High-Performance Ni₃P/meso-SiO₂ for Gas-Phase Hydrogenation of Dimethyl Oxalate to Methyl Glycolate

Abstract

Three meso-SiO 2 (RB-MSN, HMS, and MCM-41) supported Ni 3 P catalysts to be used in gas-phase hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) are prepared via the impregnation method and subsequent H 2 -reduction treatment. The as-obtained catalysts show interesting meso-SiO 2type-dependent reactivity for this reaction, which is tightly linked with the support Si−OH amount rather than the support textural/ structural properties and Ni 3 P grain size. The Ni 3 P/RB-MSN outperforms the two others, being capable of fully converting DMO with 85.0% MG selectivity and being stable for at least 500 h under mild conditions. The turnover frequency and E a of such a catalyst for this reaction are calculated to be 204.2 h −1 and 84.0 kJ mol −1 . Lack of Si−OH in RB-MSN diminishes the interaction of NiO and PO x with Si−OH groups, thereby not only enabling NiO and PO x to be easily and fully reduced to form Ni 3 P but also suppressing the formation of harmful irreducible PO x species.

High-Performance Ni3P Catalyst for C═O Hydrogenation of Ethyl Levulinate: Niδ+ as Outstanding Adsorption Sites

“…The result was consistent with the previous works in which the binding energy of Ni δ+ in Ni 3 P phase was found to be below 853 eV. For example, the binding energy of Ni δ+ was 852.8 eV in Ni 3 P/meso-SiO 2 , 852.6 eV in pure Ni 3 P, and 852.5 eV in Ni 3 P/γ-Al 2 O 3 . This electron-deficient species was ascribed to the electron transfer from Ni to P, which was also observed in several metal phosphides. , The P 2p signals of Ni-0.38P/Al 2 O 3 are shown in Figure S4.…”

Synthesis of methyl glycolate via low‐temperature hydrogenation of dimethyl oxalate over an efficient and stable Ru/activated carbon catalyst

“…Recently, Zhuang 23 reported MG selectivity of 88.1% with DMO conversion of 94.6% over Co 8 P/SiO 2 at 240 °C. The Ni 3 P/RB‐MSN was capable of fully converting DMO with 85.0% MG selectivity and being stable for at least 500 h at 190 °C 24 . Au decorated Fe/ZrO 2 nanorod catalyst was reported by Chen et al , which showed good performance on DMO hydrogenation with MG yield of 95% at 200 °C 25 .…”

Rational design of hydroxyapatite/graphite-supported bimetallic Cu–M (M = Cu, Fe, Co, Ni) catalysts for enhancing the partial hydrogenation of dimethyl oxalate to methyl glycolate

“…Nevertheless, other transition metal-based catalysts such as Cu/reduced graphene oxide, Ni 3 P/meso-SiO 2 , Cu/SiO 2 and P-modified Co/SiO 2 have been employed successfully to obtain the MG product, but the relatively low MG selectivity and the high loading ratio of Cu metal in some cases were pointed out as serious disadvantages. [8][9][10][11] Therefore, we felt necessary to develop a robust noble metal-free catalyst with low copper content for achieving high MG selectivity via the DMO hydrogenation reaction. In this perspective, bimetallic transition metal nanoparticles could be the best candidate in our DMO catalytic reaction, since the bimetallic catalysts showed promising catalytic performance in several hydrogenation reactions.…”