The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques inc...The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.展开更多
Two kinds of novel chitosan-crown ether resins, Schiff base type chitosan-benzo-15-crown-5 （CTS -B15） and chitosan-benzo-18-crown-6 （CTS -B18）, were synthesized through the reaction between -NH2 in chitosan and -C...Two kinds of novel chitosan-crown ether resins, Schiff base type chitosan-benzo-15-crown-5 （CTS -B15） and chitosan-benzo-18-crown-6 （CTS -B18）, were synthesized through the reaction between -NH2 in chitosan and -CHO in 4′-formyl benzo-crown ethers. Their structures were characterized by elemental analysis and FT-IR spectra analysis. The elemental analysis results show that the mass fractions of nitrogen in CTS -B15 and CTS -B18 are much lower than those of chitosan. The results of FT-IR spectra of CTS -B15 and CTS -B18 reveal that there exist characteristic peak of C=N, N-H and Ar, and characteristic peak of pyr anoside in the chain of chitosan-crown ether resins, showing that the structures of chitosan-crown ethers are as expected. The adsorption properties of CTS -B15 and CTS -B18 for Pd 2+ , Cu 2+ and Hg 2+ were studied and the experimental results show that these adsorbents have both good adsorption characterization and especially high particular adsorption selectivity for Pd 2+ when Cu 2+ and Hg 2+ are in coexistence, and the coefficients of selectivity of CTS -B15 and CTS -B18 for metal ions are K Pd 2+ /Cu 2+ = 7.56, K Pd 2+ /Hg 2+ = 68.00, K Cu 2+ /Hg 2+ = 9.00 and K Pd 2+ /Cu 2+ =6.00, K Pd 2+ /Hg 2+ =19.00, K Cu 2+ /Hg 2+ =3.00, respectively.展开更多
Macrocyclic arylene ether ketone was characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrum(MALDI-TOF MS)combining with nuclear magnetic resonance(NMR)spectra.No any more fragment io...Macrocyclic arylene ether ketone was characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrum(MALDI-TOF MS)combining with nuclear magnetic resonance(NMR)spectra.No any more fragment ionization peaks except for the molecular ion peak from the mass spectrum.The structure of macrocyclic dimmer was further affirmed by the NMR spectra through the analysis of chemical shifts.The MALDI-TOF MS combining with NMR technique was found an important tool to characterized Macrocyclic aromatic oligomers.展开更多
文摘The structure-performance relationship of Cu/Al_(2)O_(3) catalysts in the hydrogenation of diethyl oxalate(DEO)for the synthesis of alcohol ether esters has been investigated by various characterization techniques including XRD,XPS,N2O titration,and 27Al MAS-NMR.The results showed that when the crystal configurations of Al_(2)O_(3) were the same,increasing the specific surface area could effectively refine the size of copper nanoparticles(Cu NPs),and ultimately improve the conversion of DEO.Meanwhile,the smaller size ofγ-Al_(2)O_(3)(HSAl and SBAl)loaded Cu NPs promotes the reaction towards the deep hydrogenation to produce ethanol(EtOH)and ethylene glycol(EG).Besides,the larger size of Cu NPs on the surface of amorphous Al_(2)O_(3)(HTAl and SolAl)resulted in a lower conversion rate,where ethyl glycolate(Egly)is the main product.Despite there are differences in Al^(3+)ionic coordination in Al_(2)O_(3) with different crystal structures,the experimental data showed that the differences in Al^(3+)ionic coordination did not significantly affect the catalytic performance in the hydrogenation reaction.The formation of alcohol-ether ester chemicals is critically dependent on the interactions between Cu sites and acidic sites.Among them,EG and EtOH were dehydrated to form 2-ethoxyethanol via the SN2 mechanism,while Egly and EtOH were reacted to form ethyl ethoxyacetate(EEA)via the SN2 mechanism.This study provides a theoretical basis for the optimization of the coal-based glycol processes to achieve a diversified product portfolio.
文摘Two kinds of novel chitosan-crown ether resins, Schiff base type chitosan-benzo-15-crown-5 （CTS -B15） and chitosan-benzo-18-crown-6 （CTS -B18）, were synthesized through the reaction between -NH2 in chitosan and -CHO in 4′-formyl benzo-crown ethers. Their structures were characterized by elemental analysis and FT-IR spectra analysis. The elemental analysis results show that the mass fractions of nitrogen in CTS -B15 and CTS -B18 are much lower than those of chitosan. The results of FT-IR spectra of CTS -B15 and CTS -B18 reveal that there exist characteristic peak of C=N, N-H and Ar, and characteristic peak of pyr anoside in the chain of chitosan-crown ether resins, showing that the structures of chitosan-crown ethers are as expected. The adsorption properties of CTS -B15 and CTS -B18 for Pd 2+ , Cu 2+ and Hg 2+ were studied and the experimental results show that these adsorbents have both good adsorption characterization and especially high particular adsorption selectivity for Pd 2+ when Cu 2+ and Hg 2+ are in coexistence, and the coefficients of selectivity of CTS -B15 and CTS -B18 for metal ions are K Pd 2+ /Cu 2+ = 7.56, K Pd 2+ /Hg 2+ = 68.00, K Cu 2+ /Hg 2+ = 9.00 and K Pd 2+ /Cu 2+ =6.00, K Pd 2+ /Hg 2+ =19.00, K Cu 2+ /Hg 2+ =3.00, respectively.
文摘Macrocyclic arylene ether ketone was characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrum(MALDI-TOF MS)combining with nuclear magnetic resonance(NMR)spectra.No any more fragment ionization peaks except for the molecular ion peak from the mass spectrum.The structure of macrocyclic dimmer was further affirmed by the NMR spectra through the analysis of chemical shifts.The MALDI-TOF MS combining with NMR technique was found an important tool to characterized Macrocyclic aromatic oligomers.
