Defective g-C3N4 supported Ru3 single-cluster catalyst for ammonia synthesis through parallel reaction pathways
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Designing catalyst to achieve ammonia synthesis at mild conditions is a meaningful challenge in catalysis community. Defective g-C3N4 nanosheet supported single-cluster ruthenium and iron catalysts were investigated for their ammonia synthesis performance. Based on density functional theory (DFT) calculations and microkinetic simulations, Ru3 single-cluster anchored on defective g-C3N4 nanosheet (Ru3/Nv-g-C3N4) has a turnover frequency (TOF) 5.8 times higher than the Ru(0001) step surface at industrial reaction conditions of 673 K and 100 bar for ammonia synthesis. In other words, similar TOFs could be achieved on Ru3/Nv-g-C3N4 at much milder conditions (623 K, 30 bar) than on Ru(0001) (673 K, 100 bar). Our computations reveal the reaction proceeds parallelly on Ru3/Nv-g-C3N4 through both dissociative and alternative associative mechanisms at typical reaction conditions (600–700 K, 10–100 bar); N–N bond cleavage of *N2 and *NNH from the two respective pathways controls the reaction collectively. With increasing temperatures or decreasing pressures, the dissociative mechanism gradually prevails and associative mechanism recedes. In comparison, Fe3/Nv-g-C3N4 catalyst shows a much lower catalytic activity than Ru3/Nv-g-C3N4 by two orders of magnitude and the reaction occurs solely through the dissociative pathway. The finding provides a prospective candidate and deepens the mechanistic understanding for ammonia synthesis catalyzed by single-cluster catalysts (SCCs).
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Defective g-C3N4 supported Ru3 single-cluster catalyst for ammonia synthesis through parallel reaction pathways
Abstract
Designing catalyst to achieve ammonia synthesis at mild conditions is a meaningful challenge in catalysis community. Defective g-C3N4 nanosheet supported single-cluster ruthenium and iron catalysts were investigated for their ammonia synthesis performance. Based on density functional theory (DFT) calculations and microkinetic simulations, Ru3 single-cluster anchored on defective g-C3N4 nanosheet (Ru3/Nv-g-C3N4) has a turnover frequency (TOF) 5.8 times higher than the Ru(0001) step surface at industrial reaction conditions of 673 K and 100 bar for ammonia synthesis. In other words, similar TOFs could be achieved on Ru3/Nv-g-C3N4 at much milder conditions (623 K, 30 bar) than on Ru(0001) (673 K, 100 bar). Our computations reveal the reaction proceeds parallelly on Ru3/Nv-g-C3N4 through both dissociative and alternative associative mechanisms at typical reaction conditions (600–700 K, 10–100 bar); N–N bond cleavage of *N2 and *NNH from the two respective pathways controls the reaction collectively. With increasing temperatures or decreasing pressures, the dissociative mechanism gradually prevails and associative mechanism recedes. In comparison, Fe3/Nv-g-C3N4 catalyst shows a much lower catalytic activity than Ru3/Nv-g-C3N4 by two orders of magnitude and the reaction occurs solely through the dissociative pathway. The finding provides a prospective candidate and deepens the mechanistic understanding for ammonia synthesis catalyzed by single-cluster catalysts (SCCs).
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Acknowledgements
This work was supported financially by the National Natural Science Foundation of China (Nos. 91961125 and 22002085). This work was also supported by the “Fundamental Research Funds for the Central Universities” (No. 2018JBZ107), Guangdong Basic and Applied Basic Research Foundation (No. 2020A1515110832), “Key Program for International S&T Cooperation Projects of China” from the Ministry of Science and Technology of China (No. 2018YFE0124600), Chemistry and Chemical Engineering Guangdong Laboratory (No. 1932004), Science and Technology Project of Guangdong Province (No. 2020B0101370001), and the Project from China Petrochemical Corporation (No. S20L00151).
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