RuCl3 anchored onto post-synthetic modification MIL-101(Cr)-NH2 as heterogeneous catalyst for hydrogenation of CO2 to formic acid

• Published in: Chinese chemical letters 2019-02, Vol.30 (2), p.398-402
• Main Authors: Wang, Shengping, Hou, Shihui, Wu, Chao, Zhao, Yujun, Ma, Xinbin
• Format: Article
• Language: English
• Subjects: Anchoring Ru(III); Electron-donor substituent; MIL-101(Cr)-DPPB; Post-synthetic modification; RuCl3
• ISSN: 1001-8417; 1878-5964
• DOI: 10.1016/j.cclet.2018.06.021

A series of novel metal–organic framework-anchored RuCl3 catalysts for the CO2 hydrogenation to formic acid have been developed. RuCl3@MIL-101(Cr)-DPPB catalyst exhibited the higher catalytic performance for hydrogenation of CO2 to formic acid due to the phosphorus atom of DPPBde as a stronger electron-donor substituent to promote the insertion of CO2 into RuH bond. [Display omitted] A series of efficient ruthenium chloride (RuCl3)-anchored MOF catalysts, such as RuCl3@MIL-101(Cr)-Sal, and RuCl3@MIL-101(Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM) of the terminal amino of MIL-101(Cr)-NH2 with salicylaldehyde, 2-diphenylphosphinobenzaldehyde (DPPBde) and anchoring of Ru(III) ions. The stronger coordination electron donor interaction between Ru(III) ions and chelating groups in the RuCl3@MIL-101(Cr)-DPPB enhances its catalytic performance for CO2 hydrogenation to formic acid. The turnover number (TON) of formic acid was up to 831 in reaction time of 2h with dimethyl sulfoxide (DMSO) and water (H2O) as mixed solvent, trimethylamine (Et3N) as organic base, and PPh3 as electronic additive.