Solid surfaces usually reach thermodynamic equilibrium through particle exchange with their environment under reactive conditions.A prerequisite for understanding their functionalities is detailed knowledge of the sur...Solid surfaces usually reach thermodynamic equilibrium through particle exchange with their environment under reactive conditions.A prerequisite for understanding their functionalities is detailed knowledge of the surface composition and atomistic geometry under working conditions.Owing to the large number of possible Miller indices and terminations involved in multielement solids,extensive sampling of the compositional and conformational space needed for reliable surface energy estimation is beyond the scope of ab initio calculations.Here,we demonstrate,using the case of iron carbides in environments with varied carbon chemical potentials,that the stable surface composition and geometry of multielement solids under reactive conditions,which involve large compositional and conformational spaces,can be predicted at ab initio accuracy using an approach that combines the bond valence model,Gaussian process regression,and ab initio thermodynamics.Determining the atomistic structure of surfaces under working conditions paves the way toward identifying the true active sites of multielement catalysts in heterogeneous catalysis.展开更多
基金This work was financially supported by the National Science Fund for Distinguished Young Scholars of China(grant no.22225206)the National Key R&D Program of China(no.2022YFA1604103)+6 种基金the National Natural Science Foundation of China(nos.21972157 and 21972160)the CAS Project for Young Scientists in Basic Research(YSBR-005)the Key Research Program of Frontier Sciences CAS(ZDBS-LY-7007)the Major Research Plan of the National Natural Science Foundation of China(92045303)the Informatization Plan of the Chinese Academy of Sciences(grant no.CAS-WX2021SF0110)the Youth Innovation Promotion Association CAS(2020179)Funding support was also received from the Beijing Advanced Innovation Center for Materials Genome Engineering,Synfuels China Co.,Ltd.,and the Institute of Coal Chemistry,Chinese Academy of Sciences.
文摘Solid surfaces usually reach thermodynamic equilibrium through particle exchange with their environment under reactive conditions.A prerequisite for understanding their functionalities is detailed knowledge of the surface composition and atomistic geometry under working conditions.Owing to the large number of possible Miller indices and terminations involved in multielement solids,extensive sampling of the compositional and conformational space needed for reliable surface energy estimation is beyond the scope of ab initio calculations.Here,we demonstrate,using the case of iron carbides in environments with varied carbon chemical potentials,that the stable surface composition and geometry of multielement solids under reactive conditions,which involve large compositional and conformational spaces,can be predicted at ab initio accuracy using an approach that combines the bond valence model,Gaussian process regression,and ab initio thermodynamics.Determining the atomistic structure of surfaces under working conditions paves the way toward identifying the true active sites of multielement catalysts in heterogeneous catalysis.
