Based on an experimental phenomenon that catalytic activity of Pt and Pd for oxygen reduction reaction (ORR) changes with catalyst supports from C to TiO2, density function theory (DFT) was used to elucidate the cause...Based on an experimental phenomenon that catalytic activity of Pt and Pd for oxygen reduction reaction (ORR) changes with catalyst supports from C to TiO2, density function theory (DFT) was used to elucidate the cause behind the difference in catalysis caused by catalyst supports. First, factors closely associated with the first electron transfer of the ORR were assessed in the light of quantum chemistry. Then intermediate (atomic oxygen, O) adsorption strength on the catalyst surface was calculated. The results show that, in terms of minimum energy difference, the best orbital symmetry match, and the maximum orbital overlap, TiO2 does bring about a very positive effect on catalysts Pd/TiO2 for the first electron transfer of the ORR. Especially, TiO2 remarkably expands the space size of Pd/TiO2 HOMO orbital and improves orbital overlap of Pd/TiO2 HOMO and O2 LUMO. The analysis of deformation density and partial density of state shows that the strong interaction between Pt and Ti leads to a strong adsorption of intermediate O on Pt/TiO2, but the strong interaction between Pd and surface O causes positive net charge of Pd and a weak adsorption of intermediate O on Pd/TiO2. Thus, the ORR can proceed more smoothly on Pd/TiO2 than Pt/TiO2 in every respect of maximum orbital overlap and rate delay by intermediate O. The research also discloses that several factors lead to less activity of TiO2-supported Pt and Pd catalysts than the C-supported ones for the ORR. These factors include the poor dispersion of Pt and Pd particles on TiO2, poor electric conduction of TiO2 carrier itself, and bigger energy difference between HOMO of TiO2-carried metallic catalysts and LUMO of O2 molecule due to electrons deeply embedded in the semiconductor TiO2 carrier.展开更多
Pt is a catalyst in proton exchange membrane fuel cell (PEMFC), and its activity will be degraded in the air due to the existence of SOx impurities. On strategy is introducing of Mo into the Pt catalyst because it can...Pt is a catalyst in proton exchange membrane fuel cell (PEMFC), and its activity will be degraded in the air due to the existence of SOx impurities. On strategy is introducing of Mo into the Pt catalyst because it can improve the SOx -tolerance capacity. Based on the aforementioned phenomenon, a density function theory (DFT) study on SO x adsorbed on Pt(111) and PtMo(111) was performed to enhance Pt catalytic activity. The adsorption energy of adsorbed species, the net change, partial density of state (PDOS), and d-band center were calculated and analyzed comparatively. The results show that the presence of Mo-atom weakens the S-Pt bond strength and reduces the adsorption energies for SO2 , S and SO3 on PtMo(111). Moreover, the Mo atom weakens the effects of SO2 on the PtMo(111) electronic structure and makes the catalyst maintains its original electronic structure after SO2 adsorption as compared with Pt(111).展开更多
Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode...Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode potential (e), the surface coverage of carbon monoxide (x), and adsorbed water (y). The chemical reactions and electrode potential were coupled together through the rate constant ki = exp(ai(e ? ei)). The analysis to the established model discloses the following: there are different kinetics be- haviors in different ranges of current densities. The chemical oscillation in methanol electrooxidation is assigned to two aspects, one from poison mediate CO of methanol electrooxidation, which is the in- duced factor of the chemical oscillation, and the other from the oxygen-containing species, such as H2Oa. The formation and disappearance of H2Oa deeply depend on the electrode potential, and directly cause the chemical oscillation. The established model makes clear that the potential oscillation in methanol electrooxidation is the result of the feedback of electrode potential e on the reactions in- volving poison mediates CO and oxygen-containing species H2Oa. The numerical analysis of the estab- lished model successfully explains why the potential oscillation in methanol galvanostatic oxidation on a Pt electrode only happens in a certain range of current densities but not at any current density.展开更多
基金Supported by the National Natural Science Foundation of China (Grant No. 20676156)the Chinese Ministry of Education (Grant No. 307021)+1 种基金the National 863 Program (Grant Nos. 2006AA11A141 and 2007AA05Z124)the Chongqing Sci &Tech Key Project (Grant No. CSTC2007AB6012)
文摘Based on an experimental phenomenon that catalytic activity of Pt and Pd for oxygen reduction reaction (ORR) changes with catalyst supports from C to TiO2, density function theory (DFT) was used to elucidate the cause behind the difference in catalysis caused by catalyst supports. First, factors closely associated with the first electron transfer of the ORR were assessed in the light of quantum chemistry. Then intermediate (atomic oxygen, O) adsorption strength on the catalyst surface was calculated. The results show that, in terms of minimum energy difference, the best orbital symmetry match, and the maximum orbital overlap, TiO2 does bring about a very positive effect on catalysts Pd/TiO2 for the first electron transfer of the ORR. Especially, TiO2 remarkably expands the space size of Pd/TiO2 HOMO orbital and improves orbital overlap of Pd/TiO2 HOMO and O2 LUMO. The analysis of deformation density and partial density of state shows that the strong interaction between Pt and Ti leads to a strong adsorption of intermediate O on Pt/TiO2, but the strong interaction between Pd and surface O causes positive net charge of Pd and a weak adsorption of intermediate O on Pd/TiO2. Thus, the ORR can proceed more smoothly on Pd/TiO2 than Pt/TiO2 in every respect of maximum orbital overlap and rate delay by intermediate O. The research also discloses that several factors lead to less activity of TiO2-supported Pt and Pd catalysts than the C-supported ones for the ORR. These factors include the poor dispersion of Pt and Pd particles on TiO2, poor electric conduction of TiO2 carrier itself, and bigger energy difference between HOMO of TiO2-carried metallic catalysts and LUMO of O2 molecule due to electrons deeply embedded in the semiconductor TiO2 carrier.
基金financially supported by the National Basic Research Program of China (973 Program, 2012CB215500, 2012CB720300)the National Natural Science Foundation of China (51072239, 20936008)the Fundamental Research Funds for the Central Universities (CDJZR-12228802)
文摘Pt is a catalyst in proton exchange membrane fuel cell (PEMFC), and its activity will be degraded in the air due to the existence of SOx impurities. On strategy is introducing of Mo into the Pt catalyst because it can improve the SOx -tolerance capacity. Based on the aforementioned phenomenon, a density function theory (DFT) study on SO x adsorbed on Pt(111) and PtMo(111) was performed to enhance Pt catalytic activity. The adsorption energy of adsorbed species, the net change, partial density of state (PDOS), and d-band center were calculated and analyzed comparatively. The results show that the presence of Mo-atom weakens the S-Pt bond strength and reduces the adsorption energies for SO2 , S and SO3 on PtMo(111). Moreover, the Mo atom weakens the effects of SO2 on the PtMo(111) electronic structure and makes the catalyst maintains its original electronic structure after SO2 adsorption as compared with Pt(111).
基金Supported by the National Natural Science Foundation of China (Grant No. 20676156)the Chinese Ministry of Education (Grant No. 307021)+1 种基金China National 863 Program (Grant Nos. 2006AA11A141 and 2007AA05Z124)Chongqing Sci&Tech Key Project (Grant No. CSTC2007AB6012)
文摘Based on dual path reaction mechanism, a nonlinear dynamics model reflecting the potential oscilla- tion in electrooxidation of methanol on Pt surface was established. The model involves three variables, the electrode potential (e), the surface coverage of carbon monoxide (x), and adsorbed water (y). The chemical reactions and electrode potential were coupled together through the rate constant ki = exp(ai(e ? ei)). The analysis to the established model discloses the following: there are different kinetics be- haviors in different ranges of current densities. The chemical oscillation in methanol electrooxidation is assigned to two aspects, one from poison mediate CO of methanol electrooxidation, which is the in- duced factor of the chemical oscillation, and the other from the oxygen-containing species, such as H2Oa. The formation and disappearance of H2Oa deeply depend on the electrode potential, and directly cause the chemical oscillation. The established model makes clear that the potential oscillation in methanol electrooxidation is the result of the feedback of electrode potential e on the reactions in- volving poison mediates CO and oxygen-containing species H2Oa. The numerical analysis of the estab- lished model successfully explains why the potential oscillation in methanol galvanostatic oxidation on a Pt electrode only happens in a certain range of current densities but not at any current density.
