Selective hydrogenation of unsaturated carbonyls by Ni–Fe-based alloy catalysts

Abstract

Ni–Fe alloy catalysts prepared by a simple hydrothermal method and subsequent H2 treatment were shown to be highly selective for the hydrogenation of various unsaturated carbonyls.

Differentiation of Pt−Fe and Pt−Ni3 Surface Catalytic Mechanisms towards Contrasting Products in Chemoselective Hydrogenation of α,β‐Unsaturated Aldehydes

“…However, the di‐σ CO and end‐on mode enhanced the reactivity for C=O group and generated the desired alcohols. For the Pt−Fe(Ni 3 )/UiO‐66 catalytic system, C=O group was activated and weakened via end‐on bonding interaction (Δ E ads =−0.45 eV) on the electron‐deficient Fe surface, which attributed to the lone pair of oxygen for carbonyl group can be attracted preferentially because of anticlinal folded Pt−Fe skin (Figure S14) [24] . Meanwhile, the dissociated hydrogen molecules are transferred to attack and activate CAL to form COL. For the Pt‐Ni 3 /UiO‐66 catalytic system, the differences in product distribution can be rationalized based on the extended Huckel calculations of Delbecq and Sautet.…”

“…For the PtÀ Fe(Ni 3 )/ UiO-66 catalytic system, C=O group was activated and weakened via end-on bonding interaction (ΔE ads = À 0.45 eV) on the electron-deficient Fe surface, which attributed to the lone pair of oxygen for carbonyl group can be attracted preferentially because of anticlinal folded PtÀ Fe skin ( Figure S14). [24] Meanwhile, the dissociated hydrogen molecules are transferred to attack and activate CAL to form COL. For the Pt-Ni 3 /UiO-66 catalytic system, the differences in product distribution can be rationalized based on the extended Huckel calculations of Delbecq and Sautet. As shown in Table S6, Ni species showed unstable four-electron interactions due to a narrower d-band width compared to Fe, and the strong interactions between the conjugated C=C bond and the Ni surface form di-σ mode (ΔE ads = À 1.18 eV) lead to the favorable adsorption behavior of C=C group, thereby notably enhancing the catalytic selectivity of CAL.…”

Recent Advances in Aqueous-Phase Catalytic Conversions of Biomass Platform Chemicals Over Heterogeneous Catalysts

“…The addition of Ru promoted the reduction of Mo to strengthen the hydrogenation capacity of it. Putro et al (2017) synthesized a Ni-Fe alloy catalyst by using a hydrothermal method that achieved high selectivity in the hydrogenation of furfural. The result suggested that the electrondeficient Fe can weaken and activate the C=O bonds through a side bonding interaction of the lone pair of oxygen in the carbonyl group, making π-complexing occur between the C=O bonds and the Ni atoms, as shown in Figure 4.…”

“…Plausible mechanism for the selective hydrogenation of unsaturated alcohols over Ni-Fe-based alloy. Used with permission of Royal Society of Chemistry, fromPutro et al (2017); permission conveyed through Copyright Clearance Center, Inc.…”

Heterogeneous Catalytic Upgrading of Biofuranic Aldehydes to Alcohols

“…Most importantly, the existence of oxophilic Fe as a doped additive improves the specific surface area of the catalyst, while the dosage of unsaturated Ni active sites and the distribution of Ni active sites facilitates the adsorption of C = O bonds of FF. Putro et al (2017) adopted a simple hydrothermal method to prepare Ni-Fe alloy catalyst, and used to catalyze the reduction of FF to FFA, acquired excellent performance with a 99% FF conversion and a 95% FFA yield at 150°C for 3 h under a hydrogen pressure of 3 MPa. In order to increase the stability of the Ni-Fe catalyst, some researchers have added some supporters to the catalyst.…”