills A, ORourke C . Titania-promoted carboxylic acid alkylations of alkenes and cascade addition-cyclizations. J Org Chem. 2014; 79(3):1386-98. PMC: 3963454. DOI: 10.1021/jo4027929. View