Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions,but promoting this process remains a significant challenge.Here,by loading yttrium clusters onto a single-atom support,...Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions,but promoting this process remains a significant challenge.Here,by loading yttrium clusters onto a single-atom support,an electronic promoting effect is triggered to successfully eliminate the nitrogen chemisorption barrier and achieve highly efficient ammonia synthesis.Density functional theory calculations reveal that yttrium clusters with abundant electron orbitals can provide considerable electrons and greatly promote electron backdonation to the N2 antibonding orbitals,making the chemisorption process exothermic.Moreover,according to the“hot atom”mechanism,the energy released during exothermic N2 chemisorption would benefit subsequent N2 cleavage and hydrogenation,thereby dramatically reducing the energy barrier of the overall process.As expected,the proof-of-concept catalyst achieves a prominent NH3 yield rate of 48.1μg·h^(−1)·mg^(−1)at−0.2 V versus the reversible hydrogen electrode,with a Faradaic efficiency of up to 69.7%.This strategy overcomes one of the most serious obstacles for electrochemical ammonia synthesis,and provides a promising method for the development of catalysts with high catalytic activity and selectivity.展开更多
基金supported by the National Natural Science Foundation of China(Nos.U21A20332,52103226,and 52071226)the Outstanding Youth Foundation of Jiangsu Province(No.BK20220061)+2 种基金the Natural Science Foundation of Jiangsu Province(No.BK20201171)the Key Research and Development Plan of Jiangsu Province(No.BE2020003-3)the Fellowship of China Postdoctoral Science Foundation(No.2021M702382).
文摘Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions,but promoting this process remains a significant challenge.Here,by loading yttrium clusters onto a single-atom support,an electronic promoting effect is triggered to successfully eliminate the nitrogen chemisorption barrier and achieve highly efficient ammonia synthesis.Density functional theory calculations reveal that yttrium clusters with abundant electron orbitals can provide considerable electrons and greatly promote electron backdonation to the N2 antibonding orbitals,making the chemisorption process exothermic.Moreover,according to the“hot atom”mechanism,the energy released during exothermic N2 chemisorption would benefit subsequent N2 cleavage and hydrogenation,thereby dramatically reducing the energy barrier of the overall process.As expected,the proof-of-concept catalyst achieves a prominent NH3 yield rate of 48.1μg·h^(−1)·mg^(−1)at−0.2 V versus the reversible hydrogen electrode,with a Faradaic efficiency of up to 69.7%.This strategy overcomes one of the most serious obstacles for electrochemical ammonia synthesis,and provides a promising method for the development of catalysts with high catalytic activity and selectivity.
