4.6 Article

Chemoselective hydrogenation of cinnamaldehyde over a tailored oxygen-vacancy-rich Pd@ZrO2 catalyst

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NEW JOURNAL OF CHEMISTRY
卷 45, 期 12, 页码 5659-5681

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ROYAL SOC CHEMISTRY
DOI: 10.1039/d0nj05595f

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  1. CNMS, JAIN (Deemed-to-be University)
  2. Nano Mission, DST, Government of India [SR/NM/NS-20/2014]
  3. Centre for Nano and Material Sciences (CNMS), JAIN (Deemed-to-be University), Bangalore [II(39)/17/005/2017SG]

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The development of oxygen vacancies in Pd@ZrO2 catalysts through a two-step synthesis method was studied, and it was found that the synergistic effect between oxygen vacancies and nano-sized active Pd metals played a crucial role in enhancing the selectivity for the hydrogenation of cinnamaldehyde to hydrocinnamaldehyde. The optimized reaction parameters, including 4 wt% Pd loading, 100 degrees C temperature, and 10 bar H-2 pressure, were identified to provide efficient conversion of cinnamaldehyde with high yield and excellent recyclability of the catalyst, making oxygen-vacancy-rich Pd@ZrO2 catalysts promising for industrial applications.
Selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde is captivating due to its industrial relevance. Herein, a two-step synthesis method was adopted to develop oxygen vacancies in Pd@ZrO2 catalysts. The oxygen vacancies were developed in Pd@ZrO2 catalysts during impregnation of Pd which was confirmed by XPS and HR-TEM analyses. The characterization results revealed that there was a synergistic role of oxygen vacancies and nano-sized active Pd metals in Pd@ZrO2 catalysts that assisted in achieving selectivity for hydrocinnamaldehyde which has been discussed in this study. We also studied the effects of different reaction parameters which revealed that 4 wt% Pd loading in a Pd@ZrO2 catalyst provided enough active sites for complete conversion of CAL. Additionally, 100 degrees C temperature and 10 bar H-2 pressure provided enough energy for effective collisions and activation of reactants and catalysts to form the desired product in a reaction time of 9 h. Therefore, a defect-rich 4-Pd@ZrO2 catalyst demonstrated complete CAL conversion with 86% yield towards HCAL which is the best result amongst various Pd@ZrO2 catalysts with different Pd loading investigated for the hydrogenation of cinnamaldehyde. Moreover, a plausible mechanism was proposed to support the chemoselective hydrogenation of cinnamaldehyde over a 4-Pd@ZrO2 catalyst. Along with high catalytic performance, the 4-Pd@ZrO2 catalyst also showed impressive recyclability performance for up to six recycles. Thus, the oxygen-vacancy-rich Pd@ZrO2 can be considered as an efficient catalyst for the chemoselective hydrogenation of cinnamaldehyde.

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