Catalytic Transfer Hydrogenation of Levulinic Acid to γ-Valerolactone over Ni₃P-CePO₄ Catalysts

Abstract

A series of Ni3P-CePO4(x) catalysts were prepared by H2 temperature-programmed reduction and utilized to catalyze the transfer hydrogenation (CTH) of levulinic acid (LA) to γ-valerolactone (GVL). The characterization of the synthesized catalysts was carried out by means of XRD, N2-adsorption/desorption, NH3-TPD, CO2-TPD, TEM, EDS elemental mapping, ICP, XPS, and TG/DSC. The effects of Ce/Ni molar ratio, reaction temperature, reaction time, and hydrogen donor on the CTH performance were studied. The yield of GVL was 89.9% at an LA conversion of 99.9% at 180 °C for 2 h over the Ni3P-CePO4(0.1) catalyst using 2-propanol as the solvent. The NH3-TPD and CO2-TPD measurements and poisoning experiments verified that acidic/basic sites played a synergic role in the process. A slight decrease in LA conversion and GVL yield was observed after four consecutive cycles. The characterization of the fresh and spent catalysts indicated that the minor deactivation was due to the deposition of insoluble organics or polymers rather than the changes of the crystal phase or acidic/basic properties, or the leaching of the active sites.

Supported Bimetallic Catalysts for the Solvent-Free Hydrogenation of Levulinic Acid to γ-Valerolactone: Effect of Metal Combination (Ni-Cu, Ni-Co, Cu-Co)

“…However, the hydrogenation activity of transition metals is low compared to noble metals; therefore, higher temperatures are needed to start the hydrogenation of LA. At high temperatures (~220 • C), LA could be easily dehydrated to AL, suggesting that the AL pathway is responsible for GVL production in this work [25][26][27].…”

An Account of the Catalytic Transfer Hydrogenation and Hydrogenolysis of Carbohydrate‐Derived Renewable Platform Chemicals over Non‐Precious Heterogeneous Metal Catalysts

“…Wang and coworkers employed Ni 3 P−CePO 4 catalyst for the transfer hydrogenation of LA at 180 °C using various primary and secondary alcohols as H‐donor solvents. 100 % LA conversion and 90 % GVL selectivity were observed using 2‐propanol as H‐donor solvent, which was attributed to the lower heat of formation of acetone from 2‐propanol compared to methanol, ethanol, and n‐propanol [58] . The recyclability study revealed the reduction in LA conversion and GVL selectivity to 91 % and 78 %, respectively, in the 4 th catalytic cycle.…”

“…100 % LA conversion and 90 % GVL selectivity were observed using 2propanol as H-donor solvent, which was attributed to the lower heat of formation of acetone from 2-propanol compared to methanol, ethanol, and n-propanol. [58] The recyclability study revealed the reduction in LA conversion and GVL selectivity to 91 % and 78 %, respectively, in the 4 th catalytic cycle. The authors suggested that acid sites present on the catalyst surface were responsible for LA activation.…”

Interface Engineering in CoP/CePO4 Derived from a Prussian Blue Analogue as a Highly Efficient Electrocatalyst for Alkaline Hydrogen Evolution Reaction

“…As shown in Figure 3c, the Ce 3d XPS spectra in bare CePO 4 and CoP/CePO 4 can be deconvoluted into four peaks, which are labeled to u’, u, v’ and v peaks, respectively [37] . Peaks located at 903.94 eV (named as peak u’) and 885.47 eV (named as peak v’) belong to Ce 4+ , while peaks located at 900.12 eV (labeled as peak u) and 881.12 eV (labeled as peak v) were corresponded to Ce 3+ [38,39] .…”