Promoting NO_(x)reduction via in situ activation of perovskite supported Pd catalysts under alternating lean-burn/fuel-rich operating atmospheres

Herein,we report the excellent De-NO_(x)performance of La0.7Sr0.3MnO3(LSM)perovskite-supported Pd catalysts(Pd-LSM)in alternating lean-burn/fuel-rich atmospheres using C3H6 as reductant and describe the in situ activation of the Pd catalysts via metal-support interaction(MSI)tuning.The NO_(x)reduction conversion of the Pd-LSM catalyst increased significantly from 56.1%to 90.1%and the production of N2O was suppressed.Our results demonstrated that this behavior was mainly attributed to the in situ transformation of Pd2+into Pd0 during the reaction.The generated Pd0 species could readily activate the C3H6 reductant and achieve an eight-fold higher turnover frequency than Pd2+for the reduction of NO_(x).Moreover,excessive MSIs inhibited the in situ generation of Pd0,and thereby,lowered the De-NO_(x)activity of the catalyst even at high Pd dispersion.In addition,the Pd-LSM catalysts exhibited much higher S tolerance than conventional Al_(2)O_(3)-supported catalysts.Our study provides a new approach for analyzing and designing highly active metal catalysts operated under dynamic alternating oxidizing/reducing atmospheric conditions.

The reactive activities of natural amino acids: key principles of peptide-templated Au cluster synthesis

Coating of gold nanoclusters with peptides is an important targeting method in biomedical applications.However, their synthetic method highly influences their targeting ability. Current methods often use harsh reagents and organic solvents to control morphology, which are not preferred for biomedical applications. Recently, several peptides with specific amino acid sequences have successfully been used to reduce Au ions and synthesize biocompatible peptide-covered gold particles in situ.However, the molecular mechanism of peptide-assisted nanocluster formation is yet unclear. Thus, reactive abilities of different amino acids should be studied to improve design of peptides with predetermined amino acid content and consequently, synthesize gold nanoclusters with improved performance. In this theoretical study, we have approximated the reactive abilities of 20 natural amino acids in their neutral state using density functional theory calculations, such as Fukui indices and HOMO/LUMO composition analysis. We have found that the top reducing agents are tryptophan, histidine, and tyrosine, and thestrongest binding can be expected from methionine and cysteine. Further study of the exact reactive sites in these high reactive amino acids provided the deep insight for the peptide design route for the targeted gold nanocluster formation.