Electrochemically producing formate by oxidizing methanol is a promising way to add value to methanol.Noble metal-based electrocatalysts,which have been extensively studied for the methanol oxidation reaction,can cata...Electrochemically producing formate by oxidizing methanol is a promising way to add value to methanol.Noble metal-based electrocatalysts,which have been extensively studied for the methanol oxidation reaction,can catalyze the complete oxidation of methanol to carbon dioxide,but not the mild oxidation to formate.As a result,exploring efficient and earth-abundant electrocatalysts for formate production from methanol is of interest.Herein,we present the electro-oxidation of methanol to formate,catalyzed by iron-substituted lanthanum cobaltite(LaCo_(1-x)Fe_(x)O_(3)).The Fe/Co ratio in the oxides greatly influences the activity and selectivity.This effect is attributed to the higher affinity of Fe and Co to the two reactants:CH3OH and OH,respectively.Because a balance between these affinities is favored,LaCo_(0.5)Fe_(0.5)O_(3) shows the highest formate production rate,at 24.5 mmol h^(-1) g_(oxide)^(-1),and a relatively high Faradaic efficiency of 44.4%in a series of(LaCo_(1-x)Fe_(x)O_(3))samples(x=0.00,0.25,0.50,0.75,1.00)at 1.6 V versus a reversible hydrogen electrode.展开更多
基金This research was supported by the National Research Foundation,Prime Minister's Office,Singapore,under its Campus for Research Excellence and Technological Enterprise(CREATE)programThe work was partially supported by a Singapore Ministry of Education Tier 1 grant(2019-T1-002-125)and Tier 2 grant(MOE-T2EP10220-0001).
文摘Electrochemically producing formate by oxidizing methanol is a promising way to add value to methanol.Noble metal-based electrocatalysts,which have been extensively studied for the methanol oxidation reaction,can catalyze the complete oxidation of methanol to carbon dioxide,but not the mild oxidation to formate.As a result,exploring efficient and earth-abundant electrocatalysts for formate production from methanol is of interest.Herein,we present the electro-oxidation of methanol to formate,catalyzed by iron-substituted lanthanum cobaltite(LaCo_(1-x)Fe_(x)O_(3)).The Fe/Co ratio in the oxides greatly influences the activity and selectivity.This effect is attributed to the higher affinity of Fe and Co to the two reactants:CH3OH and OH,respectively.Because a balance between these affinities is favored,LaCo_(0.5)Fe_(0.5)O_(3) shows the highest formate production rate,at 24.5 mmol h^(-1) g_(oxide)^(-1),and a relatively high Faradaic efficiency of 44.4%in a series of(LaCo_(1-x)Fe_(x)O_(3))samples(x=0.00,0.25,0.50,0.75,1.00)at 1.6 V versus a reversible hydrogen electrode.
