Photochemically Engineering the Metal–Semiconductor Interface for Room‐Temperature Transfer Hydrogenation of Nitroarenes with Formic Acid

Li, Xin‐Hao; Cai, Yiyu; Gong, Ling-Hong; Fu, Wei; Wang, Kai‐Xue; Bao, Hongliang; Wei, Xiao; Chen, Jie‐Sheng

doi:10.1002/chem.201404325

Cited by 45 publications

(23 citation statements)

References 40 publications

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“…3e) but elevated white lines (marked with arrows in the inset of Fig. 3e) further confirm the similar oxidation state but increased electron density of Mo species [43][44][45]. All these results indicated our success in constructing a Schottky heterojunction composed of electron-rich MoC and electrondeficient N x C species.…”

Section: Catalytic Performance Of Moc@n X C Catalysts For Co 2 Hydrogenationsupporting

confidence: 72%

Mild and selective hydrogenation of CO2 into formic acid over electron-rich MoC nanocatalysts

et al. 2020

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Section: Catalytic Performance Of Moc@n X C Catalysts For Co 2 Hydrogenationsupporting

confidence: 72%

Mild and selective hydrogenation of CO2 into formic acid over electron-rich MoC nanocatalysts

et al. 2020

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“…The fact that the conversion of azoxybenzene (Figure S15) was much slower than that of nitrobenzene under fixed experimental conditions excludes the possibility of dimeric route in this LaCu 0.67 Si 1.33 catalytic system. As we know, the adsorption of nitroarene via the oxygen atoms in nitro group on the catalyst surface is a key step for the selective hydrogenation of nitro group . Therefore, adsorption of oxygen on the surface of LaCu 0.67 Si 1.33 was examined by DFT calculations to understand the origin of the interaction between catalyst surface and reactants .…”

Section: Resultsmentioning

confidence: 99%

Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions

et al. 2017

J. Am. Chem. Soc.

110

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The development of transition metal intermetallic compounds, in which active sites are incorporated in lattice frameworks, has great potential for modulating the local structure and the electronic properties of active sites, and enhancing the catalytic activity and stability. Here we report that a new copper-based intermetallic electride catalyst, LaCuSi, in which Cu sites activated by anionic electrons with low work function are atomically dispersed in the lattice framework and affords selective hydrogenation of nitroarenes with above 40-times higher turnover frequencies (TOFs up to 5084 h) than well-studied metal-loaded catalysts. Kinetic analysis utilizing isotope effect reveals that the cleavage of the H-H bond is the rate-determining step. Surprisingly, the high carrier density and low work function (LWF) properties of LaCuSi enable the activation of hydrogen molecules with extreme low activation energy (E = 14.8 kJ·mol). Furthermore, preferential adsorption of nitroarenes via a nitro group is achieved by high oxygen affinity of LaCuSi surface, resulting in high chemoselectivity. The present efficient catalyst can further trigger the hydrogenation of other oxygen-containing functional groups such as aldehydes and ketones with high activities. These findings demonstrate that the transition metals incorporated in the specific lattice site function as catalytically active centers and surpass the conventional metal-loaded catalysts in activity and stability.

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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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Photochemically Engineering the Metal–Semiconductor Interface for Room‐Temperature Transfer Hydrogenation of Nitroarenes with Formic Acid

Cited by 45 publications

References 40 publications

Mild and selective hydrogenation of CO2 into formic acid over electron-rich MoC nanocatalysts

Mild and selective hydrogenation of CO2 into formic acid over electron-rich MoC nanocatalysts

Copper-Based Intermetallic Electride Catalyst for Chemoselective Hydrogenation Reactions

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

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