Tuning the Catalytic Preference of Ruthenium Catalysts for Nitrogen Reduction by Atomic Dispersion. (12th November 2019)

• Record Type: Journal Article
• Authors: Yu, Bing; Li, Hao; White, Jai; Donne, Scott; Yi, Jiabao; Xi, Shibo; Fu, Yang; Henkelman, Graeme; Yu, Hai; Chen, Zuliang; Ma, Tianyi
• Is Part Of: Advanced functional materials. Volume 30:Number 6(2020)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2019-11-12
• Subjects: ammonia synthesis -- g‐C3N4 -- hydrogen evolution -- single atoms; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adfm.201905665
• Languages: English
• ISSNs: 1616-301X

Abstract

Abstract: Developing cost‐effective, high‐performance nitrogen reduction reaction (NRR) electrocatalysts is required for the production of green and low‐cost ammonia under ambient conditions. Here, a strategy is proposed to adjust the reaction preference of noble metals by tuning the size and local chemical environment of the active sites. This proof‐of‐concept model is realized by single ruthenium atoms distributed in a matrix of graphitic carbon nitride (Ru SAs/g‐C3 N4 ). This model is compared, in terms of the NRR activity, to bulk Ru. The as‐synthesized Ru SAs/g‐C3 N4 exhibits excellent catalytic activity and selectivity with an NH3 yield rate of 23.0 µg mgcat −1 h −1 and a Faradaic efficiency as high as 8.3% at a low overpotential (0.05 V vs the reversible hydrogen electrode), which is far better than that of the bulk Ru counterpart. Moreover, the Ru SAs/g‐C3 N4 displays a high stability during five recycling tests and a 12 h potentiostatic test. Density functional theory calculations reveal that compared to bulk Ru surfaces, Ru SAs/g‐C3 N4 has more facile reaction thermodynamics, and the enhanced NRR performance of Ru SAs/g‐C3 N4 originates from a tuning of the d‐electron energies from that of the bulk to a single‐atom, causing an up‐shift of the d‐band center toward the Fermi level. Abstract : Ru SAs/g‐C3 N4 exhibits excellent catalytic activity and selectivity, with an NH3 yield rate of 23.0 µg mgcat −1 h −1 and a Faradaic efficiency as high as 8.3% at 0.05 V versus reversible hydrogen electrode, which is far better than that of the bulk Ru counterpart. This is because Ru SAs/g‐C3 N4 has stronger N2 adsorption and less H poisoning at the reactive sites.