Palm kernel shell(PKS)biochars with different levels of carbon conversion were initially prepared using a tube furnace,after which the reactivity of each sample was assessed with a thermogravimetric analyzer under a C...Palm kernel shell(PKS)biochars with different levels of carbon conversion were initially prepared using a tube furnace,after which the reactivity of each sample was assessed with a thermogravimetric analyzer under a CO_2 atmosphere.The pore structure and carbon ordering of each biochar also examined,employing a surface area analyzer and a Raman spectroscopy.Thermogravimetric results showed that the gasification index R_sof the PKS biochar decreased from 0.0305 min^(-1) at carbon conversion(x)=20% to 0.0278 min^(-1)at x=40%.The expansion of micropores was the dominant process during the pore structure evolution,ad mesopores with sizes ranging from 6 to 20,48 to 50 nm were primarily generated during gasification under a CO_2/H_2O mixture.The proportion of amorphous carbon in the PKS biochar decreased significantly as x increased,suggesting that the proportion of ordered carbon was increased during the CO_2/H_2O mixed gasification.A significantly reduced total reaction time was observed when employing a CO_2/intermittent H_2O process along with an 83.46% reduction in the steam feed,compared with the amount required using a CO_2/H_2O atmosphere.展开更多
Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction(ORR).However,the application of Pt-transition metal alloys in fuel cells is largely limited by po...Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction(ORR).However,the application of Pt-transition metal alloys in fuel cells is largely limited by poor long-term durability because transition metals can easily leach.In this study,we developed a nonmetallic doping approach and prepared a P-doped Pt catalyst with excellent durability for the ORR.Carbon-supported core-shell nanoparticles with a P-doped Pt core and Pt shell(denoted as PtPx@Pt/C)were synthesized via heat-treatment phosphorization of commercial Pt/C,followed by acid etching.Compositional analysis using electron energy loss spectroscopy and X-ray photoelectron spectroscopy clearly demonstrated that Pt was enriched in the near-surface region(approximately 1 nm)of the carbon-supported core-shell nanoparticles.Owning to P doping,the ORR specific activity and mass activity of the PtP_(1.4)@Pt/C catalyst were as high as 0.62 mA cm^(–2)and 0.31 mAμgPt–^(1),respectively,at 0.90 V,and they were enhanced by 2.8 and 2.1 times,respectively,in comparison with the Pt/C catalyst.More importantly,PtP_(1.4)@Pt/C exhibited superior stability with negligible mass activity loss(6%after 30000 potential cycles and 25%after 90000 potential cycles),while Pt/C lost 46%mass activity after 30000 potential cycles.The high ORR activity and durability were mainly attributed to the core-shell nanostructure,the electronic structure effect,and the resistance of Pt nanoparticles against aggregation,which originated from the enhanced ability of the PtP_(1.4)@Pt to anchor to the carbon support.This study provides a new approach for constructing nonmetal-doped Pt-based catalysts with excellent activity and durability for the ORR.展开更多
基金Supported by the Key Project of the Natural Science Foundation of Shandong Province(ZR2015QZ02)the Key Research&Development Program of Shandong Province(2016GSF117005)+1 种基金the introduction of scientific and technological innovation team of Ningxia Hui Autonomous Region(2016)Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(2017-K22)
文摘Palm kernel shell(PKS)biochars with different levels of carbon conversion were initially prepared using a tube furnace,after which the reactivity of each sample was assessed with a thermogravimetric analyzer under a CO_2 atmosphere.The pore structure and carbon ordering of each biochar also examined,employing a surface area analyzer and a Raman spectroscopy.Thermogravimetric results showed that the gasification index R_sof the PKS biochar decreased from 0.0305 min^(-1) at carbon conversion(x)=20% to 0.0278 min^(-1)at x=40%.The expansion of micropores was the dominant process during the pore structure evolution,ad mesopores with sizes ranging from 6 to 20,48 to 50 nm were primarily generated during gasification under a CO_2/H_2O mixture.The proportion of amorphous carbon in the PKS biochar decreased significantly as x increased,suggesting that the proportion of ordered carbon was increased during the CO_2/H_2O mixed gasification.A significantly reduced total reaction time was observed when employing a CO_2/intermittent H_2O process along with an 83.46% reduction in the steam feed,compared with the amount required using a CO_2/H_2O atmosphere.
文摘Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction(ORR).However,the application of Pt-transition metal alloys in fuel cells is largely limited by poor long-term durability because transition metals can easily leach.In this study,we developed a nonmetallic doping approach and prepared a P-doped Pt catalyst with excellent durability for the ORR.Carbon-supported core-shell nanoparticles with a P-doped Pt core and Pt shell(denoted as PtPx@Pt/C)were synthesized via heat-treatment phosphorization of commercial Pt/C,followed by acid etching.Compositional analysis using electron energy loss spectroscopy and X-ray photoelectron spectroscopy clearly demonstrated that Pt was enriched in the near-surface region(approximately 1 nm)of the carbon-supported core-shell nanoparticles.Owning to P doping,the ORR specific activity and mass activity of the PtP_(1.4)@Pt/C catalyst were as high as 0.62 mA cm^(–2)and 0.31 mAμgPt–^(1),respectively,at 0.90 V,and they were enhanced by 2.8 and 2.1 times,respectively,in comparison with the Pt/C catalyst.More importantly,PtP_(1.4)@Pt/C exhibited superior stability with negligible mass activity loss(6%after 30000 potential cycles and 25%after 90000 potential cycles),while Pt/C lost 46%mass activity after 30000 potential cycles.The high ORR activity and durability were mainly attributed to the core-shell nanostructure,the electronic structure effect,and the resistance of Pt nanoparticles against aggregation,which originated from the enhanced ability of the PtP_(1.4)@Pt to anchor to the carbon support.This study provides a new approach for constructing nonmetal-doped Pt-based catalysts with excellent activity and durability for the ORR.
