The CALPHAD thermodynamic databases are very useful to analyze the complex chemical reactions happening in high temperature material process.The FactSage thermodynamic database can be used to calculate complex phase d...The CALPHAD thermodynamic databases are very useful to analyze the complex chemical reactions happening in high temperature material process.The FactSage thermodynamic database can be used to calculate complex phase diagrams and equilibrium phases involving refractories in industrial process.In this study,the FactSage thermodynamic database relevant to ZrO_(2)-based refractories was reviewed and the application of the database to understanding the corrosion of continuous casting nozzle refractories in steelmaking was presented.展开更多
The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_(2) catalysts for isobutene synthesis were studied.We prepared a series of monoclinic ZrO_(2) catalysts with...The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_(2) catalysts for isobutene synthesis were studied.We prepared a series of monoclinic ZrO_(2) catalysts with different crystallite size by changing calcination temperature and evaluated their catalytic performance for isobutene synthesis from syngas.ZrO_(2) with small crystalline size showed higher CO conversion and isobutene selectivity,while samples with large crystalline size preferred to form dimethyl ether(DME)instead of hydrocarbons,much less to isobutene.Oxygen defects(ODefects)analyzed by X-ray photoelectron spectroscopy(XPS)provided evidence that more ODefectsoccupied on the surface of ZrO_(2) catalysts with smaller crystalline size.Electron paramagnetic resonance(EPR)and ultraviolet–visible diffuse reflectance(UV–vis DRS)confirmed the presence of high concentration of surface defects and Zr3+on mZrO_(2)-5.9 sample,respectively.In situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS)analysis indicated that the adsorption strength of formed formate species on catalyst reduced as the crystalline size decreased.These results suggested that surface defects were responsible for CO activation and further influenced the adsorption strength of surface species,and thus the products distribution changed.This study provides an in-depth insight for active sites regulation of ZrO_(2) catalyst in CO hydrogenation reaction.展开更多
基金Tata Steel Netherlands,Posco,Hyundai Steel,Nucor Steel,RioTinto,Nippon Steel Corp.,JFE Steel,Voestalpine,RHi-Magnesita,Doosan Enerbility,Seah Besteel,Umicore,Vesuvius and Schott AG are gratefully acknowledged.
文摘The CALPHAD thermodynamic databases are very useful to analyze the complex chemical reactions happening in high temperature material process.The FactSage thermodynamic database can be used to calculate complex phase diagrams and equilibrium phases involving refractories in industrial process.In this study,the FactSage thermodynamic database relevant to ZrO_(2)-based refractories was reviewed and the application of the database to understanding the corrosion of continuous casting nozzle refractories in steelmaking was presented.
基金financially supported by the Natural Science Foundation of China(21978312,21908235 and 21802155)the Key Research Program of Frontier Sciences,CAS(QYZDB–SSW–JS C043)+1 种基金Foundation of State Key Laboratory of Highefficiency Utilization of Coal and Green Chemical Engineering(2019-KF-05 and 2018-K22)Supported by Shanxi Scholarship Council of China and Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province are also greatly appreciated。
文摘The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_(2) catalysts for isobutene synthesis were studied.We prepared a series of monoclinic ZrO_(2) catalysts with different crystallite size by changing calcination temperature and evaluated their catalytic performance for isobutene synthesis from syngas.ZrO_(2) with small crystalline size showed higher CO conversion and isobutene selectivity,while samples with large crystalline size preferred to form dimethyl ether(DME)instead of hydrocarbons,much less to isobutene.Oxygen defects(ODefects)analyzed by X-ray photoelectron spectroscopy(XPS)provided evidence that more ODefectsoccupied on the surface of ZrO_(2) catalysts with smaller crystalline size.Electron paramagnetic resonance(EPR)and ultraviolet–visible diffuse reflectance(UV–vis DRS)confirmed the presence of high concentration of surface defects and Zr3+on mZrO_(2)-5.9 sample,respectively.In situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS)analysis indicated that the adsorption strength of formed formate species on catalyst reduced as the crystalline size decreased.These results suggested that surface defects were responsible for CO activation and further influenced the adsorption strength of surface species,and thus the products distribution changed.This study provides an in-depth insight for active sites regulation of ZrO_(2) catalyst in CO hydrogenation reaction.
