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Metal–Sulfur Linkages Achieved by Organic Tethering of Ruthenium Nanocrystals for Enhanced Electrochemical Nitrogen Reduction
Author(s) -
Ahmed Muhammad Ibrar,
Liu Chuangwei,
Zhao Yong,
Ren Wenhao,
Chen Xianjue,
Chen Sheng,
Zhao Chuan
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202009435
Subject(s) - catalysis , ruthenium , surface modification , chemistry , electrochemistry , faraday efficiency , sulfur , metal , adsorption , oxide , yield (engineering) , desorption , inorganic chemistry , graphene , nanocrystal , nitrogen , chemical engineering , materials science , nanotechnology , organic chemistry , electrode , engineering , metallurgy
Inspired by the metal–sulfur (M‐S) linkages in the nitrogenase enzyme, here we show a surface modification strategy to modulate the electronic structure and improve the N 2 availability on a catalytic surface, which suppresses the hydrogen evolution reaction (HER) and improves the rate of NH 3 production. Ruthenium nanocrystals anchored on reduced graphene oxide (Ru/rGO) are modified with different aliphatic thiols to achieve M‐S linkages. A high faradaic efficiency (11 %) with an improved NH 3 yield (50 μg h −1 mg −1 ) is achieved at −0.1 V vs. RHE in acidic conditions by using dodecanethiol. DFT calculations reveal intermediate N 2 adsorption and desorption of the product is achieved by electronic structure modification along with the suppression of the HER by surface modification. The modified catalyst shows excellent stability and recyclability for NH 3 production, as confirmed by rigorous control experiments including 15 N isotope labeling experiments.