Rh-doped PdAg nanoparticles as efficient methanol tolerance electrocatalytic materials for oxygen reduction
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摘要
Direct methanol fuel cells(DMFCs)have received extensive attention on their high efficiency,high reliability,and no carbon emission.Unfortunately,the poor methanol tolerance and sluggish oxygen reduction reaction(ORR)at cathode have seriously hindered their further development.Herein we report the synthesis of a new class of Rh-doped PdAg alloy nanoparticles(NPs)for boosting ORR activity with high methanol tolerance capacity concurrently.The ORR mass activity of typical Rh_4Pd_(40)Ag_(56)NPs is 4.2 times higher than that of commercial Pt catalyst.Moreover,it shows a great methanol tolerance capability by maintaining 92.4%in ORR mass activity in alkaline solution with 0.1 mol L~(à1)methanol,against a big decrease of almost 100%for commercial Pt.Even after 30,000 potential cycles with 1.0 mol L~(à1)methanol,Rh_4Pd_(40)Ag_(56)NPs still retain ORR mass activity of up to 68.3%.DFT calculations reveal that excellent ORR performance with excellent methanol tolerance originates the active d-band-pinning engineering for an efficient site-independent electron-transfer.A generalized d-band mediated fine electron-transfer tuning path has blueprinted for effectively minimizing intrinsic ORR barriers with high current density.The present work highlights the key role of Rh doping in enhancing the ORR activity and methanol tolerance ability of PdAg NPs for future high-performance DMFCs.
Direct methanol fuel cells(DMFCs)have received extensive attention on their high efficiency,high reliability,and no carbon emission.Unfortunately,the poor methanol tolerance and sluggish oxygen reduction reaction(ORR)at cathode have seriously hindered their further development.Herein we report the synthesis of a new class of Rh-doped PdAg alloy nanoparticles(NPs)for boosting ORR activity with high methanol tolerance capacity concurrently.The ORR mass activity of typical Rh_4Pd_(40)Ag_(56)NPs is 4.2 times higher than that of commercial Pt catalyst.Moreover,it shows a great methanol tolerance capability by maintaining 92.4%in ORR mass activity in alkaline solution with 0.1 mol L~(à1)methanol,against a big decrease of almost 100%for commercial Pt.Even after 30,000 potential cycles with 1.0 mol L~(à1)methanol,Rh_4Pd_(40)Ag_(56)NPs still retain ORR mass activity of up to 68.3%.DFT calculations reveal that excellent ORR performance with excellent methanol tolerance originates the active d-band-pinning engineering for an efficient site-independent electron-transfer.A generalized d-band mediated fine electron-transfer tuning path has blueprinted for effectively minimizing intrinsic ORR barriers with high current density.The present work highlights the key role of Rh doping in enhancing the ORR activity and methanol tolerance ability of PdAg NPs for future high-performance DMFCs.
Direct methanol fuel cells(DMFCs)have received extensive attention on their high efficiency,high reliability,and no carbon emission.Unfortunately,the poor methanol tolerance and sluggish oxygen reduction reaction(ORR)at cathode have seriously hindered their further development.Herein we report the synthesis of a new class of Rh-doped PdAg alloy nanoparticles(NPs)for boosting ORR activity with high methanol tolerance capacity concurrently.The ORR mass activity of typical Rh_4Pd_(40)Ag_(56)NPs is 4.2 times higher than that of commercial Pt catalyst.Moreover,it shows a great methanol tolerance capability by maintaining 92.4%in ORR mass activity in alkaline solution with 0.1 mol L~(à1)methanol,against a big decrease of almost 100%for commercial Pt.Even after 30,000 potential cycles with 1.0 mol L~(à1)methanol,Rh_4Pd_(40)Ag_(56)NPs still retain ORR mass activity of up to 68.3%.DFT calculations reveal that excellent ORR performance with excellent methanol tolerance originates the active d-band-pinning engineering for an efficient site-independent electron-transfer.A generalized d-band mediated fine electron-transfer tuning path has blueprinted for effectively minimizing intrinsic ORR barriers with high current density.The present work highlights the key role of Rh doping in enhancing the ORR activity and methanol tolerance ability of PdAg NPs for future high-performance DMFCs.
引文
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[3]Seselj N,Engelbrekt C,Ding Y,et al.Tailored electron transfer pathways in Aucore/Ptshell-graphene nanocatalysts for fuel cells.Adv Energy Mater2018;8:1702609.
[4]Mayrhofer KJJ,Arenz M.Log on for new catalysts.Nat Mater 2009;1:518-9.
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[7]Yu H,Shang L,Bian T,et al.Nitrogen-doped porous carbon nanosheets templated from g-C3N4as metal-free electrocatalysts for efficient oxygen reduction reaction.Adv Mater 2016;28:5080-6.
[8]Mehmood A,Scibioh MA,Prabhuram J,et al.A review on durability issues and restoration techniques in long-term operations of direct methanol fuel cells.JPower Sources 2015;297:224-41.
[9]Yue X,He C,Zhong C,et al.Fluorine-doped and partially oxidized tantalum carbides as nonprecious metal electrocatalysts for methanol oxidation reaction in acidic media.Adv Mater 2016;28:2163-9.
[10]Wang A-L,Xu H,Feng J-X,et al.Design of Pd/PdNi/Pd sandwich-structured nanotube array catalysts with special shape effects and synergistic effects for ethanol electrooxidation.J Am Chem Soc 2013;135:10703-9.
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[12]Gao MR,Gao Q,Jiang J,et al.A methanol-tolerant Pt/CoSe2nanobelt cathode catalyst for direct methanol fuel cells.Angew Chem Int Ed 2011;123:5007-10.
[13]Huang X,Zhao Z,Cao L,et al.High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction.Science 2015;348:1230-4.
[14]Snyder J,Livi K,Erlebacher J.Oxygen reduction reaction performance of[mtbd][beti]-encapsulated nanoporous NiPt alloy nanoparticles.Adv Funct Mater2013;23:5494-501.
[15]Luo M,Sun Y,Zhang X,et al.Stable high-index faceted Pt skin on zigzag-like ptfe nanowires enhances oxygen reduction catalysis.Adv Mater2018;30:1705515.
[16]Chen C,Kang Y,Huo Z,et al.Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces.Science 2014;343:1339-43.
[17]Xia BY,Wu HB,Wang X,et al.One-pot synthesis of cubic PtCu3nanocages with enhanced electrocatalytic activity for the methanol oxidation reaction.J Am Chem Soc 2012;134:13934-7.
[18]Luo S,Tang M,Shen PK,et al.Atomic-scale preparation of octopod nanoframes with high-index facets as highly active and stable catalysts.Adv Mater2017;29:1601687.
[19]Li M,Zhao Z,Cheng T,et al.Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction.Science2016;354:1414-9.
[20]Bu L,Ding J,Yao J,et al.A general method for multimetallic platinum alloy nanowires as highly active and stable oxygen reduction catalysts.Adv Mater2015;27:7204.
[21]Zhang C,Sandorf W,Peng Z.Octahedral Pt2CuNi uniform alloy nanoparticle catalyst with high activity and promising stability for oxygen reduction reaction.ACS Catal 2015;5:2296-300.
[22]Bu L,Zhang N,Guo S,et al.Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis.Science 2016;354:1410-4.
[23]Cai B,Hübner R,Sasaki K,et al.Core-shell structuring of pure metallic aerogels towards highly efficient platinum utilization for the oxygen reduction reaction.Angew Chem Int Ed 2018;57:2963-6.
[24]Gan L,Heggen M,Rudi S,et al.Core-shell compositional fine structures of dealloyed PtxNi1-xnanoparticles and their impact on oxygen reduction catalysis.Nano Lett 2012;12:5423-30.
[25]Bu L,Guo S,Zhang X,et al.Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis.Nat Commun 2016;7:11850.
[26]Park J,Kanti Kabiraz M,Kwon H,et al.Radially phase segregated PtCu@PtCuNi dendrite@frame nanocatalyst for the oxygen reduction reaction.ACS Nano2017;11:10844-51.
[27]Xin L,Yang F,Rasouli S,et al.Understanding Pt nanoparticle anchoring on graphene supports through surface functionalization.ACS Catal 2016;6:2642-53.
[28]Stamenkovic VR,Fowler B,Mun BS,et al.Improved oxygen reduction activity on Pt3Ni(111)via increased surface site availability.Science 2007;315:493-7.
[29]Huang X,Zhao Z,Chen Y,et al.A rational design of carbon-supported dispersive Pt-based octahedra as efficient oxygen reduction reaction catalysts.Energy Environ Sci 2014;7:2957-62.
[30]Zhang S,Zhang X,Jiang G,et al.Tuning nanoparticle structure and surface strain for catalysis optimization.J Am Chem Soc 2014;136:7734-9.
[31]Luo M,Guo S.Strain-controlled electrocatalysis on multimetallic nanomaterials.Nat Rev Mater 2017;2:17059.
[32]Argun AA,Ashcraft JN,Hammond PT.Highly conductive,methanol resistant polyelectrolyte multilayers.Adv Mater 2008;20:1539-43.
[33]Cao X,Wang N,Han Y,et al.Ptag bimetallic nanowires:facile synthesis and their use as excellent electrocatalysts toward low-cost fuel cells.Nano Energy2015;12:105-14.
[34]Wen Z,Liu J,Li J.Core/shell Pt/C nanoparticles embedded in mesoporous carbon as a methanol-tolerant cathode catalyst in direct methanol fuel cells.Adv Mater 2008;20:743-7.
[35]Kamiya K,Kamai R,Hashimoto K,et al.Platinum-modified covalent triazine frameworks hybridized with carbon nanoparticles as methanol-tolerant oxygen reduction electrocatalysts.Nat Commun 2014;5:5040.
[36]Ud Din MA,Saleem F,Ni B,et al.Porous tetrametallic ptcubimn nanosheets with a high catalytic activity and methanol tolerance limit for oxygen reduction reactions.Adv Mater 2017;29:1604994.
[37]Pan S,Cai Z,Duan Y,et al.Tungsten diselenide/porous carbon with sufficient active edge-sites as a Co-catalyst/Pt-support favoring excellent tolerance to methanol-crossover for oxygen reduction reaction in acidic medium.Appl Catal B Environ 2017;219:18-29.
[38]Mahmood A,Xie N,Din MAU,et al.Shape controlled synthesis of porous tetrametallic PtAgBiCo nanoplates as highly active and methanol-tolerant electrocatalyst for oxygen reduction reaction.Chem Sci 2017;8:4292-8.
[39]Luo M,Sun Y,Qin Y,et al.Palladium-based nanoelectrocatalysts for renewable energy generation and conversion.Mater Today Nano 2018;1:29-40.
[40]Jiang K,Wang P,Guo S,et al.Ordered PdCu-based nanoparticles as bifunctional oxygen-reduction and ethanol-oxidation electrocatalysts.Angew Chem Int Ed2016;55:9030-5.
[41]Calderón Gómez JC,Moliner R,Lázaro MJ.Palladium-based catalysts as electrodes for direct methanol fuel cells:a last ten years review.Catalysts2016;6:130.
[42]Wu H,Li H,Zhai Y,et al.Facile synthesis of free-standing Pd-based nanomembranes with enhanced catalytic performance for methanol/ethanol oxidation.Adv Mater 2012;24:1594-7.
[43]Wang K,Qin Y,Lv F,et al.Intermetallic Pd3Pb nanoplates enhance oxygen reduction catalysis with excellent methanol tolerance.Small Methods2018;2:1700331.
[44]Xu Q,Chen W,Yan Y,et al.Multimetallic AuPd@Pd@Pt core-interlayer-shell icosahedral electrocatalysts for highly efficient oxygen reduction reaction.Sci Bull 2018;63:494-501.
[45]Jiang G,Li X,Lv X,et al.Core/shell FePd/Pd catalyst with a superior activity to Pt in oxygen reduction reaction.Sci Bull 2016;61:1248-54.
[46]Xue Q,Xu G,Mao R,et al.Polyethyleneimine modified AuPd@PdAu alloy nanocrystals as advanced electrocatalysts towards the oxygen reduction reaction.J Energy Chem 2017;26:1153-9.
[47]Wang H,Zhang J,Chen Z,et al.Size-controllable synthesis and highperformance formic acid oxidation of polycrystalline Pd nanoparticles.Rare Met 2017.https://doi.org/10.1007/s12598-017-0947-0.
[48]Zhang Y,Zhang J,Chen Z,et al.One-step synthesis of the PdPt bimetallic nanodendrites with controllable composition for methanol oxidation reaction.Sci China Mater 2017;61:697-706.
[49]Marzari N,Vanderbilt D,Payne MC.Ensemble density-functional theory for ab initio molecular dynamics of metals and finite-temperature insulators.Phys Rev Lett 1997;79:1337.
[50]Sun Y,Zhang X,Luo M,et al.Ultrathin PtPd-based nanorings with abundant step atoms enhance oxygen catalysis.Adv Mater 2018;30:1802136
[51]Liu M,Lu Y,Chen W.PdAg nanorings supported on graphene nanosheets:highly methanol-tolerant cathode electrocatalyst for alkaline fuel cells.Adv Funct Mater 2013;23:1289-96.
[2]Cui C,Gan L,Heggen M,et al.Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis.Nat Mater2013;12:765-71.
[3]Seselj N,Engelbrekt C,Ding Y,et al.Tailored electron transfer pathways in Aucore/Ptshell-graphene nanocatalysts for fuel cells.Adv Energy Mater2018;8:1702609.
[4]Mayrhofer KJJ,Arenz M.Log on for new catalysts.Nat Mater 2009;1:518-9.
[5]Debe MK.Electrocatalyst approaches and challenges for automotive fuel cells.Nature 2012;486:43-51.
[6]Shang L,Yu H,Huang X,et al.Well-dispersed ZIF-derived Co,N-Co-doped carbon nanoframes through mesoporous-silica-protected calcination as efficient oxygen reduction electrocatalysts.Adv Mater 2016;28:1668-74.
[7]Yu H,Shang L,Bian T,et al.Nitrogen-doped porous carbon nanosheets templated from g-C3N4as metal-free electrocatalysts for efficient oxygen reduction reaction.Adv Mater 2016;28:5080-6.
[8]Mehmood A,Scibioh MA,Prabhuram J,et al.A review on durability issues and restoration techniques in long-term operations of direct methanol fuel cells.JPower Sources 2015;297:224-41.
[9]Yue X,He C,Zhong C,et al.Fluorine-doped and partially oxidized tantalum carbides as nonprecious metal electrocatalysts for methanol oxidation reaction in acidic media.Adv Mater 2016;28:2163-9.
[10]Wang A-L,Xu H,Feng J-X,et al.Design of Pd/PdNi/Pd sandwich-structured nanotube array catalysts with special shape effects and synergistic effects for ethanol electrooxidation.J Am Chem Soc 2013;135:10703-9.
[11]Xu C,Wang H,Shen PK,et al.Highly ordered Pd nanowire arrays as effective electrocatalysts for ethanol oxidation in direct alcohol fuel cells.Adv Mater2007;19:4256-9.
[12]Gao MR,Gao Q,Jiang J,et al.A methanol-tolerant Pt/CoSe2nanobelt cathode catalyst for direct methanol fuel cells.Angew Chem Int Ed 2011;123:5007-10.
[13]Huang X,Zhao Z,Cao L,et al.High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction.Science 2015;348:1230-4.
[14]Snyder J,Livi K,Erlebacher J.Oxygen reduction reaction performance of[mtbd][beti]-encapsulated nanoporous NiPt alloy nanoparticles.Adv Funct Mater2013;23:5494-501.
[15]Luo M,Sun Y,Zhang X,et al.Stable high-index faceted Pt skin on zigzag-like ptfe nanowires enhances oxygen reduction catalysis.Adv Mater2018;30:1705515.
[16]Chen C,Kang Y,Huo Z,et al.Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces.Science 2014;343:1339-43.
[17]Xia BY,Wu HB,Wang X,et al.One-pot synthesis of cubic PtCu3nanocages with enhanced electrocatalytic activity for the methanol oxidation reaction.J Am Chem Soc 2012;134:13934-7.
[18]Luo S,Tang M,Shen PK,et al.Atomic-scale preparation of octopod nanoframes with high-index facets as highly active and stable catalysts.Adv Mater2017;29:1601687.
[19]Li M,Zhao Z,Cheng T,et al.Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction.Science2016;354:1414-9.
[20]Bu L,Ding J,Yao J,et al.A general method for multimetallic platinum alloy nanowires as highly active and stable oxygen reduction catalysts.Adv Mater2015;27:7204.
[21]Zhang C,Sandorf W,Peng Z.Octahedral Pt2CuNi uniform alloy nanoparticle catalyst with high activity and promising stability for oxygen reduction reaction.ACS Catal 2015;5:2296-300.
[22]Bu L,Zhang N,Guo S,et al.Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis.Science 2016;354:1410-4.
[23]Cai B,Hübner R,Sasaki K,et al.Core-shell structuring of pure metallic aerogels towards highly efficient platinum utilization for the oxygen reduction reaction.Angew Chem Int Ed 2018;57:2963-6.
[24]Gan L,Heggen M,Rudi S,et al.Core-shell compositional fine structures of dealloyed PtxNi1-xnanoparticles and their impact on oxygen reduction catalysis.Nano Lett 2012;12:5423-30.
[25]Bu L,Guo S,Zhang X,et al.Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis.Nat Commun 2016;7:11850.
[26]Park J,Kanti Kabiraz M,Kwon H,et al.Radially phase segregated PtCu@PtCuNi dendrite@frame nanocatalyst for the oxygen reduction reaction.ACS Nano2017;11:10844-51.
[27]Xin L,Yang F,Rasouli S,et al.Understanding Pt nanoparticle anchoring on graphene supports through surface functionalization.ACS Catal 2016;6:2642-53.
[28]Stamenkovic VR,Fowler B,Mun BS,et al.Improved oxygen reduction activity on Pt3Ni(111)via increased surface site availability.Science 2007;315:493-7.
[29]Huang X,Zhao Z,Chen Y,et al.A rational design of carbon-supported dispersive Pt-based octahedra as efficient oxygen reduction reaction catalysts.Energy Environ Sci 2014;7:2957-62.
[30]Zhang S,Zhang X,Jiang G,et al.Tuning nanoparticle structure and surface strain for catalysis optimization.J Am Chem Soc 2014;136:7734-9.
[31]Luo M,Guo S.Strain-controlled electrocatalysis on multimetallic nanomaterials.Nat Rev Mater 2017;2:17059.
[32]Argun AA,Ashcraft JN,Hammond PT.Highly conductive,methanol resistant polyelectrolyte multilayers.Adv Mater 2008;20:1539-43.
[33]Cao X,Wang N,Han Y,et al.Ptag bimetallic nanowires:facile synthesis and their use as excellent electrocatalysts toward low-cost fuel cells.Nano Energy2015;12:105-14.
[34]Wen Z,Liu J,Li J.Core/shell Pt/C nanoparticles embedded in mesoporous carbon as a methanol-tolerant cathode catalyst in direct methanol fuel cells.Adv Mater 2008;20:743-7.
[35]Kamiya K,Kamai R,Hashimoto K,et al.Platinum-modified covalent triazine frameworks hybridized with carbon nanoparticles as methanol-tolerant oxygen reduction electrocatalysts.Nat Commun 2014;5:5040.
[36]Ud Din MA,Saleem F,Ni B,et al.Porous tetrametallic ptcubimn nanosheets with a high catalytic activity and methanol tolerance limit for oxygen reduction reactions.Adv Mater 2017;29:1604994.
[37]Pan S,Cai Z,Duan Y,et al.Tungsten diselenide/porous carbon with sufficient active edge-sites as a Co-catalyst/Pt-support favoring excellent tolerance to methanol-crossover for oxygen reduction reaction in acidic medium.Appl Catal B Environ 2017;219:18-29.
[38]Mahmood A,Xie N,Din MAU,et al.Shape controlled synthesis of porous tetrametallic PtAgBiCo nanoplates as highly active and methanol-tolerant electrocatalyst for oxygen reduction reaction.Chem Sci 2017;8:4292-8.
[39]Luo M,Sun Y,Qin Y,et al.Palladium-based nanoelectrocatalysts for renewable energy generation and conversion.Mater Today Nano 2018;1:29-40.
[40]Jiang K,Wang P,Guo S,et al.Ordered PdCu-based nanoparticles as bifunctional oxygen-reduction and ethanol-oxidation electrocatalysts.Angew Chem Int Ed2016;55:9030-5.
[41]Calderón Gómez JC,Moliner R,Lázaro MJ.Palladium-based catalysts as electrodes for direct methanol fuel cells:a last ten years review.Catalysts2016;6:130.
[42]Wu H,Li H,Zhai Y,et al.Facile synthesis of free-standing Pd-based nanomembranes with enhanced catalytic performance for methanol/ethanol oxidation.Adv Mater 2012;24:1594-7.
[43]Wang K,Qin Y,Lv F,et al.Intermetallic Pd3Pb nanoplates enhance oxygen reduction catalysis with excellent methanol tolerance.Small Methods2018;2:1700331.
[44]Xu Q,Chen W,Yan Y,et al.Multimetallic AuPd@Pd@Pt core-interlayer-shell icosahedral electrocatalysts for highly efficient oxygen reduction reaction.Sci Bull 2018;63:494-501.
[45]Jiang G,Li X,Lv X,et al.Core/shell FePd/Pd catalyst with a superior activity to Pt in oxygen reduction reaction.Sci Bull 2016;61:1248-54.
[46]Xue Q,Xu G,Mao R,et al.Polyethyleneimine modified AuPd@PdAu alloy nanocrystals as advanced electrocatalysts towards the oxygen reduction reaction.J Energy Chem 2017;26:1153-9.
[47]Wang H,Zhang J,Chen Z,et al.Size-controllable synthesis and highperformance formic acid oxidation of polycrystalline Pd nanoparticles.Rare Met 2017.https://doi.org/10.1007/s12598-017-0947-0.
[48]Zhang Y,Zhang J,Chen Z,et al.One-step synthesis of the PdPt bimetallic nanodendrites with controllable composition for methanol oxidation reaction.Sci China Mater 2017;61:697-706.
[49]Marzari N,Vanderbilt D,Payne MC.Ensemble density-functional theory for ab initio molecular dynamics of metals and finite-temperature insulators.Phys Rev Lett 1997;79:1337.
[50]Sun Y,Zhang X,Luo M,et al.Ultrathin PtPd-based nanorings with abundant step atoms enhance oxygen catalysis.Adv Mater 2018;30:1802136
[51]Liu M,Lu Y,Chen W.PdAg nanorings supported on graphene nanosheets:highly methanol-tolerant cathode electrocatalyst for alkaline fuel cells.Adv Funct Mater 2013;23:1289-96.