hcp-phased Ni nanoparticles with generic catalytic hydrogenation activities toward different functional groups

Abstract

Catalytic hydrogenation is a vital industrial means to produce value-added fuels and fine chemicals, however, requiring highly efficient catalysts, especially the nonprecious ones. To date, the majority of high-performance industrial hydrogenation catalysts are made of precious metals-based materials, and any given catalyst could only be used to catalyze one or few specific reactions. Herein, we exemplify a crystal phase engineering approach to empower Ni nanoparticles (NPs) with superb intrinsic catalytic activities toward a wide spectrum of hydrogenation reactions. A facile pyrolysis approach is used to directly convert a Ni-imidazole MOF precursor into hexagonal close-packed (hcp)-phased Ni NPs on carbon support. The as-synthesized hcp-phased Ni NPs exhibit unprecedented hydrogenation catalytic activities in pure water towards nitro-, aldehyde-, ketone-, alkene-and N heterocyclic-compounds, outperforming the face-centered cubic (fcc)-Ni counterpart and the reported transition metalsbased catalysts. The density functional theory calculations unveil that the presence of hcp-Ni boosts the intrinsic catalytic hydrogenation activity by coherently enhancing the substrate adsorption strength and lowering the reaction barrier energy of the rate-determining step. We anticipate that the crystal phase engineering design approach unveiled in this work would be adoptable to other types of reactions.

Recent progress in strategies for preparation of metal-organic frameworks and their hybrids with different dimensions

“…The single-crystal-to-single-crystal (SCSC) conversion is an intriguing and essential process in chemistry and material science and is an important feature in the preparation of coordination polymers [132][133][134][135][136][137][138][139] . Over the last few decades, much research demonstrated that SCSC conversions of MOFs could be triggered by external stimuli, including physical and chemical processes, such as temperature, pressure, gas adsorption, etc.…”

Research progress on the role of common metal catalysts in biomass pyrolysis: a state-of-the-art review

“…42 The d% of Ni is 40, Lv et al prepared nanoscale hcp-phased Ni supported on carbon that exhibited outstanding hydrogenation catalytic activities in pure water towards nitro-, aldehyde-, ketone-, alkene-and N heterocycliccompounds. 43 In addition, the particle size of the catalyst has different effects on different catalytic reactions. For some catalytic reactions, the best catalytic effect may be achieved within a certain particle size scale.…”

“…42 The d% of Ni is 40, Lv et al prepared nanoscale hcp-phased Ni supported on carbon that exhibited outstanding hydrogenation catalytic activities in pure water towards nitro-, aldehyde-, ketone-, alkene- and N heterocyclic-compounds. 43…”

Ultra-low temperature direct reconstruction of biomass fermentation of ethanol to higher alcohols in water over thermostable hcp-Ni

“…Reducing the catalytic dehydrogenation barrier (the key rate-controlling step) is crucial for ethanol coupling under mild conditions. 27,28 The hexagonal-close-packed (hcp) Ni is quite active in de-/hydrogenation reactions due to its unique spatial arrangement and electronic structure compared to traditional face-centered-cubic (fcc) Ni, [29][30][31][32][33][34][35] but its fabrication is still challenging due to the thermodynamically metastable nature of hcp-Ni. 4,26,34,36,37 Herein, we developed a facile surfactant-induced carbonization strategy, which uses the amide-containing polymer polyvinylpyrrolidone (PVP) as an inducer and carbon source, to construct the thermostable hcp-Ni dominated hcp/fcc-Ni@C catalyst.…”