Rhodium nanoparticles in ZrO2 on N-doped carbon leads to ultra-high catalytic selectivity and activity in nitroarene hydrogenation

DOI: 10.1016/j.apcatb.2025.125686

Authors: Luna Ruan (Jiangxi University of Science and Technology; Ganjiang Innovation Academy, Chinese Academy of Sciences) , Xinyu Han (Ganjiang Innovation Academy, Chinese Academy of Sciences) , Lihua Zhu (Jiangxi University of Science and Technology; The University of Hong Kong) , Congxiao Shang (The University of Hong Kong) , Anna Kroner (Diamond Light Source) , Kaijie Liu (Ganjiang Innovation Academy, Chinese Academy of Sciences) , Yibo Zhang (Ganjiang Innovation Academy, Chinese Academy of Sciences) , Bing Hui Chen (Xiamen University Malaysia; Xiamen University (China)) , Zhengxiao Guo (The University of Hong Kong)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Applied Catalysis B: Environment And Energy , VOL 379

State: Published (Approved)
Published: December 2025

Abstract: Metal nanoparticles are widely considered for heterogeneous catalysis due to their high atomic efficiency and tunable active microenvironment, but their specific functional tendencies are still unclear. Here, we report that a Rh@ZrO2/NC catalyst with only 0.1 wt% Rh exhibits exceptional catalytic performance and high selectivity (p-nitroacetophenone conversion-98.6 %, p-aminoacetophenone selectivity-100 %, r-56.4 molp-nitroacetophenone/(molRh·min)) towards the hydrogenation of the -NO2 group in nitroarene to -NH2. This is because the interaction between Rh species and “ZrO2-N” results in significant hydrogen spillover in the catalyst, as supported by DFT calculations. Extensive characterizations from TG, DTG, NAP-XPS, in-situ Raman spectroscopy, in-situ DRIFT spectroscopy and DFT calculations further confirm the adsorption, activation and dissociation of hydrogen on Rh nanoparticles. The H* species migrate readily over ZrO2-NC, to facilitate the catalytic activity and selectivity for the hydrogenation of nitroarene. This study presents a new approach to develop highly efficient and selective metal nanoparticle-catalysts for cost-effective hydrogenation reactions.

Journal Keywords: Rh nanoparticles; Rh@ZrO2/NC; Nitroarene hydrogenation; Hydrogen spillover

Subject Areas: Chemistry, Materials


Instruments: B18-Core EXAFS

Added On: 16/07/2025 09:37

Discipline Tags:

Physical Chemistry Catalysis Chemistry Materials Science Nanoscience/Nanotechnology

Technical Tags:

Spectroscopy X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS) X-ray Absorption Near Edge Structure (XANES)