Top‐down synthesis has been used to prepare catalytic materials with nanometer sizes,but fabricating atomically dispersed metal catalysts remains a challenge because surface single metal atoms are prone to aggregatio...Top‐down synthesis has been used to prepare catalytic materials with nanometer sizes,but fabricating atomically dispersed metal catalysts remains a challenge because surface single metal atoms are prone to aggregation or coalescence.A top‐down strategy is used to synthesize atomically dispersed metal catalysts,based on supported Ag nanoparticles.The changes of the geometric and electronic structures of the Ag atoms during the top‐down process are studied using the in situ synchrotron X‐ray diffraction technique,ex situ X‐ray absorption spectroscopy,and transmission electron microscopy.The experimental results,coupled with the density functional theory calculations,demonstrate that the electronic perturbation of the Ag frontier orbitals,induced by the Ag‐O interactions at the perimeter of the metal‐support interface,is the driving force of the top‐down process.The top‐down synthesis has two important functions:to increase the number of catalytic active sites and to facilitate the study of complex reaction mechanisms(e.g.,formaldehyde oxidation)by developing single‐site model catalysts.展开更多
29Si-NMR and 1H-NMR were used to follow up the basic hydrolysis of tetraethyl orthosilicate (TOES) and the results showed that species of monomer, dimer, trimer, cyclic and polymer silicates were formed. The monomer...29Si-NMR and 1H-NMR were used to follow up the basic hydrolysis of tetraethyl orthosilicate (TOES) and the results showed that species of monomer, dimer, trimer, cyclic and polymer silicates were formed. The monomer and dimer were favorable for the high activity of zeolite. XRD, 13C CP/MAS and 29Si NMR were used to trace the crystallization process of hollow titanium silicalite zeolites (HTS). The results showed that the induction period of HTS was 80 min, and subsequently it took next 10 min to form HTS and the remaining time of the crystallization period might function for cleaning up the pores and/or washing off the impurities from the HTS zeolite. The catalytic oxidation performance of HTS zeolite is different from that of the acid activity of zeolite in which the conventional definition of crystallinity does not reflect the catalytic oxidation activity proportionally. The synthesized HTS samples were character- ized by XRD, FT-IR, UV-Vis and Raman spectra. It was confirmed that Ti was incorporated into the zeolite framework. The synthesized HTS samples revealed good repeatability and high activity for oxidation of phenol into diphenol.展开更多
The mesoporous Ti O2 has been synthesized by evaporation induced self assembly(EISA) method. The thermogravimetric/differential scanning calorimetric(TG/DSC), X-ray diffraction(XRD), high-resolution transmission elect...The mesoporous Ti O2 has been synthesized by evaporation induced self assembly(EISA) method. The thermogravimetric/differential scanning calorimetric(TG/DSC), X-ray diffraction(XRD), high-resolution transmission electron microscopy(HR-TEM) and N2 adsorption desorption and adsorption are used to study the effects of the synthesized process condition on the microstructure of the as-synthesized mesoporous Ti O2. The photocatalytic performances of as-synthesized samples are evaluated by the degradation of the formaldehyde under ultraviolet light irradiations. The results demonstrate that the as-synthesized mesoporous Ti O2 are anatase with the uniform size about 20-40 nm. The sample is prepared using cetyltrimethyl ammonium bromide(CTAB) as the template with average pore size distribution of 8.12 nm, specific surface area of 68.47 m2/g and pore volume of 0.213 m L/g. The samples show decomposition of formaldehyde 95.8% under ultraviolet light irradiations for 90 min. These results provide a basic experimental process for preparation mesoporous Ti O2, which will posses a broad prospect in terms of the applications in improving indoor air quality.展开更多
In this work, we demonstrated a simple and efficacious two-step method for the synthesis of Ag@Au core-shell nanoparticles (Ag@AuNPs) and the Ag/Au hollow nanocages (Ag/AuNCs) with Ag nanoparticles (AgNPs) as se...In this work, we demonstrated a simple and efficacious two-step method for the synthesis of Ag@Au core-shell nanoparticles (Ag@AuNPs) and the Ag/Au hollow nanocages (Ag/AuNCs) with Ag nanoparticles (AgNPs) as seeds by adjusting pH, and the preparation of hybrid Ag@AuNPs- or Ag/AuNCs-graphene oxide nanocomposites (Ag@AuNPs-GO or Ag/AuNCs-GO) based on the self-assembly. It was noticed from the elec- trostatic assembly experiment that the loading amount of Ag/AuNCs on GO nanosheet was more than that of Ag@AuNPs. The as-synthesized hybrid materials were characterized by transmission electron microscopy, atomic force microscopy, ξ-potential, high-angle annular dark- field scanning transmission electron microscopy, thermo- gravimetric analyzer and X-ray diffraction. Catalytic activities of Ag@AuNPs, Ag/AuNCs and Ag/AuNCs-GO nanostructures were investigated in the reduction of 4-, 3-or 2-nitrophenol to 4-, 3- or 2-aminophenol, and on the basis of comparative kinetic studies the following trend was obtained for the related catalytic activity: Ag/AuNCs- GO 〉 Ag/AuNCs 〉 Ag@AuNPs. These observations were attributed to the simultaneous effects of surface area available for catalytic reaction and composition of the hybrid nanostructures.展开更多
基金supported by the National Natural Science Foundation of China(21477023)the Science and Technology Commission of Shanghai Municipality(14JC1400400)~~
文摘Top‐down synthesis has been used to prepare catalytic materials with nanometer sizes,but fabricating atomically dispersed metal catalysts remains a challenge because surface single metal atoms are prone to aggregation or coalescence.A top‐down strategy is used to synthesize atomically dispersed metal catalysts,based on supported Ag nanoparticles.The changes of the geometric and electronic structures of the Ag atoms during the top‐down process are studied using the in situ synchrotron X‐ray diffraction technique,ex situ X‐ray absorption spectroscopy,and transmission electron microscopy.The experimental results,coupled with the density functional theory calculations,demonstrate that the electronic perturbation of the Ag frontier orbitals,induced by the Ag‐O interactions at the perimeter of the metal‐support interface,is the driving force of the top‐down process.The top‐down synthesis has two important functions:to increase the number of catalytic active sites and to facilitate the study of complex reaction mechanisms(e.g.,formaldehyde oxidation)by developing single‐site model catalysts.
基金Project supported by the National Science Foundation of China(2006CB202508)
文摘29Si-NMR and 1H-NMR were used to follow up the basic hydrolysis of tetraethyl orthosilicate (TOES) and the results showed that species of monomer, dimer, trimer, cyclic and polymer silicates were formed. The monomer and dimer were favorable for the high activity of zeolite. XRD, 13C CP/MAS and 29Si NMR were used to trace the crystallization process of hollow titanium silicalite zeolites (HTS). The results showed that the induction period of HTS was 80 min, and subsequently it took next 10 min to form HTS and the remaining time of the crystallization period might function for cleaning up the pores and/or washing off the impurities from the HTS zeolite. The catalytic oxidation performance of HTS zeolite is different from that of the acid activity of zeolite in which the conventional definition of crystallinity does not reflect the catalytic oxidation activity proportionally. The synthesized HTS samples were character- ized by XRD, FT-IR, UV-Vis and Raman spectra. It was confirmed that Ti was incorporated into the zeolite framework. The synthesized HTS samples revealed good repeatability and high activity for oxidation of phenol into diphenol.
基金Projects(51102026,51272032) supported by the Program for the National Natural Science Foundation of ChinaProject(11A014) supported by the Scientific Research Fund of Hunan Provincial Education DepartmentProject supported by the Aid Program for Science and Technology Innovative Research Team in Higher Educational Instituions of Hunan Province,China
文摘The mesoporous Ti O2 has been synthesized by evaporation induced self assembly(EISA) method. The thermogravimetric/differential scanning calorimetric(TG/DSC), X-ray diffraction(XRD), high-resolution transmission electron microscopy(HR-TEM) and N2 adsorption desorption and adsorption are used to study the effects of the synthesized process condition on the microstructure of the as-synthesized mesoporous Ti O2. The photocatalytic performances of as-synthesized samples are evaluated by the degradation of the formaldehyde under ultraviolet light irradiations. The results demonstrate that the as-synthesized mesoporous Ti O2 are anatase with the uniform size about 20-40 nm. The sample is prepared using cetyltrimethyl ammonium bromide(CTAB) as the template with average pore size distribution of 8.12 nm, specific surface area of 68.47 m2/g and pore volume of 0.213 m L/g. The samples show decomposition of formaldehyde 95.8% under ultraviolet light irradiations for 90 min. These results provide a basic experimental process for preparation mesoporous Ti O2, which will posses a broad prospect in terms of the applications in improving indoor air quality.
基金Acknowledgments This work was supported by the National Nalural Science Foundation of China (21 105042), the Science Foundation of China Postdoctor (2014M560572), the Natural Science Foundation of Shandong Province IZR2015BM024), and Tai-Shan Scholar Research Fund of Shandong Province. The sludy was partially supported by grant NIH IR01DA037838 to Drs. Li and Nair.
文摘In this work, we demonstrated a simple and efficacious two-step method for the synthesis of Ag@Au core-shell nanoparticles (Ag@AuNPs) and the Ag/Au hollow nanocages (Ag/AuNCs) with Ag nanoparticles (AgNPs) as seeds by adjusting pH, and the preparation of hybrid Ag@AuNPs- or Ag/AuNCs-graphene oxide nanocomposites (Ag@AuNPs-GO or Ag/AuNCs-GO) based on the self-assembly. It was noticed from the elec- trostatic assembly experiment that the loading amount of Ag/AuNCs on GO nanosheet was more than that of Ag@AuNPs. The as-synthesized hybrid materials were characterized by transmission electron microscopy, atomic force microscopy, ξ-potential, high-angle annular dark- field scanning transmission electron microscopy, thermo- gravimetric analyzer and X-ray diffraction. Catalytic activities of Ag@AuNPs, Ag/AuNCs and Ag/AuNCs-GO nanostructures were investigated in the reduction of 4-, 3-or 2-nitrophenol to 4-, 3- or 2-aminophenol, and on the basis of comparative kinetic studies the following trend was obtained for the related catalytic activity: Ag/AuNCs- GO 〉 Ag/AuNCs 〉 Ag@AuNPs. These observations were attributed to the simultaneous effects of surface area available for catalytic reaction and composition of the hybrid nanostructures.