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Catalytic Hydrogen Production from Formaldehyde over Immobilized Ruthenium Complexes

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Abstract

Formaldehyde is an important industrial chemical. Recently, it become an alternative material for hydrogen production since the development of hydrogen energy. Formaldehyde exists as methanediol in water, and could decompose into hydrogen under low temperature. Ruthenium complex is a homogeneous catalyst which has high activity and selectivity for formaldehyde decomposition. But a common problem is that it is difficult to be recycled from solution. In this research, we prepared a novel 2D covalent triazine framework (CTF) for Ru(p-Cymene)Cl2 immobilization, and obtained the heterogeneous catalyst for formaldehyde decomposition. We found the mole ratio of H2 to CO2 is not 2 during formaldehyde decomposition, which is inconsistent with the chemical equation (HCHO + H2O = 2 H2 + CO2). The mole ratio decreases continuously, even below 2. It indicates the formaldehyde decomposition is not a one-step process over the immobilized ruthenium. Firstly, hydrogen and formic acid were produced through formaldehyde-water shift reaction. Thus, there’s not enough carbon dioxide could be detected at the beginning of formaldehyde decomposition. The TOF achieves to 1650 h−1 in this process at 90 °C. Then, formic acid could further decompose into hydrogen and carbon dioxide. A significant ruthenium hydride was detected by FTIR during formaldehyde decomposition, which plays an important role in both formaldehyde-water shift reaction and formic acid decomposition. This work proposed a novel method for organometallic immobilization and hydrogen production from formaldehyde decomposition.

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Acknowledgements

The authors are grateful for financial support granted by the National Natural Science Foundation of China (No. 21902115), China Postdoctoral Science Foundation (No. 2018M632406).

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Yulu Zhan

  2. School of Materials Science and Engineering, Institute of Materials Science and Devices, Suzhou University of Science and Technology, Suzhou, 215009, China

    Shengxing Zhou, Ying Xu & Yangbin Shen

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  1. Yulu Zhan
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  2. Shengxing Zhou
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Correspondence to Yulu Zhan or Yangbin Shen.

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Zhan, Y., Zhou, S., Xu, Y. et al. Catalytic Hydrogen Production from Formaldehyde over Immobilized Ruthenium Complexes. Catal Lett 154, 808–815 (2024). https://doi.org/10.1007/s10562-023-04349-4

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  • DOI: https://doi.org/10.1007/s10562-023-04349-4

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