The selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines(py-THQ) and its derivatives has attracted a considerable amount of attention as they show great versatility in many pharmaceuticals, agrochemic...The selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines(py-THQ) and its derivatives has attracted a considerable amount of attention as they show great versatility in many pharmaceuticals, agrochemicals, and fine chemicals. Over the past few decades, great breakthroughs have been achieved in the controlled synthesis of efficient heterogeneous catalysts used for the selective hydrogenation of functionalized quinoline compounds, which allow one to correlate the structure-property relationships. In this review, we will summarize the recent significant progress achieved in this field covering the synthetic strategies, microstructural and chemical features, catalytic performance, and internal relationships. State-of-the-art noble metal-based single(Pd, Pt, Ru, Rh, Ir and Au) and bi/multi-metallic catalysts(RuCu, AuPd, and PdNi) are first introduced, followed by a summary of earth-abundant metal-based catalysts(Co, Fe, Ni, and Cu). Finally, the dehydrogenation of N-heterocycles is introduced to form a reversible hydrogenation/dehydrogenation system for H2 storage, which can be employed in a liquid organic hydrogen system. Furthermore, the reaction mechanism and future research direction in these areas are also discussed. This review will deepen our understanding of the catalytic transformation of N-heterocycles and provide guidance for researchers on the rational design of catalysts.展开更多
Photocatalytic production of hydrogen peroxide(H_(2)O_(2))has attracted much attentions as a promising method for sustainable solar fuel.Here,we demonstrate that trace water can drastically boost highefficiency photoc...Photocatalytic production of hydrogen peroxide(H_(2)O_(2))has attracted much attentions as a promising method for sustainable solar fuel.Here,we demonstrate that trace water can drastically boost highefficiency photocatalytic production of H_(2)O_(2) with a record-high concentration of 113 mmol L^(-1) using alkali-assisted C_(3)N_(4) as photocatalyst in water/alcohol mixture solvents.By electron paramagnetic resonance(EPR)measurement,the radical species generated during the photocatalytic process of H_(2)O_(2) are identified.We propose alcohol is used to provide and stabilize-OOH radicals through hydrogen bond,while trace water could trigger photocatalytic production of H_(2)O_(2) via providing and transferring indispensable free protons to completely consume OOH radicals,which breaks the reaction balance of-OOH radical generation from alcohol.Thus-OOH radicals could be supplied by alcohol continuously to serve as a reservoir for high-efficiency production of H_(2)O_(2).These results pave the way towards photocatalytic method on semiconductor catalysts as an outstanding approach for production of hydrogen peroxide.展开更多
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
基金supported by the National Postdoctoral Innovative Talent Support Program(Z86101001)China Postdoctoral Science Foundation(Z741010006)Preferred Postdoctoral Research Projects Foundation of Zhejiang Province(Z87101003)~~
文摘The selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines(py-THQ) and its derivatives has attracted a considerable amount of attention as they show great versatility in many pharmaceuticals, agrochemicals, and fine chemicals. Over the past few decades, great breakthroughs have been achieved in the controlled synthesis of efficient heterogeneous catalysts used for the selective hydrogenation of functionalized quinoline compounds, which allow one to correlate the structure-property relationships. In this review, we will summarize the recent significant progress achieved in this field covering the synthetic strategies, microstructural and chemical features, catalytic performance, and internal relationships. State-of-the-art noble metal-based single(Pd, Pt, Ru, Rh, Ir and Au) and bi/multi-metallic catalysts(RuCu, AuPd, and PdNi) are first introduced, followed by a summary of earth-abundant metal-based catalysts(Co, Fe, Ni, and Cu). Finally, the dehydrogenation of N-heterocycles is introduced to form a reversible hydrogenation/dehydrogenation system for H2 storage, which can be employed in a liquid organic hydrogen system. Furthermore, the reaction mechanism and future research direction in these areas are also discussed. This review will deepen our understanding of the catalytic transformation of N-heterocycles and provide guidance for researchers on the rational design of catalysts.
基金supported by the National Natural Science Foundation of China(21625604 and 91934302).
文摘Photocatalytic production of hydrogen peroxide(H_(2)O_(2))has attracted much attentions as a promising method for sustainable solar fuel.Here,we demonstrate that trace water can drastically boost highefficiency photocatalytic production of H_(2)O_(2) with a record-high concentration of 113 mmol L^(-1) using alkali-assisted C_(3)N_(4) as photocatalyst in water/alcohol mixture solvents.By electron paramagnetic resonance(EPR)measurement,the radical species generated during the photocatalytic process of H_(2)O_(2) are identified.We propose alcohol is used to provide and stabilize-OOH radicals through hydrogen bond,while trace water could trigger photocatalytic production of H_(2)O_(2) via providing and transferring indispensable free protons to completely consume OOH radicals,which breaks the reaction balance of-OOH radical generation from alcohol.Thus-OOH radicals could be supplied by alcohol continuously to serve as a reservoir for high-efficiency production of H_(2)O_(2).These results pave the way towards photocatalytic method on semiconductor catalysts as an outstanding approach for production of hydrogen peroxide.
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.
