The development of bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N‐heterocycles is a challenge.In this study,Ru_(2)P/AC effectively promoted reversible transformations bet...The development of bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N‐heterocycles is a challenge.In this study,Ru_(2)P/AC effectively promoted reversible transformations between unsaturated and saturated N‐heterocycles affording yields of 98%and 99%,respectively.Moreover,a remarkable enhancement in the reusability of Ru_(2)P/AC was observed compared with other Ru‐based catalysts.According to density functional theory calculations,the superior performance of Ru_(2)P/AC was ascribed to specific synergistic factors,namely geometric and electronic effects induced by P.P greatly reduced the large Ru‐Ru ensembles and finely modified the electronic structures,leading to a low reaction barrier and high desorption ability of the catalyst,further boosting the hydrogenation and acceptorless dehydrogenation processes.展开更多
Developing highly active, low-cost and organic surfactants-free Pd-based catalysts for ethanol oxidation reaction（EOR） is now critically important for direct ethanol fuel cells. Herein, surface-clean low-doped PdB/C...Developing highly active, low-cost and organic surfactants-free Pd-based catalysts for ethanol oxidation reaction（EOR） is now critically important for direct ethanol fuel cells. Herein, surface-clean low-doped PdB/C catalysts（typically ca. 1.5 at% of B） are successfully prepared in an aqueous condition without adding any organic surfactants. TEM characterization shows that as-prepared low-doped Pd B nanoparticles are evenly distributed on carbon support. Cyclic voltommagrams of as-prepared low-doped PdB/C in 0.5 M NaOH ＋ 1 M C2H5OH indicate that its onset oxidation potential of ethanol is ca. 80-120 mV more negative than that on commercial Pd/C. Meanwhile, the EOR mass activity of our home-made catalysts is up to 4018 m A·mg-1 Pd. Moreover, the durability on low-doped PdB/C catalysts is at most 2 times higher than that on commercial Pd/C. Geometric and electronic effects are adopted to understand the above mentioned enhancement of activity and durability. This work may provide a facile, low-cost and green strategy on preparing electrocatalysts toward EOR in alkaline media.展开更多
Identification of the catalytically active sites emerges as the prerequisite for an atomic-level comprehensive understanding and further rational design of highly efficient catalysts.Here,we demonstrate a kinetics str...Identification of the catalytically active sites emerges as the prerequisite for an atomic-level comprehensive understanding and further rational design of highly efficient catalysts.Here,we demonstrate a kinetics strategy to identify the active sites of Au catalyst for the disentanglement of geometric and electronic effects on the selective oxidation of propylene to acrolein.Both the Ti-containing titanium-silicalite-1(TS-1)and Ti-free silicalite-1(S-1)were employed as supports to immobilize Au catalysts,which were investigated by a combination of multiple characterization,kinetics analysis,crystal structure modelling.The Au(111)sites are identified as the main active site for acrolein formation,while their electronic effects are highly relevant to the presence or absence of Ti.Moreover,propylene epoxide(PO)formation mainly involves the co-participation of Au and Ti sites,the proximity between Au and Ti sites is found to have less influences on PO formation in a certain distance.In comparison,acrolein is very likely to generate over Au(111)sites via the hydrogen-assisted O_(2) activation to oxygenated species for its oxidizing propylene.The insights gained here could guide the design and preparation of Au catalysts for selective propylene oxidation.展开更多
文摘The development of bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N‐heterocycles is a challenge.In this study,Ru_(2)P/AC effectively promoted reversible transformations between unsaturated and saturated N‐heterocycles affording yields of 98%and 99%,respectively.Moreover,a remarkable enhancement in the reusability of Ru_(2)P/AC was observed compared with other Ru‐based catalysts.According to density functional theory calculations,the superior performance of Ru_(2)P/AC was ascribed to specific synergistic factors,namely geometric and electronic effects induced by P.P greatly reduced the large Ru‐Ru ensembles and finely modified the electronic structures,leading to a low reaction barrier and high desorption ability of the catalyst,further boosting the hydrogenation and acceptorless dehydrogenation processes.
基金supported by NSFC (No.21603177)the Natural Science Foundation of Sichuan Province (No.2016JY0212)+1 种基金the Fundamental Research Funds for the Central Universities (No.2017NGJPY05)the Innovation Funds for SMU students (No. 201710656023)
文摘Developing highly active, low-cost and organic surfactants-free Pd-based catalysts for ethanol oxidation reaction（EOR） is now critically important for direct ethanol fuel cells. Herein, surface-clean low-doped PdB/C catalysts（typically ca. 1.5 at% of B） are successfully prepared in an aqueous condition without adding any organic surfactants. TEM characterization shows that as-prepared low-doped Pd B nanoparticles are evenly distributed on carbon support. Cyclic voltommagrams of as-prepared low-doped PdB/C in 0.5 M NaOH ＋ 1 M C2H5OH indicate that its onset oxidation potential of ethanol is ca. 80-120 mV more negative than that on commercial Pd/C. Meanwhile, the EOR mass activity of our home-made catalysts is up to 4018 m A·mg-1 Pd. Moreover, the durability on low-doped PdB/C catalysts is at most 2 times higher than that on commercial Pd/C. Geometric and electronic effects are adopted to understand the above mentioned enhancement of activity and durability. This work may provide a facile, low-cost and green strategy on preparing electrocatalysts toward EOR in alkaline media.
基金the National Key R&D Program of China(No.2021YFA1501403)the National Natural Science Foundation of China(Nos.21922803,22038003,92034301,22008066,and 21776077)+3 种基金the Innovation Program of Shanghai Municipal Education Commission,the Program of Shanghai Academic/Technology Research Leader(No.21XD1421000)the Shanghai Science and Technology Innovation Action Plan(No.22JC1403800)the China Postdoctoral Science Foundation(No.BX20190116)111 Project of the Ministry of Education of China(No.B08021).
文摘Identification of the catalytically active sites emerges as the prerequisite for an atomic-level comprehensive understanding and further rational design of highly efficient catalysts.Here,we demonstrate a kinetics strategy to identify the active sites of Au catalyst for the disentanglement of geometric and electronic effects on the selective oxidation of propylene to acrolein.Both the Ti-containing titanium-silicalite-1(TS-1)and Ti-free silicalite-1(S-1)were employed as supports to immobilize Au catalysts,which were investigated by a combination of multiple characterization,kinetics analysis,crystal structure modelling.The Au(111)sites are identified as the main active site for acrolein formation,while their electronic effects are highly relevant to the presence or absence of Ti.Moreover,propylene epoxide(PO)formation mainly involves the co-participation of Au and Ti sites,the proximity between Au and Ti sites is found to have less influences on PO formation in a certain distance.In comparison,acrolein is very likely to generate over Au(111)sites via the hydrogen-assisted O_(2) activation to oxygenated species for its oxidizing propylene.The insights gained here could guide the design and preparation of Au catalysts for selective propylene oxidation.
