Two-dimensional(2D)ordered carbon–nitrogen binary compounds(C_(x)N_(y))show great potential in many fields owing to their diverse structures and outstanding properties.However,the scalable and selective synthesis of ...Two-dimensional(2D)ordered carbon–nitrogen binary compounds(C_(x)N_(y))show great potential in many fields owing to their diverse structures and outstanding properties.However,the scalable and selective synthesis of 2D C_(x)N_(y)compounds remain a challenge due to the variable C/N stoichiometry induced coexistence of graphitic,pyridinic,and pyrrolic N species and the competitive growth of graphene.Here,this work systematically explored the mechanism of selective growth of a series of 2D ordered C_(x)N_(y)compounds,namely,the g-C_(3)N_(4),C_(2)N,C_(3)N,and C_(5)N,on various epitaxial substrates via first-principles calculations.By establishing the thermodynamic phase diagram,it is revealed that the individualized surface interaction and symmetry match between 2D C_(x)N_(y)compounds and substrates together enable the selective epitaxial growth of single crystal 2D C_(x)N_(y)compounds within distinct chemical potential windows of feedstock.The kinetics behaviors of the diffusion and attachment of the decomposed feedstock C/N atoms to the growing C_(x)N_(y)clusters further confirmed the feasibility of the substrate mediated selective growth of 2D C_(x)N_(y)compounds.Moreover,the optimal experimental conditions,including the temperature and partial pressure of feedstock,are suggested for the selective growth of targeted 2D C_(x)N_(y)compound on individual epitaxial substrates by carefully considering the chemical potential of carbon/nitrogen as the functional of experimental parameters based on the standard thermochemical tables.This work provides an insightful understanding on the mechanism of selective epitaxial growth of 2D ordered C_(x)N_(y)compounds for guiding the future experimental design.展开更多
基金supported by the National Key R&D Program of China(2021YFA1500703 and 2023ZD0120704)the National Natural Science Foundation of China(22222302,22033002 and T2321002)+2 种基金the"Shuang Chuang"Talent Program(JSSCRC2021489)the Major Project of Natural Science Foundation(BK20222007)of Jiangsu Provincethe Fundamental Research Funds for the Central Universities(2242023k30028)。
文摘Two-dimensional(2D)ordered carbon–nitrogen binary compounds(C_(x)N_(y))show great potential in many fields owing to their diverse structures and outstanding properties.However,the scalable and selective synthesis of 2D C_(x)N_(y)compounds remain a challenge due to the variable C/N stoichiometry induced coexistence of graphitic,pyridinic,and pyrrolic N species and the competitive growth of graphene.Here,this work systematically explored the mechanism of selective growth of a series of 2D ordered C_(x)N_(y)compounds,namely,the g-C_(3)N_(4),C_(2)N,C_(3)N,and C_(5)N,on various epitaxial substrates via first-principles calculations.By establishing the thermodynamic phase diagram,it is revealed that the individualized surface interaction and symmetry match between 2D C_(x)N_(y)compounds and substrates together enable the selective epitaxial growth of single crystal 2D C_(x)N_(y)compounds within distinct chemical potential windows of feedstock.The kinetics behaviors of the diffusion and attachment of the decomposed feedstock C/N atoms to the growing C_(x)N_(y)clusters further confirmed the feasibility of the substrate mediated selective growth of 2D C_(x)N_(y)compounds.Moreover,the optimal experimental conditions,including the temperature and partial pressure of feedstock,are suggested for the selective growth of targeted 2D C_(x)N_(y)compound on individual epitaxial substrates by carefully considering the chemical potential of carbon/nitrogen as the functional of experimental parameters based on the standard thermochemical tables.This work provides an insightful understanding on the mechanism of selective epitaxial growth of 2D ordered C_(x)N_(y)compounds for guiding the future experimental design.
