Effect of reduction pretreatment on the structure and catalytic performance of Ir-In_(2)O_(3)catalysts for CO_(2) hydrogenation to methanol

In_(2)O_(3)has been found a promising application in CO_(2)hydrogenation to methanol,which is beneficial to the utilization of CO_(2).The oxygen vacancy(O_(v))site is identified as the catalytic active center of this reaction.However,there remains a great challenge to understand the relations between the state of oxygen species in In_(2)O_(3)and the catalytic performance for CO_(2)hydrogenation to methanol.In the present work,we compare the properties of multiple In_(2)O_(3)and Ir-promoted In_(2)O_(3)(Ir-In_(2)O_(3))catalysts with different Ir loadings and after being pretreated under different reduction temperatures.The CO_(2)conversion rate of Ir-In_(2)O_(3)is more promoted than that of pure In_(2)O_(3).With only a small amount of Ir loading,the highly dispersed Ir species on In_(2)O_(3)increase the concentration of O_(v)sites and enhance the activity.By finely tuning the catalyst structure,Ir-In_(2)O_(3)with an Ir loading of 0.16 wt.%and pre-reduction treatment under 300℃exhibits the highest methanol yield of 146 mgCH_(3)OH/(gcat·hr).Characterizations of Raman,electron paramagnetic resonance,X-ray photoelectron spectroscopy,CO_(2)-temperature programmed desorption and CO_(2)-pulse adsorption for the catalysts confirm that more O_(v)sites can be generated under higher reduction temperature,which will induce a facile CO_(2)adsorption and desorption cycle.Higher performance for methanol production requires an adequate dynamic balance among the surface oxygen atoms and vacancies,which guides us to find more suitable conditions for catalyst pretreatment and reaction.