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Ru/SiO2 Catalyst for Highly Selective Hydrogenation of Dimethyl Malate to 1,2,4-Butanetriol at Low Temperatures in Aqueous Solvent

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Abstract

Catalytic selective hydrogenation of esterified malic acid to produce 1,2,4-butanetriol (1,2,4-BT) using H2 as the reducing reagent suffers from the low 1,2,4-BT selectivity. Here, Ru/SiO2 catalyst was employed for selective hydrogenation of dimethyl malate (DM) to produce 1,2,4-BT, which gave abnormal high DM conversion (100%) and 1,2,4-BT selectivity (92.4%) in aqueous solvent at 363 K, especially, the 1,2,4-BT yield even is higher than the optimal catalyst reported (Ru-Re, 79.8%). The reaction pathways for the DM hydrogenation on Ru/SiO2 were also proposed, suggesting that extremely high 1,2,4-BT selectivity require for the much high hydrogenation rates at low temperatures, where side-reaction transesterification rates are relatively low. The extremely high hydrogenation activity and 1,2,4-BT selectivity on Ru/SiO2 in aqueous solvent at low temperatures arise from that H2O may coordinate to Ru2+ and prevent the reduction of Ru2+ to Ru under high H2 pressure. Ru/SiO2 surface presents abundant Ru2+ in aqueous solvent, can activate H2 through heterolytic cleavage mode to form hydride, which can significantly increase hydrogenation rates of C = O groups at low temperatures. In addition, the activity and 1,2,4-BT selectivity on Ru/SiO2 catalyst only reduced by 2.3% and 2.6%, respectively over a period of 550 h.

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Acknowledgements

All authors thank the financial supports from the Strategic Priority Research Program of Chinese Academy of Sciences (Grant No. XDA 21060900), the Project of the National Natural Science Foundation of China (Grant Nos. 22102205 and 21808235), the Foundation of Shandong Energy Research Institute (SEI I202132), and the State Key Laboratory of Bio-Fibers and Eco-Textiles (Qingdao University, No. KF2020211).

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Author notes

  1. Pei Yu and Junxiang Jiang have contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Biofuels, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, Shandong, People’s Republic of China

    Pei Yu, Junxiang Jiang, Can Chen, Zhong Wang, Da Wang, Guangci Li & Xuebing Li

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  1. Pei Yu
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  2. Junxiang Jiang
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  3. Can Chen
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  4. Zhong Wang
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  5. Da Wang
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  6. Guangci Li
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Contributions

PY: investigation, visualization, writing—original draft, formal analysis; JJ: investigation, formal analysis; CC: investigation, validation; ZW: data curation, resources; DW: project administration; GL: formal analysis, supervision, writing—review and editing; XL: funding acquisition, conceptualization.

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Correspondence to Guangci Li or Xuebing Li.

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Yu, P., Jiang, J., Chen, C. et al. Ru/SiO2 Catalyst for Highly Selective Hydrogenation of Dimethyl Malate to 1,2,4-Butanetriol at Low Temperatures in Aqueous Solvent. Catal Lett 152, 3046–3057 (2022). https://doi.org/10.1007/s10562-021-03877-1

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