Effect of copper loading on texture,structure and catalytic performance of Cu/SiO_2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol

Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation （UHDP） technique have been proposed focusing on the effect of copper loading.The texture,structure and composition are systematically characterized by ICP,FTIR,N 2-physisorption,N2O chemisorption,TPR,XRD and XPS.The formation of copper phyllosilicate is observed in Cu/SiO2 catalyst by adopting UHDP method,and the amount of copper phyllosilicate is related to copper loading.It is found the structure properties and catalytic performance is profoundly affected by the amount of copper phyllosilicate.The excellent catalytic activity is attributed to the synergetic effect between Cu0 and Cu ＋.DMO conversion and EG selectivity are determined by the amount of Cu0 and Cu＋,respectively.The proper copper loading （30 wt%） provides with the highest ratio of Cu ＋ /Cu0,giving rise to the highest EG yield of 95% under the reaction conditions of p=2.0 MPa,T=473 K,H2/DMO=80 and LHSV=1.0h-1.

Enhanced selective hydrogenation of glycolaldehyde to ethylene glycol over Cu^(0)-Cu^(+)sites

Selective hydrogenation of hydroxyaldehydes to polyalcohols is challenging due to the competitive hydrogenation of C=O and CAO.This study develops heterogeneous Cu catalysts for the selective synthesis of ethylene glycol via batch liquid-phase hydrogenation of glycolaldehyde.SiO_(2)supported Cu,fabricated by ammonia evaporation,enables to catalyze the C=O bond hydrogenation with retaining the CAO bond intact,yielding higher selective hydrogenation activity with ethylene glycol selectivity up to 99.8%relative to MgO,Al_(2)O_(3),CeO_(2),and TiO_(2)supports and Cu/SiO_(2)synthesized by deposition–precipitation and impregnation.Characterizations confirm that highly efficient 20Cu/SiO_(2)-AE-623 K catalyst fabricated by ammonia evaporation is featured with larger Cu^(0)and Cu^(+)surface areas,of which the Cu^(+)species created from reducing copper phyllosilicate exhibit higher reactivity.A synergistic effect between Cu^(+)and Cu^(0)facilitates the selective adsorption/activation of glycolaldehyde on Cu^(+)sites and the dissociation of H_(2)on Cu^(0)sites,bringing a remarkable improvement in the selective hydrogenation performance.

Selective hydrogenation of dimethyl maleate to tetrahydrofuran over Cu/SiO_2 catalyst:Effect of Cu^+ on the catalytic performance

Cu/SiO2 catalysts prepared by different methods have been investigated focusing on the influence of Cu^＋on the catalytic performance.The composition,structure and copper valence state were characterized by means of BET,XRD,XPS,FTIR,N2O-titration.It was found that the Cu/SiO2 prepared by ammoniaevaporation（AE） method had much higher TOF value than that prepared by wetness-impregnation（WI）with the same THF selectivity.The higher TOF value was attributed to the coexistence of Cu^＋ and Cu^0species in the activated AE-Cu/SiO2.while only Cu° species existing in the activated Wl-Cu/SiO2.Researches suggest that Cu^＋ can adsorb and polarize the C=0 bond of DMM.It is concluded that Cu°could be the main active site and the synergistic effect between Cu^0 and Cu^＋ could contribute to hydrogenation of DMM to THF.