本文利用 HRuCo_3(CO)_(12)原子簇化合物制备了 Ru-Co/SiO_2双金属催化剂,并研究了它们在 CO 加氢反应中的催化性能。结果表明,若和由[Et_4N][HRu_3(CO)_(11)]、Co_4(CO)_(12)以及 Co_4(CO)_(12)+[Et4N][HRu_3(CO0)_(11)]和 CoCl2+RuCl_...本文利用 HRuCo_3(CO)_(12)原子簇化合物制备了 Ru-Co/SiO_2双金属催化剂,并研究了它们在 CO 加氢反应中的催化性能。结果表明,若和由[Et_4N][HRu_3(CO)_(11)]、Co_4(CO)_(12)以及 Co_4(CO)_(12)+[Et4N][HRu_3(CO0)_(11)]和 CoCl2+RuCl_3制备的 Ru/SiO_2、Co/SiO_2和 Ru/SiO_2+Co/SiO_2催化剂相比,由 HRuCO_3(CO)_(12)制备的催化剂在 CO 加氢反应中显示了很高的 CO 转化率和含氧化合物的选择性。通过光电子能谱方法可认为,具有近距离的 Ru-Co^(2+)双金属原子中心是 CO 加氢反应中形成含氧化含物的活性中心。展开更多
Metal cluster chemistry is an active studying field nowadays. It is possible that metal clusters can be developed as new homogeneous catalysts with special functions. Organoiron clusters, which could be easily synthes...Metal cluster chemistry is an active studying field nowadays. It is possible that metal clusters can be developed as new homogeneous catalysts with special functions. Organoiron clusters, which could be easily synthesized at lower price, are very important in metal cluster chemistry. Fe<sub>3</sub>（CO）<sub>12</sub> is a very useful compound with higher activity than Fe（CO）<sub>5</sub> in展开更多
An efficient,inexpensive and simple method for the reduction of variousα,β-unsaturated ketones to corre-sponding saturated ketones using tosyl hydrazide as a hydrogen donor in DMF using calcium oxide powder has been...An efficient,inexpensive and simple method for the reduction of variousα,β-unsaturated ketones to corre-sponding saturated ketones using tosyl hydrazide as a hydrogen donor in DMF using calcium oxide powder has been reported.A variety of enones underwent reduction without forming undesirable side products.High chemose-lectivity,broad functional group tolerance and good yields are the noteworthy features of this protocol.展开更多
A series of heterotrinuclear Ti_(2)Ni(CO)_(n)^(-)(n=6-9)carbonyls have been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectrosco...A series of heterotrinuclear Ti_(2)Ni(CO)_(n)^(-)(n=6-9)carbonyls have been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectroscopy.Quantum chemical calculations have been carried out to identify the structures and understand the experimental spectral features.The results indicate that a building block of Ti-Ti-Ni-C four-membered ring with the C atom bonded to Ti,Ti,and Ni is dominated in the n=6-8 complexes,whereas a structural motif of Ti-Ti-Ni triangle core is preferred in n=9.These complexes are found to be capable of simultaneously accommodating all the main modes of metal-CO coordination(i.e.,terminal,bridging,and side-on modes),where the corresponding mode points to the weak,moderate,high C-O bond activation,respectively.The number of CO ligands for a specific bonding mode varies with the cluster size.These findings have important implications for molecular-level understanding of the interaction of CO with alloy surfaces/interfaces and tuning the appropriate CO activation via the selection of different metals.展开更多
The series of heterodinuclear metal oxide carbonyls in the form of TaNiO(CO)_(n)(n=5-8) are generated in the pulsed-laser vaporization source and characterized by mass-selected photoelectron velocity-map spectroscopy....The series of heterodinuclear metal oxide carbonyls in the form of TaNiO(CO)_(n)(n=5-8) are generated in the pulsed-laser vaporization source and characterized by mass-selected photoelectron velocity-map spectroscopy.During the consecutive CO adsorption,the μ^(2)-O-bent structure initially is the most favorable for TaNiO(CO)_(5),and subsequently both μ^(2)-O-bent and μ^(2)-O-linear structures are degenerate for TaNiO(CO)_(6),then the μ^(2)-O-linear structure is most preferential for TaNiO(CO)_(7),and finally the η^(2)-CO_(2)-tagged structure is the most ene rgetically competitive one for TaNiO(CO)_(8),i.e., the CO oxidation occurs at n=8.ln contrast to the literature reported CO oxidation on heteronuclear metal oxide complexes generally proceeding via Langmuir-Hinshelwood-like mechanism,complementary theo retical calculations suggest that both Langmuir-Hinshelwood-like and Eley-Rideal-like mechanisms prevail for the CO oxidation reaction on TaNiO(CO)_(8) complex.Our findings provide new insight into the composition-selective mechanism of CO oxidation on heteronuclear metal complexes,of which the composition be tailored to fulfill the desired chemical behaviors.展开更多
Cluster catalysts are rapidly growing into an important sub-field in heterogeneous catalysis,owing to their distinct geometric structure,neighboring metal sites,and unique electronic structure.Although the thermodynam...Cluster catalysts are rapidly growing into an important sub-field in heterogeneous catalysis,owing to their distinct geometric structure,neighboring metal sites,and unique electronic structure.Although the thermodynamics and kinetics of the formation of nanoparticles have been largely investigated,the precise synthesis of clusters in wet chemical methods still faces great challenges.In the study,a quenching strategy of asymmetric temperature in solution for the rapid generation of vacancy-defect rich clusters is reported.The quenching process can be used to synthesize multitudinous metal compound clusters,including metal oxides,fluorides,oxygen-sulfur compounds,and tungstate.For oxygen evolution reaction(OER),IrO_(2)clusters with abundant oxygen vacancies were obtained and uniformly dispersed in the solution.Compared to commercial IrO_(2),the prepared IrO_(2)cluster can be directly loaded on carbon paper and used as binder-free electrodes,which exhibit higher OER activity and long-term operational stability in alkaline electrolytes.The quenching strategy provides a simple and efficient method for the synthesis of clusters,which has tremendous potential for industrial-scale preparation and application,especially can be further applied to flow electrochemical generators.展开更多
文摘本文利用 HRuCo_3(CO)_(12)原子簇化合物制备了 Ru-Co/SiO_2双金属催化剂,并研究了它们在 CO 加氢反应中的催化性能。结果表明,若和由[Et_4N][HRu_3(CO)_(11)]、Co_4(CO)_(12)以及 Co_4(CO)_(12)+[Et4N][HRu_3(CO0)_(11)]和 CoCl2+RuCl_3制备的 Ru/SiO_2、Co/SiO_2和 Ru/SiO_2+Co/SiO_2催化剂相比,由 HRuCO_3(CO)_(12)制备的催化剂在 CO 加氢反应中显示了很高的 CO 转化率和含氧化合物的选择性。通过光电子能谱方法可认为,具有近距离的 Ru-Co^(2+)双金属原子中心是 CO 加氢反应中形成含氧化含物的活性中心。
基金Project supported by the National Natural Science Foundation of ChinaState Key Laboratory of Structural Chemistry+1 种基金Shanghai Laboratory of Organometallic ChemistryChinese Academy of Sciences
文摘Metal cluster chemistry is an active studying field nowadays. It is possible that metal clusters can be developed as new homogeneous catalysts with special functions. Organoiron clusters, which could be easily synthesized at lower price, are very important in metal cluster chemistry. Fe<sub>3</sub>（CO）<sub>12</sub> is a very useful compound with higher activity than Fe（CO）<sub>5</sub> in
基金University Grant Commission-Basic Science Research(Order no DV-5/662/RFSMS/2012-13),New Delhi,India for financial support.
文摘An efficient,inexpensive and simple method for the reduction of variousα,β-unsaturated ketones to corre-sponding saturated ketones using tosyl hydrazide as a hydrogen donor in DMF using calcium oxide powder has been reported.A variety of enones underwent reduction without forming undesirable side products.High chemose-lectivity,broad functional group tolerance and good yields are the noteworthy features of this protocol.
基金supported by the National Natural Science Foundation of China(Nos.21873097,22103082,92061203,22125303 and 22288201)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(CAS,No.2020187)the Strategic Priority Research Program of CAS(No.XDB17000000)。
文摘A series of heterotrinuclear Ti_(2)Ni(CO)_(n)^(-)(n=6-9)carbonyls have been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectroscopy.Quantum chemical calculations have been carried out to identify the structures and understand the experimental spectral features.The results indicate that a building block of Ti-Ti-Ni-C four-membered ring with the C atom bonded to Ti,Ti,and Ni is dominated in the n=6-8 complexes,whereas a structural motif of Ti-Ti-Ni triangle core is preferred in n=9.These complexes are found to be capable of simultaneously accommodating all the main modes of metal-CO coordination(i.e.,terminal,bridging,and side-on modes),where the corresponding mode points to the weak,moderate,high C-O bond activation,respectively.The number of CO ligands for a specific bonding mode varies with the cluster size.These findings have important implications for molecular-level understanding of the interaction of CO with alloy surfaces/interfaces and tuning the appropriate CO activation via the selection of different metals.
基金supported by the National Natural Science Foundation of China (Nos.21603130,21673231,21688102 and 21873097)the Key Research Program (No.KGZD-EW-T05)+2 种基金the Strategic Priority Research Program (No.XDB17000000) of the Chinese Academy of Sciencethe Shanxi Province Science Foundation for Youths (No. 201901D211395)the 1331 Engineering of Shanxi Province and the Start-up Fund from Shanxi Normal University for support。
文摘The series of heterodinuclear metal oxide carbonyls in the form of TaNiO(CO)_(n)(n=5-8) are generated in the pulsed-laser vaporization source and characterized by mass-selected photoelectron velocity-map spectroscopy.During the consecutive CO adsorption,the μ^(2)-O-bent structure initially is the most favorable for TaNiO(CO)_(5),and subsequently both μ^(2)-O-bent and μ^(2)-O-linear structures are degenerate for TaNiO(CO)_(6),then the μ^(2)-O-linear structure is most preferential for TaNiO(CO)_(7),and finally the η^(2)-CO_(2)-tagged structure is the most ene rgetically competitive one for TaNiO(CO)_(8),i.e., the CO oxidation occurs at n=8.ln contrast to the literature reported CO oxidation on heteronuclear metal oxide complexes generally proceeding via Langmuir-Hinshelwood-like mechanism,complementary theo retical calculations suggest that both Langmuir-Hinshelwood-like and Eley-Rideal-like mechanisms prevail for the CO oxidation reaction on TaNiO(CO)_(8) complex.Our findings provide new insight into the composition-selective mechanism of CO oxidation on heteronuclear metal complexes,of which the composition be tailored to fulfill the desired chemical behaviors.
基金the National Natural Science Foundation of China(Nos.51902027,51788104,61874014,61874013,61974011,and 61976025)the National Basic Research of China(Nos.2016YFE0102200 and 2018YFB0104404)+4 种基金Beijing Natural Science Foundation(No.JQ19005)Fund of State Key Laboratory of Information Photonics and Optical Communications(Beijing University of Posts and Telecommunications,China),BUPT Excellent Ph.D.Students Foundation(No.CX2020119)Guangdong Hydrogen Energy Institute of WHUT under Guangdong Key Areas Research and Development Program(No.2019B090909003)Guangdong Basic and Applied Basic Research Foundation(No.2020B1515120042)Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(No.XHD2020-002).
文摘Cluster catalysts are rapidly growing into an important sub-field in heterogeneous catalysis,owing to their distinct geometric structure,neighboring metal sites,and unique electronic structure.Although the thermodynamics and kinetics of the formation of nanoparticles have been largely investigated,the precise synthesis of clusters in wet chemical methods still faces great challenges.In the study,a quenching strategy of asymmetric temperature in solution for the rapid generation of vacancy-defect rich clusters is reported.The quenching process can be used to synthesize multitudinous metal compound clusters,including metal oxides,fluorides,oxygen-sulfur compounds,and tungstate.For oxygen evolution reaction(OER),IrO_(2)clusters with abundant oxygen vacancies were obtained and uniformly dispersed in the solution.Compared to commercial IrO_(2),the prepared IrO_(2)cluster can be directly loaded on carbon paper and used as binder-free electrodes,which exhibit higher OER activity and long-term operational stability in alkaline electrolytes.The quenching strategy provides a simple and efficient method for the synthesis of clusters,which has tremendous potential for industrial-scale preparation and application,especially can be further applied to flow electrochemical generators.
