Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-...Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.展开更多
In the semiconductor-based photocatalysts for overall water splitting, loading proper cocatalysts play a crucial role in enhancing the photocatalytic activity. In this work, we have chosen Ni_n/α-Ga_2O_3 as a model a...In the semiconductor-based photocatalysts for overall water splitting, loading proper cocatalysts play a crucial role in enhancing the photocatalytic activity. In this work, we have chosen Ni_n/α-Ga_2O_3 as a model and provided detailed density functional theory calculations to investigate the function of cocatalysts in hydrogen evolution reaction(HER). We have studied the formation and stability of Ni_n(n = 1–4) cluster on two stable surfaces of α-Ga_2O_3(001) and(012). In a Ni_n/α-Ga_2O_3 system, as the Ni 3d states well overlap with O and Ga states, the excited electrons transferred from Ga to Ni may participate in HER. We theoretically predict that introduction of Nincluster on(012) surface can elevate the Fermi level toward the conduction band, which is favorable for the occurrence of HER. Electrochemical computations are used to explore the mechanism of HER. It is found that, in most of Ni_n/α-Ga_2O_3 systems, the active sites of HER are on Ni_n clusters. Loading Ni_n clusters not only importantly reduces the Gibbs free energy of HER but also improves the reaction activity of surface O and Ga sites in HER. Our calculations reasonably explain the experimental observation on significant enhancement of activity for generating hydrogen after loading nickel oxide cocatalysts.展开更多
基金supported by the National Key R&D Program of China(2023YFD1701504)the 2115 Talent Development Program of China Agricultural University Fund(1011-00109018)the Beijing Innovation Team of the Modern Agricultural Research System(BAIC08-2023-FQ02)。
文摘Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.
基金financially supported by the National Natural Science Foundation of China under Grants 21473183 and 21303079
文摘In the semiconductor-based photocatalysts for overall water splitting, loading proper cocatalysts play a crucial role in enhancing the photocatalytic activity. In this work, we have chosen Ni_n/α-Ga_2O_3 as a model and provided detailed density functional theory calculations to investigate the function of cocatalysts in hydrogen evolution reaction(HER). We have studied the formation and stability of Ni_n(n = 1–4) cluster on two stable surfaces of α-Ga_2O_3(001) and(012). In a Ni_n/α-Ga_2O_3 system, as the Ni 3d states well overlap with O and Ga states, the excited electrons transferred from Ga to Ni may participate in HER. We theoretically predict that introduction of Nincluster on(012) surface can elevate the Fermi level toward the conduction band, which is favorable for the occurrence of HER. Electrochemical computations are used to explore the mechanism of HER. It is found that, in most of Ni_n/α-Ga_2O_3 systems, the active sites of HER are on Ni_n clusters. Loading Ni_n clusters not only importantly reduces the Gibbs free energy of HER but also improves the reaction activity of surface O and Ga sites in HER. Our calculations reasonably explain the experimental observation on significant enhancement of activity for generating hydrogen after loading nickel oxide cocatalysts.
