Promoting H₂ Activation over Molybdenum Carbide by Modulation of Metal‐Support Interaction for Efficient Catalytic Hydrogenation

Abstract

Transition metal carbides (TMCs) have been used extensively as catalysts for hydrogenation reactions. However, TMC catalysts suffer from low activity for H 2 activation, which is vital to their hydrogenation performance. Herein, we report a feasible strategy to improve the ability of TMCs (e. g., Mo 2 C) for H 2 activation by modulation of the metal-support interaction (MSI). The MSI can be tuned by introducing N element into carbon supports. Specifically, N can modulate the orbital structure of Mo to promote H 2 activation. Experimental and theoretical results reveal that H 2 activation ability of the metal sites can be altered by loading them onto carbon supports, and optimized by doping N into the corresponding carbon matrices. Consequently, N-doped carbon-supported Mo 2 C (Mo 2 C/NC) catalyst, possessing improved H 2 activation ability, displays remarkably enhanced catalytic hydrogenation performance for the reduction of nitro compounds. The conversion and selectivity over Mo 2 C/NC are nearly 100 % under mild conditions.

Protein–metal ion networks coated carbon matrix as a precursor: to construct carbon-supported Mo-based catalysts with highly exposed active sites for hydrogenation of nitro compounds

“…The calculation of the conversion, selectivity, and turnover frequency (TOF) follows the methodology established in our previous studies. 21,33,34 The performance evaluation of all catalysts was repeated more than 5 times, with further details on other additional reaction conditions given in graphs or table notes.…”

“…However, this method still faces challenges, such as high protein costs and low char yield. [29][30][31][32][33][34][35] Herein, protein-Mo ion networks (PMINs) were coated on microsphere carbons (MCs). The PMINs-coated MC was employed as a precursor, which was then subjected to pyrolysis to produce a carbon-supported Mo catalyst (Mo@C/MC) (see Fig.…”

Oxygen Vacancy-Reinforced Water-Assisted Proton Hopping for Enhanced Catalytic Hydrogenation

“…The peak of Pd/MoO 3−x -50 shifts to a lower temperature compared with that of Pd/ MoO 3−x -25, which suggests that the adsorption strength toward hydrogen decreases significantly. 40,41 Overall, the oxygen vacancies are conducive to hydrogen spillover and water adsorption. Density functional theory (DFT) was applied to theoretically explore the mechanism.…”

Ru Nanoclusters Supported on Ti3C2Tx Nanosheets for Catalytic Hydrogenation of Quinolines

“…In general, the electronic structure of the active metal sites can be tailored by metal−support interaction (MSI) through loading metal onto supports. 17,18 For example, Sun's groups prepared Ru/γ-TiO 2 catalysts, where γ-TiO 2 can regulate the electronic structures of Ru. As a result, the Ru/ γ-TiO 2 catalyst showed higher catalytic performance in alkaline HER than its companion metallic Ru, due to its weakened desorption towards OH*.…”

“…Among them, Ru has received particular attention owing to its relatively low cost. , However, Ru suffers from low H desorption and strong adsorption towards hydrogenated substrates, owing to its strong affinity to H and intermediates, which seriously compromises its catalytic hydrogenation activity. , As we know, the adsorption of reactants or/and intermediates on metal sites is highly related to their electronic structures. In general, the electronic structure of the active metal sites can be tailored by metal–support interaction (MSI) through loading metal onto supports. , For example, Sun’s groups prepared Ru/γ-TiO 2 catalysts, where γ-TiO 2 can regulate the electronic structures of Ru. As a result, the Ru/γ-TiO 2 catalyst showed higher catalytic performance in alkaline HER than its companion metallic Ru, due to its weakened desorption towards OH* .…”