Plasma-assisted manipulation of vanadia nanoclusters for efficient selective catalytic reduction of NOx

Yong Yin; Bingcheng Luo; Kezhi Li; Benjamin M Moskowitz; Bar Mosevizky Lis; Israel E Wachs; Minghui Zhu; Ye Sun; Tianle Zhu; Xiang Li

doi:10.1038/s41467-024-47878-1

Plasma-assisted manipulation of vanadia nanoclusters for efficient selective catalytic reduction of NO_x

Nat Commun. 2024 Apr 27;15(1):3592. doi: 10.1038/s41467-024-47878-1.

Authors

Yong Yin^#¹, Bingcheng Luo^#², Kezhi Li³, Benjamin M Moskowitz⁴, Bar Mosevizky Lis⁴, Israel E Wachs⁵, Minghui Zhu⁶, Ye Sun¹, Tianle Zhu¹, Xiang Li⁷

Affiliations

¹ School of Space and Environment, Beihang University, Beijing, 100191, China.
² College of Science, China Agricultural University, Beijing, 100083, China.
³ Institute of Engineering Technology, Sinopec Catalyst Co. Ltd., Beijing, 101111, China.
⁴ Operando Molecular Spectroscopy & Catalysis Laboratory, Department of Chemical and Biomolecular Engineering, Lehigh University, Bethlehem, PA, 18015, USA.
⁵ Operando Molecular Spectroscopy & Catalysis Laboratory, Department of Chemical and Biomolecular Engineering, Lehigh University, Bethlehem, PA, 18015, USA. iew0@lehigh.edu.
⁶ State Key Laboratory of Chemical Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China. minghuizhu@ecust.edu.cn.
⁷ School of Space and Environment, Beihang University, Beijing, 100191, China. xiangli@buaa.edu.cn.

^# Contributed equally.

Abstract

Supported nanoclusters (SNCs) with distinct geometric and electronic structures have garnered significant attention in the field of heterogeneous catalysis. However, their directed synthesis remains a challenge due to limited efficient approaches. This study presents a plasma-assisted treatment strategy to achieve supported metal oxide nanoclusters from a rapid transformation of monomeric dispersed metal oxides. As a case study, oligomeric vanadia-dominated surface sites were derived from the classic supported V₂O₅-WO₃/TiO₂ (VWT) catalyst and showed nearly an order of magnitude increase in turnover frequency (TOF) value via an H₂-plasma treatment for selective catalytic reduction of NO with NH₃. Such oligomeric surface VO_x sites were not only successfully observed and firstly distinguished from WO_x and TiO₂ by advanced electron microscopy, but also facilitated the generation of surface amide and nitrates intermediates that enable barrier-less steps in the SCR reaction as observed by modulation excitation spectroscopy technologies and predicted DFT calculations.