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Partial oxidation of methane (POM) co-fed with CO2 to syngas in a novel catalytic BaCo0.6Fe0.2Ta0.2O3-d oxygen permeable membrane reactor was successfully reported. Adding CO2 to the partial oxidation of methane reaction not only alters the ratio of CO/H2, but also increases the oxygen permeation flux and CH4 conversion. Around 96% CH4 conversion with more than 93% CO2 conversion and 100% CO selectivity is achieved, which shows an excellent reaction performance. A steady oxygen permeation flux of 15 mL/(cm2 min) is obtained during the 100-h operation, which shows good stability as well.