CO_(2),as a greenhouse gas,has excessive emissions that lead to many environmental problems and is a rich and cheap C1 resource.Effective utilization and transformation of CO_(2)has become an important means of achiev...CO_(2),as a greenhouse gas,has excessive emissions that lead to many environmental problems and is a rich and cheap C1 resource.Effective utilization and transformation of CO_(2)has become an important means of achieving carbon neutrality.Oxazolidinones are important intermediates in pharmaceutical chemistry that can be synthesized by carboxylation cyclization of CO_(2)with propargyl amines or cycloaddition of CO_(2)with aziridines.Owing to CO_(2)’s high stability,these reactions typically require harsh conditions,such as high temperatures or pressures.It is desirable,but challenging,to find a catalyst that can catalyze these two types of reactions under relatively mild conditions.Metal-organic frameworks(MOFs)are an emerging class of heterogeneous catalysts that with great potential in the catalytic conversion of CO_(2)to value-added products because of their attractive features,such as abundant metal active sites,inherent porosity,and easy functionalities.Herein,a unique three-dimensional(3D)MOF,{(CH_(3)NH_(2)CH_(3))_(2)[Co_(3)(BCP)_(2)]·6H_(2)O·4DMF}n(1)(H_(4)BCP:5‐(2,6‐bis(4‐carboxyphenyl)pyridin‐4‐yl)isophthalic acid;DMF:N,N'‐dimethylformamide),was synthesized using carboxylic acid ligands and cobalt salts via a solvothermal method.According to structural analysis,[Co_(3)]clusters as secondary building units(SBU)are bridged by BCP4−ligands,forming an anion framework with flu topology,and dimethylamine cations act as counter ions in the pores.The framework has rectangular channels of approximately 0.4 nm×0.9 nm along the a-axis direction,exhibiting its porous property.Infrared spectroscopy(IR)and X-ray photoelectron spectroscopy(XPS)characterizations proved the coordination interaction between the carboxyl groups in the ligands and the metal ions.The powder X-Ray diffraction(PXRD)test further confirmed the phase purity of the synthesized samples.PXRD and thermogravimetry(TG)analyses indicated that 1 possessed good solvent and thermal stabilities.The catalytic experiments revealed that 1 could effectively catalyze CO_(2)with aziridines or propargyl amines to prepare oxazolidinones.In the cycloaddition of CO_(2)with aziridines,1 can facilitate the reaction under relatively mild conditions compared to other reported MOF-based catalysts.It shows excellent universality for substrates with various substitutions on the N atom or benzene ring.Investigation of the mechanism indicated that the coordination interaction of cobalt metal sites with the nitrogen atoms of aziridines can activate the substrates.For the carboxylative cyclization of CO_(2)with propargylic amines,this catalyst also has a broad substrate scope.Control experiments and nuclear magnetic resonance(NMR)tests suggest that Lewis acid metal sites are responsible for the high catalytic efficiency achieved by activating the alkyne groups.Moreover,1 showed good reusability in both reactions.Compound 1 represents a new catalyst that enables“two birds with one stone”in the catalytic synthesis of oxazolidinones using CO_(2).展开更多
The sluggish kinetics of the sulfur redox reaction(SRR)and the shuttling effect of lithium polysulfides(LiPSs)both restrict the practical application of lithium-sulfur(Li-S)batteries.Heterostructures,with their pronou...The sluggish kinetics of the sulfur redox reaction(SRR)and the shuttling effect of lithium polysulfides(LiPSs)both restrict the practical application of lithium-sulfur(Li-S)batteries.Heterostructures,with their pronounced electroactivity and structural stability,showcase their potential as electrodes/functional separators for lithium-sulfur batteries.Herein,we proposed a bifunctional catalyst exhibiting strong adsorption and rapid catalytic conversion of LiPSs through in situ UV photocatalytic synthesis of Ti_(3)C_(2)@TiO_(2)heterostructure.The TiO_(2)nanoparticles act as the anchoring center for LiPSs,while the electrically conductive Ti_(3)C_(2)ensures the rapid diffusion of these LiPSs from TiO_(2)to the catalytically active Ti_(3)C_(2)layer across heterogeneous interfaces.The Li-S batteries with Ti_(3)C_(2)@TiO_(2)-40 min-PP separator delivered a high initial capacity of 1283 mA∙h/g,which decreased slightly to 691 mA∙h/g after 200 cycles at 1C.This work advances the understanding of the synergistic effect of polysulfide adsorbents and conductive agents in inhibiting shuttle effects,and offers a method for designing polysulfide barriers in lithium-sulfur batteries.展开更多
文摘CO_(2),as a greenhouse gas,has excessive emissions that lead to many environmental problems and is a rich and cheap C1 resource.Effective utilization and transformation of CO_(2)has become an important means of achieving carbon neutrality.Oxazolidinones are important intermediates in pharmaceutical chemistry that can be synthesized by carboxylation cyclization of CO_(2)with propargyl amines or cycloaddition of CO_(2)with aziridines.Owing to CO_(2)’s high stability,these reactions typically require harsh conditions,such as high temperatures or pressures.It is desirable,but challenging,to find a catalyst that can catalyze these two types of reactions under relatively mild conditions.Metal-organic frameworks(MOFs)are an emerging class of heterogeneous catalysts that with great potential in the catalytic conversion of CO_(2)to value-added products because of their attractive features,such as abundant metal active sites,inherent porosity,and easy functionalities.Herein,a unique three-dimensional(3D)MOF,{(CH_(3)NH_(2)CH_(3))_(2)[Co_(3)(BCP)_(2)]·6H_(2)O·4DMF}n(1)(H_(4)BCP:5‐(2,6‐bis(4‐carboxyphenyl)pyridin‐4‐yl)isophthalic acid;DMF:N,N'‐dimethylformamide),was synthesized using carboxylic acid ligands and cobalt salts via a solvothermal method.According to structural analysis,[Co_(3)]clusters as secondary building units(SBU)are bridged by BCP4−ligands,forming an anion framework with flu topology,and dimethylamine cations act as counter ions in the pores.The framework has rectangular channels of approximately 0.4 nm×0.9 nm along the a-axis direction,exhibiting its porous property.Infrared spectroscopy(IR)and X-ray photoelectron spectroscopy(XPS)characterizations proved the coordination interaction between the carboxyl groups in the ligands and the metal ions.The powder X-Ray diffraction(PXRD)test further confirmed the phase purity of the synthesized samples.PXRD and thermogravimetry(TG)analyses indicated that 1 possessed good solvent and thermal stabilities.The catalytic experiments revealed that 1 could effectively catalyze CO_(2)with aziridines or propargyl amines to prepare oxazolidinones.In the cycloaddition of CO_(2)with aziridines,1 can facilitate the reaction under relatively mild conditions compared to other reported MOF-based catalysts.It shows excellent universality for substrates with various substitutions on the N atom or benzene ring.Investigation of the mechanism indicated that the coordination interaction of cobalt metal sites with the nitrogen atoms of aziridines can activate the substrates.For the carboxylative cyclization of CO_(2)with propargylic amines,this catalyst also has a broad substrate scope.Control experiments and nuclear magnetic resonance(NMR)tests suggest that Lewis acid metal sites are responsible for the high catalytic efficiency achieved by activating the alkyne groups.Moreover,1 showed good reusability in both reactions.Compound 1 represents a new catalyst that enables“two birds with one stone”in the catalytic synthesis of oxazolidinones using CO_(2).
基金Project(2023JJ10062)supported by the Hunan Province Funds for Distinguished Young Scientists,ChinaProject(2023RC3051)supported by the Science and Technology Innovation Program of Hunan Province of ChinaProject(kh2401026)supported by the Science and Technology Program of Changsha of China。
文摘The sluggish kinetics of the sulfur redox reaction(SRR)and the shuttling effect of lithium polysulfides(LiPSs)both restrict the practical application of lithium-sulfur(Li-S)batteries.Heterostructures,with their pronounced electroactivity and structural stability,showcase their potential as electrodes/functional separators for lithium-sulfur batteries.Herein,we proposed a bifunctional catalyst exhibiting strong adsorption and rapid catalytic conversion of LiPSs through in situ UV photocatalytic synthesis of Ti_(3)C_(2)@TiO_(2)heterostructure.The TiO_(2)nanoparticles act as the anchoring center for LiPSs,while the electrically conductive Ti_(3)C_(2)ensures the rapid diffusion of these LiPSs from TiO_(2)to the catalytically active Ti_(3)C_(2)layer across heterogeneous interfaces.The Li-S batteries with Ti_(3)C_(2)@TiO_(2)-40 min-PP separator delivered a high initial capacity of 1283 mA∙h/g,which decreased slightly to 691 mA∙h/g after 200 cycles at 1C.This work advances the understanding of the synergistic effect of polysulfide adsorbents and conductive agents in inhibiting shuttle effects,and offers a method for designing polysulfide barriers in lithium-sulfur batteries.
