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Updated: Jun 4, 2026

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
Interconversion between formic acid and H(2)/CO(2) using rhodium and ruthenium catalysts for CO(2) fixation and H(2)
Yuichiro Himeda1, Satoru Miyazawa, Takuji Hirose
1Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, Tsukuba Central 5-2, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan. himeda.y@aist.go.jp
Abstract:
The interconversion between formic acid and H(2)/CO(2) using half-sandwich rhodium and ruthenium catalysts with 4,4'-dihydroxy-2,2'-bipyridine (DHBP) was investigated. The influence of substituents of the bipyridine ligand was studied. Chemical shifts of protons in bipyridine linearly correlated with Hammett substituent constants. In the hydrogenation of CO(2) /bicarbonate to formate under basic conditions, significant activations of the catalysts were caused by the electronic effect of oxyanions generated by deprotonation of the hydroxyl group. Initial turnover frequencies of the ruthenium- and rhodium-DHBP complexes increased 65- and 8-fold, respectively, compared to the corresponding unsubstituted bipyridine complexes. In the decomposition of formic acid under acidic conditions, activity enhancement by the electronic effect of the hydroxyl group was observed for the ruthenium catalyst. The rhodium-DHBP catalyst showed high activity without CO contamination in a relatively wide pH range. Pressurized H(2) can be obtained using an autoclave reactor. The highest turnover frequency and number were obtained at 80 °C. The catalytic system provides valuable insight into the use of CO(2) as a H(2) storage material by combining CO(2) hydrogenation with formic acid decomposition.
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