A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the term...A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the terminal amino of MIL-101(Cr)-NH_2 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 RuCl_3@MIL-101 (Cr)-DPPB enhances its catalytic performance for CO_2 hydrogenation to formic acid. The turnover number (TON) of formic acid was up to 831 in reaction time of 2 h with dimethyl sulfoxide (DMSO) and water (H_2O) as mixed solvent, trimethylamine (Et_3N) as organic base, and PPh_3 as electronic additive.展开更多
Summary of main observation and conclusion RuCl3 catalyst system has many advantages for the hydro-esterification of methyl formate and ethylene to methyl propionate.However,the unsatisfied performance restricts the d...Summary of main observation and conclusion RuCl3 catalyst system has many advantages for the hydro-esterification of methyl formate and ethylene to methyl propionate.However,the unsatisfied performance restricts the development of this route.In this work,high-performance RuCl3 catalyst systems (RuCl3-[PPN]Cl-Et4NI and RuCl3-Nal) are firstly reported for this reaction.In RuCl3-[PPN]Cl-Et4NI catalyst system,the conversion of methyl formate and the selectivity to methyl propionate are 93.9% and 90.9% at mild reaction conditions (165 ℃,2.5 MPa),respectively.Noticeably,a simple inorganic RuCl3-Nal catalyst system achieves 88.8% conversion of methyl formate and 97.6% selectivity to methyl propionate (86.7% yield) at same conditions.Nal,as a promoter,may inhibit the decomposition of methyl formate and be conducive to the formation of methyl propionate.The effects of solvents and promoters are investigated in detail.In addition,the reaction mechanism has been also analyzed.It is hoped to lay a certain foundation for further industrial application.展开更多
基金Financial support from the National Natural Science Foundation of China(NSFC, Nos. 21776211, 21325626)the Program for New Century Excellent Talents in University(No. NCET-13-0411)the Program of Introducing Talents of Discipline to Universities(No. B06006)
文摘A series of efficient ruthenium chloride (RuCl_3)-anchored MOF catalysts,such as RuCl_3@MIL-101 (Cr)-Sal,and RuCl_3@MIL-101 (Cr)-DPPB, have been successfully synthesized by post-synthetic modification (PSM)of the terminal amino of MIL-101(Cr)-NH_2 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 RuCl_3@MIL-101 (Cr)-DPPB enhances its catalytic performance for CO_2 hydrogenation to formic acid. The turnover number (TON) of formic acid was up to 831 in reaction time of 2 h with dimethyl sulfoxide (DMSO) and water (H_2O) as mixed solvent, trimethylamine (Et_3N) as organic base, and PPh_3 as electronic additive.
基金supported by the National Key R&D Program of China (Nos.2017YFA0206802,2017YFA0700103)the National Natural Science Foundation of China (Nos.91545201,91645116)+2 种基金the Programs of the Chinese Academy of Sciences (Nos.ZDRW-CN-2016-1,QYZDJ-SSW-SLH028)the Natural Science Foundation of Fujian Province (No.2018J06005)Youth Innovation Promotion Association CAS,China Postdoctoral Science Foundation (No.2016LH0018).
文摘Summary of main observation and conclusion RuCl3 catalyst system has many advantages for the hydro-esterification of methyl formate and ethylene to methyl propionate.However,the unsatisfied performance restricts the development of this route.In this work,high-performance RuCl3 catalyst systems (RuCl3-[PPN]Cl-Et4NI and RuCl3-Nal) are firstly reported for this reaction.In RuCl3-[PPN]Cl-Et4NI catalyst system,the conversion of methyl formate and the selectivity to methyl propionate are 93.9% and 90.9% at mild reaction conditions (165 ℃,2.5 MPa),respectively.Noticeably,a simple inorganic RuCl3-Nal catalyst system achieves 88.8% conversion of methyl formate and 97.6% selectivity to methyl propionate (86.7% yield) at same conditions.Nal,as a promoter,may inhibit the decomposition of methyl formate and be conducive to the formation of methyl propionate.The effects of solvents and promoters are investigated in detail.In addition,the reaction mechanism has been also analyzed.It is hoped to lay a certain foundation for further industrial application.
