One of the primary challenges in relation to phosphoric acid fuel cells is catalyst poisoning by phosphate anions that occurs at the interface between metal nanoparticles and the electrolyte.The strong adsorption of p...One of the primary challenges in relation to phosphoric acid fuel cells is catalyst poisoning by phosphate anions that occurs at the interface between metal nanoparticles and the electrolyte.The strong adsorption of phosphate anions on the catalyst surface limits the active sites for the oxygen reduction reaction(ORR),significantly deteriorating fuel cell performance.Here,antipoisoning catalysts consisting of Pt-based nanoparticles encapsulated in an ultrathin carbon shell that can be used as a molecular sieve layer are rationally designed.The pore structure of the carbon shells is systematically regulated at the atomic level by high-temperature gas treatment,allowing O_(2) molecules to selectively react on the active sites of the metal nanoparticles through the molecular sieves.Besides,the carbon shell,as a protective layer,effectively prevents metal dissolution from the catalyst during a long-term operation.Consequently,the defect-controlled carbon shell leads to outstanding ORR activity and durability of the hybrid catalyst even in phosphoric acid electrolytes.展开更多
The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited o...The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited on Pt/C from Bi3＋ containing acidic solution from 0 to 90% coverage degree. The stability of the Bi layer in acid and alkaline corresponded to previous studies and started to dissolve at 0.7 V and 0.8 V versus re- versible hydrogen electrode （RIIE）, respectively. However, in neutral phosphate buffer the layer showed remarkable stability to at least 1.2V versus RHE. Bi modification at low （20%） and high （80%） coverage showed the highest increase in the activity of Pt/C toward GOR by a factor up to 7 due to the increased poisoning resistance of the modified catalyst. The effect of poisoning was especially reduced at high Bi coverage （80%）, which shows that adsorbate blocked by Bi through the third-body effect is effective. Finally, with or without Bi modification GOR on PtIC was most active in alkaline conditions.展开更多
Sulfur poisoning of V_2O_5/BaSO_4–TiO_2（VBT）,V_2O_5/WO_3–TiO_2（VWT） and V_2O_5/BaSO_4–WO_3–TiO_2（VBWT） catalysts was performed in wet air at 350℃ for 3 hr,and activities for the selective catalytic reductio...Sulfur poisoning of V_2O_5/BaSO_4–TiO_2（VBT）,V_2O_5/WO_3–TiO_2（VWT） and V_2O_5/BaSO_4–WO_3–TiO_2（VBWT） catalysts was performed in wet air at 350℃ for 3 hr,and activities for the selective catalytic reduction of NO_x with NH_3 were evaluated for 200–500℃.The VBT catalyst showed higher NO_x conversions after sulfur poisoning than the other two catalysts.The introduction of barium sulfate contributed to strong acid sites for the as-received catalyst,and eliminated the redox cycle of active vanadium oxide to some extent,which resulted in a certain loss of activity.Readily decomposable sulfate species formed on VBT-S instead of inactive sulfates on VWT-S.These decomposable sulfates increased the number of strong acid sites significantly.Some sulfate species escaped during catalyst preparation and barium sulfate was reproduced during sulfur poisoning,which protects vanadia from sulfur oxide attachment to a great extent.Consequently,the VBT catalyst exhibited the best resistance to sulfur poisoning.展开更多
Catalyzed diesel particulate filter(CDPF)combines the functions of the oxidization catalyst and the diesel particulate filter.Due to good redox capacity and oxygen storage capacity,CeO2 is used as the catalyst of CDPF...Catalyzed diesel particulate filter(CDPF)combines the functions of the oxidization catalyst and the diesel particulate filter.Due to good redox capacity and oxygen storage capacity,CeO2 is used as the catalyst of CDPF.Since the effects of key factors on the performance of Ce02-based CDPF were rarely reported,it was performed in this study based on a zero-dimensional numerical model using plug flow reactor in which a reaction mechanism was established and validated by the experiment of the thermal gravimetric analyzer.The effects of exhaust gas temperature and three defined parameters including the ratios of NO2 in NO,(α),NOx to soot(β),and catalyst coated amount to carbon loading amount(y)on catalyst poisoning temperature,N20 concentration,NOx reduction rate and soot regeneration rate were investigated.The results show that the rising exhaust gas temperature causes the reduction of NOx concentration,and the NOx reduction rate comes to 66%when the catalyst poisoning temperature is reached.The soot regeneration rate and the N2O concentration first increase and then decrease as the exhaust gas temperature increases.Meanwhile,the higher exhaust gas temperature suppresses the production of N2O,but raises the possibility of catalyst poisoning.The increasing a and p result in the increase of soot regeneration rate and the decrease of NOx reduction rate.The catalyst poisoning temperature is improved at higher a and lower p.The soot regeneration rate has a fast increase with y at first and then stabilizes rapidly.The results of this study are valuable to optimize the operation of CDPF.展开更多
基金National Research Foundation of Korea(NRF),Grant/Award Number:2021R1A2C2012685Korea Institute of Energy Technology Evaluation and Planning(KETEP),Grant/Award Number:20203020030010Ministry of Trade,Industry&Energy(MOTIE,Korea),Grant/Award Number:20020400。
文摘One of the primary challenges in relation to phosphoric acid fuel cells is catalyst poisoning by phosphate anions that occurs at the interface between metal nanoparticles and the electrolyte.The strong adsorption of phosphate anions on the catalyst surface limits the active sites for the oxygen reduction reaction(ORR),significantly deteriorating fuel cell performance.Here,antipoisoning catalysts consisting of Pt-based nanoparticles encapsulated in an ultrathin carbon shell that can be used as a molecular sieve layer are rationally designed.The pore structure of the carbon shells is systematically regulated at the atomic level by high-temperature gas treatment,allowing O_(2) molecules to selectively react on the active sites of the metal nanoparticles through the molecular sieves.Besides,the carbon shell,as a protective layer,effectively prevents metal dissolution from the catalyst during a long-term operation.Consequently,the defect-controlled carbon shell leads to outstanding ORR activity and durability of the hybrid catalyst even in phosphoric acid electrolytes.
基金Jane and Aatos Erkko FoundationJenny and Antti Wihuri Foundation for funding
文摘The effect of irreversibly adsorbed Bi on commercial Pt/C catalyst toward glucose electro-oxidation re- action （GOR） in different electrolytes （acidic, neutral, alkaline） is studied. Bi is successfully deposited on Pt/C from Bi3＋ containing acidic solution from 0 to 90% coverage degree. The stability of the Bi layer in acid and alkaline corresponded to previous studies and started to dissolve at 0.7 V and 0.8 V versus re- versible hydrogen electrode （RIIE）, respectively. However, in neutral phosphate buffer the layer showed remarkable stability to at least 1.2V versus RHE. Bi modification at low （20%） and high （80%） coverage showed the highest increase in the activity of Pt/C toward GOR by a factor up to 7 due to the increased poisoning resistance of the modified catalyst. The effect of poisoning was especially reduced at high Bi coverage （80%）, which shows that adsorbate blocked by Bi through the third-body effect is effective. Finally, with or without Bi modification GOR on PtIC was most active in alkaline conditions.
基金the financial support from projects of the Ministry of Science and Technology,China(Nos.2015AA034603,2016YFC0205200)the Science and Technology Department of Zhejiang Province,China(No.2015C31015)
文摘Sulfur poisoning of V_2O_5/BaSO_4–TiO_2（VBT）,V_2O_5/WO_3–TiO_2（VWT） and V_2O_5/BaSO_4–WO_3–TiO_2（VBWT） catalysts was performed in wet air at 350℃ for 3 hr,and activities for the selective catalytic reduction of NO_x with NH_3 were evaluated for 200–500℃.The VBT catalyst showed higher NO_x conversions after sulfur poisoning than the other two catalysts.The introduction of barium sulfate contributed to strong acid sites for the as-received catalyst,and eliminated the redox cycle of active vanadium oxide to some extent,which resulted in a certain loss of activity.Readily decomposable sulfate species formed on VBT-S instead of inactive sulfates on VWT-S.These decomposable sulfates increased the number of strong acid sites significantly.Some sulfate species escaped during catalyst preparation and barium sulfate was reproduced during sulfur poisoning,which protects vanadia from sulfur oxide attachment to a great extent.Consequently,the VBT catalyst exhibited the best resistance to sulfur poisoning.
基金This work is supported by National Natural Science Foundation of China(Grant No.51976016 and 51806250)We also thank to the support by Open Research Subject of State Key Laboratory of Engines,China(Grant No.K2018-07)Open Research Subject of Key Laboratory of Advanced Manufacture Technology for Automobile Parts(Grant No.2017KLMT02,Chongqing University of Technology).
文摘Catalyzed diesel particulate filter(CDPF)combines the functions of the oxidization catalyst and the diesel particulate filter.Due to good redox capacity and oxygen storage capacity,CeO2 is used as the catalyst of CDPF.Since the effects of key factors on the performance of Ce02-based CDPF were rarely reported,it was performed in this study based on a zero-dimensional numerical model using plug flow reactor in which a reaction mechanism was established and validated by the experiment of the thermal gravimetric analyzer.The effects of exhaust gas temperature and three defined parameters including the ratios of NO2 in NO,(α),NOx to soot(β),and catalyst coated amount to carbon loading amount(y)on catalyst poisoning temperature,N20 concentration,NOx reduction rate and soot regeneration rate were investigated.The results show that the rising exhaust gas temperature causes the reduction of NOx concentration,and the NOx reduction rate comes to 66%when the catalyst poisoning temperature is reached.The soot regeneration rate and the N2O concentration first increase and then decrease as the exhaust gas temperature increases.Meanwhile,the higher exhaust gas temperature suppresses the production of N2O,but raises the possibility of catalyst poisoning.The increasing a and p result in the increase of soot regeneration rate and the decrease of NOx reduction rate.The catalyst poisoning temperature is improved at higher a and lower p.The soot regeneration rate has a fast increase with y at first and then stabilizes rapidly.The results of this study are valuable to optimize the operation of CDPF.
