Ultra‐Dense Supported Ruthenium Oxide Clusters via Directed Ion Exchange for Efficient Valorization of 5‐Hydroxymethylfurfural

Author:

Lei Can1,Chen Zhe1,Jiang Tao1,Wang Shaoyan1,Du Wei1,Cha Shuangshuang1,Hao Yaming1,Wang Ran1,Cao Xueting1,Gong Ming1ORCID

Affiliation:

1. Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Fudan University Shanghai 200438 P. R. China

Abstract

AbstractMaximizing the loadings of active centers without aggregation for a supported catalyst is a grand challenge but essential for achieving high gravimetric catalytic activity, especially toward multi‐step reactions. The oxidation of 5‐hydroxymethylfurfural (HMF), a key biomass‐derived platform molecule, into 2,5‐furandicarboxylic acid (FDCA), a promising alternative to polyester monomer, is such a multi‐step reaction that involves 6 proton and electron transfers. This process often demands strong alkaline environment but also suffers from the alkali‐driven polymerization side‐reaction. Meanwhile, neutral media ameliorates the polymerization, but lacks efficient catalyst toward deep oxidation. Herein, we devised a strategy of creating ultra‐dense supported Ru oxide clusters via directed ion exchange in a Co hydroxyanion (CoHA) support material. Pyrimidine ligands were first incorporated into the CoHA interlayers, and the subsequent evacuation of pyrimidines created porous channels for the directed ion exchange with the built‐in anions in CoHA, which allowed the dense and mono‐disperse functionalization of RuCl62− anions and their resulting Ru oxide clusters. These ultra‐dense Ru oxide clusters not only enable high HMF electrooxidation currents under neutral conditions but also create microscopic channels in‐between the clusters for the expedited re‐adsorption and oxidation of intermediates toward highly oxidized product, such as 5‐formyl‐2‐furoic acid (FFCA) and FDCA. A two‐stage HMF oxidation process, consisting of ambient conversion of HMF into FFCA and FFCA oxidation into FDCA under 60 °C, was eventually developed to first achieve a high FDCA yield of 92.1 % under neutral media with significantly reduced polymerization.

Funder

National Natural Science Foundation of China

Publisher

Wiley

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