The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-...The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-C bond cleavages in the hydrodeoxygenation of palmitic acid over Ni-Mo_(2)C catalyst.The catalytic activity on Ni doped Mo_(2)C with TOF of 6.9×10^(3)h^(-1)is much superior to intrinsic Mo_(2)C catalyst,which is also higher than most noble metal catalysts.Structurally,the doped Ni raises the active particle dispersion and the coordination numbers of Mo species(Mo-C and Mo-O),improves the graphitization degree to promote the electron transfer,and increases the amount of Lewis and Br?nsted acid,which are responsible for the excellent hydrodeoxygenation performance.The Ni promotes simultaneously C-O and C-C bonds cleavage to produce pentadecane and hexadecane owing to the increase of electron-rich Mo sites after Ni doping.These findings contribute to the understanding of the nature of Ni-doped Mo_(2)C on the roles as catalytic active sites for C-O and C-C bonds cleavage.展开更多
Previous measurements of peroxyacetyl nitrate （PAN） in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., mad...Previous measurements of peroxyacetyl nitrate （PAN） in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., made at an urban site （CMA） in Beijing from 25 January to 22 March 2010. The hourly concentration of PAN averaged 0.70 × 10^-9 mol/mol （0.23 × 10^9-3.51 × 10^9 mol/mol） and was well correlated with that of NOa but not O3, indicating that the variations of the winter concentrations of PAN and O3 in urban Beijing are decoupled with each other. Wind conditions and transport of air masses exert very significant impacts on O3, PAN, and other species. Air masses arriving at the site originated either from the boundary layer over the highly polluted N-S-W sector or from the free troposphere over the W-N sector. The descending free-tropospheric air was rich in O3, with an average PAN/O3 ratio smaller than 0.O31, while the boundary layer air over the polluted sector contained higher levels of PAN and primary pollutants, with an average PAN/O3 ratio of 0.11. These facts related with transport conditions can well explain the observed PAN-O3 decoupling. Photochemical production is important to PAN in the winter over Beijing. The concentration of the peroxyacetyl （PA） radicai was estimated to be in the range of 0.0014 × 10^-12～0.0042 × 10^-12 mol/mol. The contributions of the formation reaction and thermal decomposition to PAN＇s variation were calculated and found to be significant even in the colder period in air over Beijing, with the production exceeding the decomposition.展开更多
Cyclic polymers exhibit distinct properties compared with their linear counterparts due to the lack of chain ends.However,the scalable synthesis of cyclic polymers remains a major challenge,especially for ring-closure...Cyclic polymers exhibit distinct properties compared with their linear counterparts due to the lack of chain ends.However,the scalable synthesis of cyclic polymers remains a major challenge,especially for ring-closure method.Herein,we report a novel strategy for large-scale preparation of cyclic polymers,which relies on the prior self-folding of anthracene-telechelic amphiphilic random copolymers(poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate)),P(OEGA-co-DDA))into single-chain polymeric nanoparticles(SCPNs)in water.Subsequent ultraviolet(UV)-induced cyclization occurs in the hydrophobic nano-domain.The formation of SCPNs leads to a shortened distance between the end groups of the linear precursors and spatially separated cyclization loci,and significantly enhances the efficiency of UV-induced cyclization.This self-folding technique permits access to the synthesis of cyclic polymers not only with high molecular weights(M_(n)>10^(5) g/mol),but also in a decent scale(40 g/L),breaking through the limitations of ring-closure method.Furthermore,the dense pendants of the copolymers can magnify the macromolecules by increasing the mass density along the backbones,thus making the polymers more readily detectable by the microscopy.The transmission electron microscopy(TEM)and atomic force microscopy(AFM)images allow us to observe the topological structures directly and provide crucial evidence to confirm the cyclization.展开更多
基金supported by the National Natural Science Foundation of China (22131010,52021002)the Fundamental Research Funds for the Central Universities(WK2060000012)。
基金financially supported by the National Natural Science Foundation of China(21972099)the Application Foundation Program of Sichuan Province(2021YJ0305)+1 种基金the 111 project(B17030).Shanghai Synchrotron Radiation Facility(SSRF)for XAS experiments and the support by the project from NPL of CAEP(2019BB08)。
文摘The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-C bond cleavages in the hydrodeoxygenation of palmitic acid over Ni-Mo_(2)C catalyst.The catalytic activity on Ni doped Mo_(2)C with TOF of 6.9×10^(3)h^(-1)is much superior to intrinsic Mo_(2)C catalyst,which is also higher than most noble metal catalysts.Structurally,the doped Ni raises the active particle dispersion and the coordination numbers of Mo species(Mo-C and Mo-O),improves the graphitization degree to promote the electron transfer,and increases the amount of Lewis and Br?nsted acid,which are responsible for the excellent hydrodeoxygenation performance.The Ni promotes simultaneously C-O and C-C bonds cleavage to produce pentadecane and hexadecane owing to the increase of electron-rich Mo sites after Ni doping.These findings contribute to the understanding of the nature of Ni-doped Mo_(2)C on the roles as catalytic active sites for C-O and C-C bonds cleavage.
基金supported by the China Special Fund for Meteorological Research in the Public Interest(No.GY-HY201206015,GYHY201106050)the Basic Research Fund of CAMS(2011Z003)the National Natural Science Foundation of China(No.40775074)
文摘Previous measurements of peroxyacetyl nitrate （PAN） in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., made at an urban site （CMA） in Beijing from 25 January to 22 March 2010. The hourly concentration of PAN averaged 0.70 × 10^-9 mol/mol （0.23 × 10^9-3.51 × 10^9 mol/mol） and was well correlated with that of NOa but not O3, indicating that the variations of the winter concentrations of PAN and O3 in urban Beijing are decoupled with each other. Wind conditions and transport of air masses exert very significant impacts on O3, PAN, and other species. Air masses arriving at the site originated either from the boundary layer over the highly polluted N-S-W sector or from the free troposphere over the W-N sector. The descending free-tropospheric air was rich in O3, with an average PAN/O3 ratio smaller than 0.O31, while the boundary layer air over the polluted sector contained higher levels of PAN and primary pollutants, with an average PAN/O3 ratio of 0.11. These facts related with transport conditions can well explain the observed PAN-O3 decoupling. Photochemical production is important to PAN in the winter over Beijing. The concentration of the peroxyacetyl （PA） radicai was estimated to be in the range of 0.0014 × 10^-12～0.0042 × 10^-12 mol/mol. The contributions of the formation reaction and thermal decomposition to PAN＇s variation were calculated and found to be significant even in the colder period in air over Beijing, with the production exceeding the decomposition.
基金supported by the National Natural Science Foundation of China(22201276,22131010,52021002)the Fundamental Research Funds for the Central Universities(WK2060000012).
文摘Cyclic polymers exhibit distinct properties compared with their linear counterparts due to the lack of chain ends.However,the scalable synthesis of cyclic polymers remains a major challenge,especially for ring-closure method.Herein,we report a novel strategy for large-scale preparation of cyclic polymers,which relies on the prior self-folding of anthracene-telechelic amphiphilic random copolymers(poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate)),P(OEGA-co-DDA))into single-chain polymeric nanoparticles(SCPNs)in water.Subsequent ultraviolet(UV)-induced cyclization occurs in the hydrophobic nano-domain.The formation of SCPNs leads to a shortened distance between the end groups of the linear precursors and spatially separated cyclization loci,and significantly enhances the efficiency of UV-induced cyclization.This self-folding technique permits access to the synthesis of cyclic polymers not only with high molecular weights(M_(n)>10^(5) g/mol),but also in a decent scale(40 g/L),breaking through the limitations of ring-closure method.Furthermore,the dense pendants of the copolymers can magnify the macromolecules by increasing the mass density along the backbones,thus making the polymers more readily detectable by the microscopy.The transmission electron microscopy(TEM)and atomic force microscopy(AFM)images allow us to observe the topological structures directly and provide crucial evidence to confirm the cyclization.
