Reductive Amination of Cyclohexanone via Bimetallic Rh-Ni Catalysts: A Pathway to Improved Catalytic Efficiency

Reductive amination of cyclohexanone with NH3 and H2 over Rh and Rh-Ni catalysts on SiO2 has been studied. Research has focused on the catalytic efficiency of monometallic and bimetallic catalysts in the production of cyclohexylamine, a key intermediate in the synthesis of numerous fine chemicals. Through the wet impregnation method, Rh and Rh-Ni catalysts with varying nickel loadings (1, 2, 5, and 10 wt.%) were synthesized and characterized using techniques such as N2 physisorption, TEM, HAADF-STEM, XRD, XPS, H2-TPR, and NH3-TPD. The catalytic reactions were conducted under controlled conditions using a glass-coated reactor, using ammonia as nitrogen source. Rh-Ni bimetallic catalysts exhibited the highest conversion rates on reductive amination, attributed to enhanced dispersion and advantageous surface properties. High metal dispersion and small particle sizes were confirmed by TEM, HAADF-STEM, and XRD. XPS analysis confirmed the reduced state of Rh and mainly oxidized state of Ni, while H2-TPR and NH3-TPD results indicated improved reducibility and acidity, respectively, which are critical for catalytic activity. Monometallic Rh/SiO2 catalyst showed 83.4% of conversion after 300 min and selectivity of 99.1% toward the desired product cyclohexylamine. The addition of nickel, a cheap and easily available metal, increases the activity without compromising selectivity. At 300 min of the reaction, the 2 wt.% NiRh/SiO2 catalyst exhibited the highest conversion, yield, and selectivity for the desired product cyclohexylamine, 99.8%, 96.4%, and 96.6% respectively. Additionally, this catalyst is recyclable after the fourth cycle, showing 99.5% selectivity and 74.0% yield for cyclohexylamine at 75.7% conversion. Recycling tests confirmed the stability of bimetallic catalysts, maintaining performance over multiple cycles without significant deactivation.