Photoinduced Reduction of Nitroarenes Using a Transition-Metal-Loaded Silicon Semiconductor under Visible Light Irradiation

Tsutsumi, Keisuke; Uchikawa, Fumito; Sakai, Kentaro; Tabata, Kenji

doi:10.1021/acscatal.6b00886

Cited by 65 publications

(62 citation statements)

References 43 publications

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“…[13] Among them, FA is almosta ni deal candidate for CTH because of its nontoxicity, convenience, and recyclability. [14,15] Unfortunately,m any of the reportede fficient catalysts for CTH generally necessitate the use of noble metals, [9,[16][17][18][19][20] seriously limiting the large-scale applications owing to the highe conomic cost and low availability.…”

Section: Introductionmentioning

confidence: 99%

Cobalt Entrapped in N,S‐Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid

et al. 2019

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Catalysts with Co nanoparticles (NPs) entrapped in N,S‐codoped carbon shells were successfully fabricated by pyrolysis of porous organic polymers (POPs) with cobalt salts. The encapsulated structure consisting of Co NPs and N,S‐codoped carbon layers was verified by TEM, XRD, and X‐ray photoelectron spectroscopy. The catalysts displayed excellent activity and stability for the catalytic transfer hydrogenation (CTH) of nitrobenzene with formic acid under base‐free conditions. Furthermore, the resultant catalysts allowed for highly efficient and selective transfer hydrogenation of various functionalized nitroarenes to the corresponding anilines. Through control experiments, the covered Co NPs were identified as active sites for CTH. The incorporation of S into the N‐doped carbon lattice promoted the electron transfer from metallic cobalt NPs to their shells, which played a significant role in the acceleration of CTH. Moreover, the Co‐NSPC‐850 catalyst pyrolyzed at 850 °C showed excellent stability in the recycling experiments.

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Section: Introductionmentioning

confidence: 99%

Cobalt Entrapped in N,S‐Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid

et al. 2019

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“…However, in most of the photocatalytic hydrogenation routes, hydrogen donors such as formic acid, isopropyl alcohol or triethanolamine were used instead of gaseous H2. [11][12][13] Recently, we reported a photocatalytic reduction of nitroarenes with H2 using graphene-supported CoS2 particles as the catalyst under mild condition, however with unsatisfactory activity. 14 For catalytic hydrogenation of nitroarenes, dissociation of H2 is the rate-determining step.…”

Section: Introductionmentioning

confidence: 99%

Synergistic Effect of Segregated Pd and Au Nanoparticles on Semiconducting SiC for Efficient Photocatalytic Hydrogenation of Nitroarenes

Hao

Guo

Sankar

et al. 2018

ACS Appl. Mater. Interfaces

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Efficient catalytic hydrogenation of nitroarenes to anilines with molecular hydrogen at room temperature is still a challenge. In this study, this transformation was achieved by using a photocatalyst of SiC-supported segregated Pd and Au nanoparticles. Under visible-light irradiation, the nitrobenzene hydrogenation reached a turnover frequency as high as 1715 h at 25 °C and 0.1 MPa of H pressure. This exceptional catalytic activity is attributed to a synergistic effect of Pd and Au nanoparticles on the semiconducting SiC, which is different from the known electronic or ensemble effects in Pd-Au catalysts. This kind of synergism originates from the plasmonic electron injection of Au and the Mott-Schottky contact at the interface between Pd and SiC. This three-component system changes the electronic structures of the SiC surface and produces more active sites to accommodate the active hydrogen that spills over from the surface of Pd. These active hydrogen species have weaker interactions with the SiC surface and thus are more mobile than on an inert support, resulting in an ease in reacting with the N═O bonds in nitrobenzene absorbed on SiC to produce aniline.

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“…18,19 Besides TiO 2 , Pd/Si, Ag/Bi 2 MoO 6 , PbBiO 2 X, and CdS have also been used for hydrogenation of the nitro group. 20−24 A Pt-deposited Ti(IV) metal-organic framework has been reported for nitro reduction reactions with an initial reaction rate of 132 μmol h –1 g –1 . 25 Weiss et al have reported that electron transfer, not proton transfer, is the rate-limiting step for nitrobenzene reduction.…”

Section: Introductionmentioning

confidence: 99%

In Situ Preparation of CoP@CdS and Its Catalytic Activity toward Controlling Nitro Reduction under Visible-Light Irradiation

Chen

2018

ACS Omega

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CoP was synthesized in situ on the surface of CdS nanowires using a cobalt–ammine complex as a precursor. The generated CoP@CdS photocatalyst was well characterized by X-ray diffraction, transmission electron microscopy, selected-area electron diffraction, and diffuse reflectance spectra. A more efficient charge transfer was successfully achieved owing to the close contact between CoP and CdS. The hybrid photocatalyst showed excellent activity for the reduction of nitroarenes to the corresponding anilines or azobenzene compounds in water. In present work, hydrogen evolution and nitro reduction were concurrent and with the consumption of substrate, the rate of hydrogen evolution increased. The driving force for the reduction originated from the activated hydrogen species in the photocatalytic reaction rather than from dihydrogen. The photocatalytic activity of as-prepared CoP@CdS in situ is comparable to that of the catalysts formed using a noble metal loaded onto CdS. Mechanistic investigation showed that the condensation route is the major pathway for nitro reduction in the present system, and azo compounds could be obtained with less irradiation time, while aniline will be obtained via long-time irradiation.

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Photoinduced Reduction of Nitroarenes Using a Transition-Metal-Loaded Silicon Semiconductor under Visible Light Irradiation

Cited by 65 publications

References 43 publications

Cobalt Entrapped in N,S‐Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid

Cobalt Entrapped in N,S‐Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid

Synergistic Effect of Segregated Pd and Au Nanoparticles on Semiconducting SiC for Efficient Photocatalytic Hydrogenation of Nitroarenes

In Situ Preparation of CoP@CdS and Its Catalytic Activity toward Controlling Nitro Reduction under Visible-Light Irradiation

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