Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Co...Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.展开更多
To reduce the environmental pollution and meet the needs for wearable electronic devices, new requirements for electromagnetic interference(EMI) shielding materials include flexibility, biodegradability, and biocompat...To reduce the environmental pollution and meet the needs for wearable electronic devices, new requirements for electromagnetic interference(EMI) shielding materials include flexibility, biodegradability, and biocompatibility. Herein, we reported a polypyrrole-coated zein/epoxy(PPy/ZE) ultrafine fiber mat which was inherently biodegradable and skin-friendly. In addition, it could maintain its ultrafine fibrous structure after coating, which could provide the mat with mechanical compliance, high porosity, and a large specific area for high EMI shielding. With the assistance of the epoxide cross-linking, the breaking stresses of the PPy/ZE fiber mats could achieve 3.3 MPa and 1.4 MPa and the strains were 40.1% and 83.0% in dry and wet states, respectively, which met the needs of various wearable electronic devices. Along with the extension in the PPy treatment duration, more PPy was loaded on the fiber surfaces, which formed more integrated and conductive paths to generate increasing conductivities up to 401.76 S·m^(-1). Moreover, the EMI shielding performance was raised to 26.84 dB. The biobased mats provide a green and efficient choice for EMI shielding materials, which may be a promising strategy to address EMI problems in multiple fields.展开更多
基金supported by the National Natural Science Foundation of China(22302115,22072079)the Fundamental Research Program of Shanxi Province(202303021221056).
文摘Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO_(2)catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH_(2)=CH_(2)and CH_(3)CH=O at the FLP sites constructed on CeO_(2)(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(H^(δ−))forms a stable H−O bond with the surface O atom,while at the FLP site,H^(δ−)is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed C_(C=C)and O_(C=O)atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH_(2)=CH_(2)and CH_(3)CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH_(2)=CH_(2)with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH_(3)CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO_(2)(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.
基金Fundamental Research Funds for the Central Universities,China(No. 2232022D-13)Fundamental Research Funds of Shanghai Collaborative Innovation Center of High Performance Fibers and Composites (Province-M inistry Joint),China(No. X12812101/015)。
文摘To reduce the environmental pollution and meet the needs for wearable electronic devices, new requirements for electromagnetic interference(EMI) shielding materials include flexibility, biodegradability, and biocompatibility. Herein, we reported a polypyrrole-coated zein/epoxy(PPy/ZE) ultrafine fiber mat which was inherently biodegradable and skin-friendly. In addition, it could maintain its ultrafine fibrous structure after coating, which could provide the mat with mechanical compliance, high porosity, and a large specific area for high EMI shielding. With the assistance of the epoxide cross-linking, the breaking stresses of the PPy/ZE fiber mats could achieve 3.3 MPa and 1.4 MPa and the strains were 40.1% and 83.0% in dry and wet states, respectively, which met the needs of various wearable electronic devices. Along with the extension in the PPy treatment duration, more PPy was loaded on the fiber surfaces, which formed more integrated and conductive paths to generate increasing conductivities up to 401.76 S·m^(-1). Moreover, the EMI shielding performance was raised to 26.84 dB. The biobased mats provide a green and efficient choice for EMI shielding materials, which may be a promising strategy to address EMI problems in multiple fields.
