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Hollow Co@HCN Derived from ZIF-67 as a Highly Efficient Catalyst for Hydrogenation of o-Cresol to o-Methyl Cyclohexanol

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Abstract

The selective hydrogenation of o-cresol to produce o-methyl cyclohexanol, an important chemical intermediate, is an attractive approach. The design and development of efficient non-precious metal catalysts for the selective o-cresol hydrogenation remain a great challenge. Herein, cobalt nanoparticles embedded in nitrogen-doped carbon with hollow structure (Co@HCN) were fabricated by direct pyrolysis of hollow zeolitic imidazolate framework-67 (HZIF-67), and were applied in the selective hydrogenation of o-cresol to o-methyl cyclohexanol for the first time. The pyrolysis temperature and Co(NO3)2·6H2O concentration jointly regulate the morphology and physicochemical properties of the Co@HCN-T-x catalysts (T represents the pyrolysis temperature and x represents the Co(NO3)2·6H2O concentration in octanol), and significantly affect their catalytic properties. Co@HCN-500-0.1 exhibits superior catalytic activity, which is 3.3 times higher than Co@HCN-700-0.1 and 1.3 times higher than Co@HCN-500-0.4. Large ratio of meso-/macro-porous specific surface area and pore volume, small Co size with uniform dispersion, and abundant surface Co and CoNx contents together contribute to the superior catalytic activity of Co@HCN-500-0.1. More importantly, Co@HCN-500-0.1 displays convenient magnetic recoverability, superior catalytic recyclability and universal applicability. This work provides significant insights for the design of efficient non-precious metal catalysts to be applied in the selective hydrogenation of o-cresol.

Graphical Abstract

Hollow Co@HCN nanospheres were synthesized by one-step pyrolysis of HZIF-67, and the morphology, pore structure, Co size and distribution, surface composition, and yield can be adjusted by the pyrolysis temperature and Co(NO3)2·6H2O concentration. The presence of the hollow shell layer not only enhances the diffusion of the reactants, but also facilitates the dispersion and exposure of Co species, which in turn improves the catalytic performance for the selective hydrogenation of o-cresol to o-methyl cyclohexanol.

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Acknowledgements

The financial support from the National Key R&D Program (2021YFC3001103), the National Natural Science Foundation (22278209, 22178165, 21921006, 22208149), the Natural Science Foundation of Jiangsu Province (BK20211262, BK20220354), a project funded by the priority academic program development of Jiangsu higher education institutions (PAPD), and the State Key Laboratory of Materials-Oriented Chemical Engineering (ZK201902) of China are gratefully acknowledged.

Funding

Funding was provided by National Natural Science Foundation of China (Grant Nos. 22278209, 22178165, 21921006, 22208149) and Natural Science Foundation of Jiangsu Province of China (Grant Nos. BK20211262, BK20220354) and National Key R&D Program of China (Grant No. 2021YFC3001103).

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  1. State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing, 211816, China

    Chaoqun Fan, Hang Zhu, Jiuxuan Zhang, Hong Jiang & Rizhi Chen

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Fan, C., Zhu, H., Zhang, J. et al. Hollow Co@HCN Derived from ZIF-67 as a Highly Efficient Catalyst for Hydrogenation of o-Cresol to o-Methyl Cyclohexanol. Catal Lett 154, 280–294 (2024). https://doi.org/10.1007/s10562-023-04304-3

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