Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pos...Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges.Herein,we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics.An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles(2-6 nm in diameter)loaded on BO_(x) substrates(AuBO_(x)),in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles.The electrochemical results show that Au-BO_(x) possesses excellent NRR activity(NH_(3) yield of 48.52μg h^(-1)mg_(cat)^(-1),Faraday efficiency of 56.18%),and exhibits high stability and reproducibility throughout the electrocatalytic NRR process.Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au-B coupling bond.which considerably facilitates the hydrogenation of~*N_(2)^(-)~*NH_(3).The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process,utilizing boron clusters as reducing and stabilizing agents.展开更多
Ammonia(NH_(3)), as an important chemical substance and clean energy carrier, plays an indispensable role in industrial and agricultural production. The electrocatalytic synthesis of NH+3 under mild conditions has att...Ammonia(NH_(3)), as an important chemical substance and clean energy carrier, plays an indispensable role in industrial and agricultural production. The electrocatalytic synthesis of NH+3 under mild conditions has attracted worldwide attention in the energy field due to its environmental friendliness and cost efficiency,but unsatisfactory NH_(3) yields and Faradaic efficiencies are restricting its development. The introduction of defect has been demonstrated as a feasible way to overcome the disadvantages of electrochemistry, as it can regulate the electronic structure and modulate coordination environment of electrocatalysts, which further create active sites and enhance nitrogen adsorption. In this regard, it is necessary to understand the effects of various types of defects on electrocatalysts based on the latest progress in the defect engineering for nitrogen reduction reaction(NRR). In this review, the concept, classifications, and characterization of defects as well as the approaches to create them in electrocatalysts are firstly discussed.Then, certain types of defects(vacancy, dopant, amorphism, edge/corner, and porousness) affecting the performances of various electrocatalysts are further described. Finally, the summary and challenges of electrocatalytic ammonia synthesis are proposed to design advanced electrocatalysts with high efficiency.展开更多
基金supported by the National Natural Science Foundation of China(22075133,62288102,22375091,21971114,and 21701086)the Jiangsu Provincial Funds(BX2022013)。
文摘Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges.Herein,we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics.An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles(2-6 nm in diameter)loaded on BO_(x) substrates(AuBO_(x)),in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles.The electrochemical results show that Au-BO_(x) possesses excellent NRR activity(NH_(3) yield of 48.52μg h^(-1)mg_(cat)^(-1),Faraday efficiency of 56.18%),and exhibits high stability and reproducibility throughout the electrocatalytic NRR process.Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au-B coupling bond.which considerably facilitates the hydrogenation of~*N_(2)^(-)~*NH_(3).The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process,utilizing boron clusters as reducing and stabilizing agents.
基金supported by the National Natural Science Foundation of China (Nos. 22075133 and 21701086)。
文摘Ammonia(NH_(3)), as an important chemical substance and clean energy carrier, plays an indispensable role in industrial and agricultural production. The electrocatalytic synthesis of NH+3 under mild conditions has attracted worldwide attention in the energy field due to its environmental friendliness and cost efficiency,but unsatisfactory NH_(3) yields and Faradaic efficiencies are restricting its development. The introduction of defect has been demonstrated as a feasible way to overcome the disadvantages of electrochemistry, as it can regulate the electronic structure and modulate coordination environment of electrocatalysts, which further create active sites and enhance nitrogen adsorption. In this regard, it is necessary to understand the effects of various types of defects on electrocatalysts based on the latest progress in the defect engineering for nitrogen reduction reaction(NRR). In this review, the concept, classifications, and characterization of defects as well as the approaches to create them in electrocatalysts are firstly discussed.Then, certain types of defects(vacancy, dopant, amorphism, edge/corner, and porousness) affecting the performances of various electrocatalysts are further described. Finally, the summary and challenges of electrocatalytic ammonia synthesis are proposed to design advanced electrocatalysts with high efficiency.
