Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented ...Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented examples of tetradecanuclear vanadium clusters,namely,[(C_(2)H_(8)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V_(14)-1),[(C_(3)H_(10)N_(2))_(6)(CH_(3)O)_(8)(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V14^(-2)),[(C_(6)H_(14)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)]·5H_(2)O(V14^(-3))and[(C_(4)H_(12)N_(2)O)_(4)(C_(4)H_(11)N_(2)O)_(2)(CH_(3)O)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(28)]·6H_(2)O(V_(14)-4),have been triumphantly designed and constructed under solvothermal conditions.Among them,compounds V_(14)-1–4 are the first cases of tetradecanuclear vanadium clusters without the introduction of inorganic acid radical ions.Two main units[V_(10)^(Ⅳ)V_(4)ⅤO_(26)]8+and[V10ⅣV4ⅤO28]4+represent brand-new configurations of tetradecanuclear vanadium clusters.Given the fact that the presence of V^(Ⅳ)/V^(Ⅴ)can potentially facilitate electron transfer and consequently expedite catalytic reactions,we explored the catalytic activities of these compounds.Remarkably,V_(14)-1 was further used as a heterogeneous catalyst in the CO_(2)fixation into cyclic carbonates under milder conditions(60℃,0.5 MPa)and exhibited higher catalytic activity.Also,the experimental results indicated that V_(14)-1 could efficiently catalyze the sulfoxidation,which could fully convert most sulfides within 40 min at room temperature.Moreover,as a stable heterogeneous catalyst employed in CO_(2)fixation with epoxides and oxidation of sulfides,V_(14)-1 could be consecutively used multiple cycles without losing its catalytic activity.展开更多
通过排水法研究了采用混合催化剂Co_2B/Pr_6O_(11)的硼氢化钠的水解过程。Co_2B与Pr_6O_(11)的比例和混合催化剂Co_2B/Pr_6O_(11)的加入量对硼氢化钠放氢量的影响非常明显。当掺杂量在1%~6%之间变化时,试样的放氢速率随着掺杂量先增加...通过排水法研究了采用混合催化剂Co_2B/Pr_6O_(11)的硼氢化钠的水解过程。Co_2B与Pr_6O_(11)的比例和混合催化剂Co_2B/Pr_6O_(11)的加入量对硼氢化钠放氢量的影响非常明显。当掺杂量在1%~6%之间变化时,试样的放氢速率随着掺杂量先增加后减少。相比之下,混合催化剂Co_2B/Pr_6O_(11)的加入量以及混合比例对NaBH_4的放氢量的影响并不明显。然而,NaBH_4被Co_2B/Pr_6O_(11)催化后,硼氢化钠的放氢量明显被改变了,所有的掺杂试样的放氢量在410~525 mL之间。在所有试样中,掺杂量4%的(70%Co_2B/30%Pr_6O_(11))试样具有最大的放氢速率540 mL/min和最大的放氢量540 mL 。展开更多
The copolymerizations of ethylene with 1-hexene or 1-0ctene by using TiC14/MgCI2/THF catalysts modified with different metal halide additives （ZnCI2, SIC14, and the combined ZnC12-SiCl4） were investigated based on c...The copolymerizations of ethylene with 1-hexene or 1-0ctene by using TiC14/MgCI2/THF catalysts modified with different metal halide additives （ZnCI2, SIC14, and the combined ZnC12-SiCl4） were investigated based on catalytic activity and copolymer properties. It was found that the catalyst modified with mixed ZnC12-SiC14 revealed the highest activities for both ethylene/1-hexene and ethylene/1-0ctene copolymerization. The increase in activities was due to the formation of acidic sites by modifying the catalysts with Lewis acids. Based on the FTIR measurements, the characteristic C--O--C peaks of the catalysts modified with metal halide additives were slightly shifted to lower wavenumber when compared to the unmodified catalyst. This showed that the modified catalysts could generate more acid sites in the TiC14/MgC12/THF catalytic system leading to an increase in activities as well as comonomer insertion （as proven by IaC-NMR）. However, Lewis acid- modifications did not affect the microstructure of the copolymers obtained. By comparison on the properties of copolymers prepared with the unmodified catalyst, it was found that polymers with ZnC12 and/or SIC14 modification exhibited a slight decrease in melting temperature, crystallinity and density. It is suggested that these results were obtained based on the different amount of ct-olefins insertion, regardless of the types of Lewis acids and comonomer.展开更多
基金supported by the Natural Science Foundation of Jiangsu(BK20191359)the National Natural Science Foundation of China(92161109)+1 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_1343)the Social Science Foundation of Jiangsu(19TQB002)。
文摘Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented examples of tetradecanuclear vanadium clusters,namely,[(C_(2)H_(8)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V_(14)-1),[(C_(3)H_(10)N_(2))_(6)(CH_(3)O)_(8)(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V14^(-2)),[(C_(6)H_(14)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)]·5H_(2)O(V14^(-3))and[(C_(4)H_(12)N_(2)O)_(4)(C_(4)H_(11)N_(2)O)_(2)(CH_(3)O)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(28)]·6H_(2)O(V_(14)-4),have been triumphantly designed and constructed under solvothermal conditions.Among them,compounds V_(14)-1–4 are the first cases of tetradecanuclear vanadium clusters without the introduction of inorganic acid radical ions.Two main units[V_(10)^(Ⅳ)V_(4)ⅤO_(26)]8+and[V10ⅣV4ⅤO28]4+represent brand-new configurations of tetradecanuclear vanadium clusters.Given the fact that the presence of V^(Ⅳ)/V^(Ⅴ)can potentially facilitate electron transfer and consequently expedite catalytic reactions,we explored the catalytic activities of these compounds.Remarkably,V_(14)-1 was further used as a heterogeneous catalyst in the CO_(2)fixation into cyclic carbonates under milder conditions(60℃,0.5 MPa)and exhibited higher catalytic activity.Also,the experimental results indicated that V_(14)-1 could efficiently catalyze the sulfoxidation,which could fully convert most sulfides within 40 min at room temperature.Moreover,as a stable heterogeneous catalyst employed in CO_(2)fixation with epoxides and oxidation of sulfides,V_(14)-1 could be consecutively used multiple cycles without losing its catalytic activity.
基金National Natural Science Foundation of China(50806007)Shanxi National Science Foundation(2014JM7262)Chang’an University School Fund(310831163501)
文摘通过排水法研究了采用混合催化剂Co_2B/Pr_6O_(11)的硼氢化钠的水解过程。Co_2B与Pr_6O_(11)的比例和混合催化剂Co_2B/Pr_6O_(11)的加入量对硼氢化钠放氢量的影响非常明显。当掺杂量在1%~6%之间变化时,试样的放氢速率随着掺杂量先增加后减少。相比之下,混合催化剂Co_2B/Pr_6O_(11)的加入量以及混合比例对NaBH_4的放氢量的影响并不明显。然而,NaBH_4被Co_2B/Pr_6O_(11)催化后,硼氢化钠的放氢量明显被改变了,所有的掺杂试样的放氢量在410~525 mL之间。在所有试样中,掺杂量4%的(70%Co_2B/30%Pr_6O_(11))试样具有最大的放氢速率540 mL/min和最大的放氢量540 mL 。
基金financially supported by the Dusadeepipat scholarship at Graduate school of Chulalongkorn Universitythe Thailand Research Fund(TRF)+1 种基金the Higher Education Promotion and National Research University Development(AM1088A)the office of the Higher Education Commission(CHE)
文摘The copolymerizations of ethylene with 1-hexene or 1-0ctene by using TiC14/MgCI2/THF catalysts modified with different metal halide additives （ZnCI2, SIC14, and the combined ZnC12-SiCl4） were investigated based on catalytic activity and copolymer properties. It was found that the catalyst modified with mixed ZnC12-SiC14 revealed the highest activities for both ethylene/1-hexene and ethylene/1-0ctene copolymerization. The increase in activities was due to the formation of acidic sites by modifying the catalysts with Lewis acids. Based on the FTIR measurements, the characteristic C--O--C peaks of the catalysts modified with metal halide additives were slightly shifted to lower wavenumber when compared to the unmodified catalyst. This showed that the modified catalysts could generate more acid sites in the TiC14/MgC12/THF catalytic system leading to an increase in activities as well as comonomer insertion （as proven by IaC-NMR）. However, Lewis acid- modifications did not affect the microstructure of the copolymers obtained. By comparison on the properties of copolymers prepared with the unmodified catalyst, it was found that polymers with ZnC12 and/or SIC14 modification exhibited a slight decrease in melting temperature, crystallinity and density. It is suggested that these results were obtained based on the different amount of ct-olefins insertion, regardless of the types of Lewis acids and comonomer.
