Nickel carbide (Ni<sub>3</sub>C) nanoparticles for catalytic hydrogenation of model compounds in solvent

André, Rémi F.; Meyniel, Léna; Carenco, Sophie

doi:10.1039/d2cy00894g

Cited by 10 publications

(7 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The hydrogen desorption peaks in the range of 50–300 °C are mainly ascribed to the removal of chemisorbed hydrogen on the metal surface, and the area of the desorption peak represents the amount of desorbed hydrogen. Ni/C-400 catalyst exhibits the highest amount of chemisorbed hydrogen, which has an association with surface electron-deficient Ni species [ 40 ]. However, higher treatment temperatures lead to Ni aggregation and the formation of a carbon layer, which may cover and decrease the surface active Ni content, leading to a decline in the ability to adsorb and dissociate H 2 .…”

Section: Resultsmentioning

confidence: 99%

Reticular Coordination Induced Interfacial Interstitial Carbon Atoms on Ni Nanocatalysts for Highly Selective Hydrogenation of Bio-Based Furfural under Facile Conditions

Liu

Feng

et al. 2023

Nanomaterials

View full text Add to dashboard Cite

A rational design of transition metal catalysts to achieve selective hydrogenation of furfural (FFR) to tetrahydrofurfuryl alcohol (THFA) under facile conditions is a promising option. In this work, a series of Ni catalysts were synthesized by controlled thermal treatment of Ni-based metal-organic frameworks (MOFs), with the purpose of modulating the interface of nickel nanoparticles by the reticular coordination in MOF precursors. The catalytic performance indicates that Ni/C catalyst obtained at 400 °C exhibits efficient conversion of FFR (>99%) and high selectivity to THFA (96.1%), under facile conditions (80 °C, 3 MPa H2, 4.0 h). The decomposition of MOF at low temperatures results in highly dispersed Ni0 particles and interfacial charge transfer from metal to interstitial carbon atoms induced by coordination in MOF. The electron-deficient Ni species on the Ni surface results in an electropositive surface of Ni nanoparticles in Ni/C-400, which ameliorates furfural adsorption and enhances the hydrogen heterolysis process, finally achieving facile hydrogenation of FFR to THFA.

show abstract

Section: Resultsmentioning

confidence: 99%

Reticular Coordination Induced Interfacial Interstitial Carbon Atoms on Ni Nanocatalysts for Highly Selective Hydrogenation of Bio-Based Furfural under Facile Conditions

Liu

Feng

et al. 2023

Nanomaterials

View full text Add to dashboard Cite

show abstract

“…Firstly, we confirmed that the catalysis was not due to homogeneous species and that the strong activity enhancement was due to the nano-urchins associated with the phosphine by testing the supernatant activity, following a procedure developed in earlier works. [5,[39][40][41] After the reaction, the reaction mixture was centrifuged, and the supernatant was collected and refilled with fresh phenylacetylene (Scheme S1). No further conversion was detected, excluding the formation of catalytically active leached cobalt species.…”

Section: Post-mortem Analysismentioning

confidence: 99%

Phosphine‐Enhanced Semi‐Hydrogenation of Phenylacetylene by Cobalt Phosphide Nano‐Urchins

Ropp,

André,

Carenco

2023

ChemPlusChem

Self Cite

View full text Add to dashboard Cite

Transition metal phosphides are promising, selective, and air‐stable nanocatalysts for hydrogenation reactions. However, they often require fairly high temperatures and H2 pressures to provide quantitative conversions. This work reports the positive effect of phosphine additives on the activity of cobalt phosphide nano‐urchins for the semi‐hydrogenation of phenylacetylene. While the nanocatalyst's activity was low under mild conditions (7 bar of H2, 100 °C), the addition of a catalytic amount of phosphine remarkably increased the conversion, e. g., from 13 % to 98 % in the case of PnBu3. The heterogeneous nature of the catalyst was confirmed by negative supernatant activity tests. The catalyst integrity was carefully verified by post‐mortem analyses (TEM, XPS, and liquid 31P NMR). A stereo‐electronic map was proposed to rationalize the activity enhancement provided over a selection of nine phosphines: the strongest effect was observed for low to moderately hindered phosphines, associated with strong electron donor abilities. A threshold in phosphine stoichiometry was revealed for the enhancement of activity to occur, which was related to the ratio of phosphine to surface cobalt atoms.

show abstract

“…Nowadays, there is a strong interest in developing nanocatalysts as colloidal suspensions, − targeting milder operating conditions, typically below 100 °C and with only a few bars of gas . Under such conditions, two goals can be achieved.…”

Section: Introductionmentioning

confidence: 99%

Phosphines on Colloidal Nickel Nanocatalysts to Lower the Onset Temperature of Terminal Alkynes Hydrogenation

Azouzi,

Ropp,

Carenco

2024

ACS Catal.

Self Cite

View full text Add to dashboard Cite

Catalysis by colloidal suspensions of metal nanoparticles (NPs) is becoming more and more attractive as it may combine mild reaction conditions with the use of organic ligands as surface modifiers. While most examples focus on increasing the selectivity of the catalytic process, there is also an opportunity to use the ligands to boost the conversion and trigger the onset of activity at a temperature where NPs alone would not be active. This may be achieved because the ligands modify the electronic and steric environments at the surface active site. In this work, we show that phosphines with adequate steric hindrance (e.g., P n Bu 3 and P i Bu 3 ) lower the onset temperature for phenylacetylene hydrogenation by nickel NPs under 7 bar of H 2 , by ca 10 to 20 °C depending on the NP diameter. This result is not expected to have practical repercussions for the reaction at stake, as it is already well-mastered; yet, it is of conceptual value because the hydrogenation may have been driven by the frustrated Lewis pair (FLP) between the Lewis basic phosphine and the Lewis acid nickel surface, forming a so-called "NanoFLP". We investigated this proposal using 10 phosphines and used a stereoelectronic map to rationalize their ability to boost the conversion, showing that moderately hindered and fairly donating phosphines are most adequate. Moreover, we demonstrated that less than 2 phosphines per Ni surface atom are enough for the effect to arise. We showed that other terminal alkynes, like 1-octyne, can be hydrogenated with this method. Lastly, a comparison of conversions for 5 para-substituted phenylacetylenes was used to discuss the effects of electronic donation and steric hindrance at the surface active site.

show abstract

Nickel carbide (Ni₃C) nanoparticles for catalytic hydrogenation of model compounds in solvent

Abstract: Finely divided nickel is one of the main heterogeneous catalysts for liquid phase hydrogenation of nitro and alkyne moieties. However, it constitutes a major safety hazard due to its pyrophoric...

Cited by 10 publications

References 46 publications

Reticular Coordination Induced Interfacial Interstitial Carbon Atoms on Ni Nanocatalysts for Highly Selective Hydrogenation of Bio-Based Furfural under Facile Conditions

Reticular Coordination Induced Interfacial Interstitial Carbon Atoms on Ni Nanocatalysts for Highly Selective Hydrogenation of Bio-Based Furfural under Facile Conditions

Phosphine‐Enhanced Semi‐Hydrogenation of Phenylacetylene by Cobalt Phosphide Nano‐Urchins

Phosphines on Colloidal Nickel Nanocatalysts to Lower the Onset Temperature of Terminal Alkynes Hydrogenation

Contact Info

Product

Resources

About

Nickel carbide (Ni3C) nanoparticles for catalytic hydrogenation of model compounds in solvent

Abstract: Finely divided nickel is one of the main heterogeneous catalysts for liquid phase hydrogenation of nitro and alkyne moieties. However, it constitutes a major safety hazard due to its pyrophoric...

Cited by 10 publications

References 46 publications

Reticular Coordination Induced Interfacial Interstitial Carbon Atoms on Ni Nanocatalysts for Highly Selective Hydrogenation of Bio-Based Furfural under Facile Conditions

Reticular Coordination Induced Interfacial Interstitial Carbon Atoms on Ni Nanocatalysts for Highly Selective Hydrogenation of Bio-Based Furfural under Facile Conditions

Phosphine‐Enhanced Semi‐Hydrogenation of Phenylacetylene by Cobalt Phosphide Nano‐Urchins

Phosphines on Colloidal Nickel Nanocatalysts to Lower the Onset Temperature of Terminal Alkynes Hydrogenation

Contact Info

Product

Resources

About

Nickel carbide (Ni₃C) nanoparticles for catalytic hydrogenation of model compounds in solvent