Efficient catalytic hydrogen generation by intermetallic platinum-lead nanostructures with highly tunable porous feature
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摘要
The water-gas shift(WGS) reaction is an essential industrial reaction for upgrading hydrogen(H2) by removing carbon monoxide(CO), while highly efficient platinum(Pt)-based catalysts for WGS with simultaneously high activity and stability are still yet to be developed due to the poisoning issue during the reaction. Herein, we report on the porous PtPb peanut nanocrystals(porous PtPb PNCs) and porous PtPb octahedron nanocrystals(porous PtPb ONCs) with controllable ratios of Pt/Pb as extremely active and stable catalysts towards WGS reaction. It exhibits the composition-dependent activity with porous PtPb PNCs-40/ZnO being the most active for WGS to H_2, 16.9 times higher than that of the commercial Pt/C. The porous PtPb PNCs-40/ZnO also display outstanding durability with barely activity decay and negligible structure and composition changes after ten successive reaction cycles. X-ray photoelectron spectroscopy(XPS) results reveal that the suitable binding energy of Pt 4f_(7/2) and the high ratio of Pt(0)to Pt(II) in porous PtPb PNCs/ZnO and porous PtPb ONCs/ZnO are crucial for the enhanced WGS activity.The CO stripping results indicate the optimized CO adsorption strength on the Pt surface ensure the excellent WGS activity and the outstanding durability. The present work demonstrates an important advance in tuning the porous metal nanomaterials as highly efficient and durable catalysts for catalysis,energy conversion and beyond.
The water-gas shift(WGS) reaction is an essential industrial reaction for upgrading hydrogen(H2) by removing carbon monoxide(CO), while highly efficient platinum(Pt)-based catalysts for WGS with simultaneously high activity and stability are still yet to be developed due to the poisoning issue during the reaction. Herein, we report on the porous PtPb peanut nanocrystals(porous PtPb PNCs) and porous PtPb octahedron nanocrystals(porous PtPb ONCs) with controllable ratios of Pt/Pb as extremely active and stable catalysts towards WGS reaction. It exhibits the composition-dependent activity with porous PtPb PNCs-40/ZnO being the most active for WGS to H_2, 16.9 times higher than that of the commercial Pt/C. The porous PtPb PNCs-40/ZnO also display outstanding durability with barely activity decay and negligible structure and composition changes after ten successive reaction cycles. X-ray photoelectron spectroscopy(XPS) results reveal that the suitable binding energy of Pt 4f_(7/2) and the high ratio of Pt(0)to Pt(II) in porous PtPb PNCs/ZnO and porous PtPb ONCs/ZnO are crucial for the enhanced WGS activity.The CO stripping results indicate the optimized CO adsorption strength on the Pt surface ensure the excellent WGS activity and the outstanding durability. The present work demonstrates an important advance in tuning the porous metal nanomaterials as highly efficient and durable catalysts for catalysis,energy conversion and beyond.
The water-gas shift(WGS) reaction is an essential industrial reaction for upgrading hydrogen(H2) by removing carbon monoxide(CO), while highly efficient platinum(Pt)-based catalysts for WGS with simultaneously high activity and stability are still yet to be developed due to the poisoning issue during the reaction. Herein, we report on the porous PtPb peanut nanocrystals(porous PtPb PNCs) and porous PtPb octahedron nanocrystals(porous PtPb ONCs) with controllable ratios of Pt/Pb as extremely active and stable catalysts towards WGS reaction. It exhibits the composition-dependent activity with porous PtPb PNCs-40/ZnO being the most active for WGS to H_2, 16.9 times higher than that of the commercial Pt/C. The porous PtPb PNCs-40/ZnO also display outstanding durability with barely activity decay and negligible structure and composition changes after ten successive reaction cycles. X-ray photoelectron spectroscopy(XPS) results reveal that the suitable binding energy of Pt 4f_(7/2) and the high ratio of Pt(0)to Pt(II) in porous PtPb PNCs/ZnO and porous PtPb ONCs/ZnO are crucial for the enhanced WGS activity.The CO stripping results indicate the optimized CO adsorption strength on the Pt surface ensure the excellent WGS activity and the outstanding durability. The present work demonstrates an important advance in tuning the porous metal nanomaterials as highly efficient and durable catalysts for catalysis,energy conversion and beyond.
引文
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[4]Sun Y,Hla SS,Duffy GJ,et al.A comparative study of CeO2-La2O3-based Cu catalysts for the production of hydrogen from simulated coal-derived syngas.Appl Catal A Gen 2010;390:201-9.
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[10]Qiao BT,Wang AQ,Yang XF,et al.Single-atom catalysis of CO oxidation using Pt1/FeOx.Nat Chem 2011;3:634-41.
[11]Shang L,Bian T,Zhang B,et al.Graphene-supported ultrafine metal nanoparticles encapsulated by mesoporous silica:robust catalysts for oxidation and reduction reactions.Angew Chem Int Ed 2014;53:250-4.
[12]Miao DY,Goldbach A,Xu HY,et al.Platinum/apatite water-gas shift catalysts.ACS Catal 2016;6:775-83.
[13]Casado-Rivera E,Volpe DJ,Alden L,et al.Electrocatalytic activity of ordered intermetallic phases for fuel cell applications.J Am Chem Soc2004;126:4043-9.
[14]Huang YY,Cai JD,Liu MY,et al.Fabrication of a novel PtPbBi/C catalyst for ethanol electro-oxidation in alkaline medium.Electrochim Acta 2012;83:1-6.
[15]Feng YG,Bu LZ,Guo SJ,et al.3D platinum-lead nanowire networks as highly efficient ethylene glycol oxidation electrocatalysts.Small 2016;12:4464-70.
[16]Gilroy KD,Ruditskiy A,Peng HC,et al.Bimetallic nanocrystals:syntheses,properties,and applications.Chem Rev 2016;116:10414-72.
[17]Wang D,Li Y.Bimetallic nanocrystals:liquid-phase synthesis and catalytic applications.Adv Mater 2011;23:1044-60.
[18]Khan MU,Wang LB,Liu Z,et al.Pt3Co octapods as superior catalysts of CO2hydrogenation.Angew Chem Int Ed 2016;55:9548-52.
[19]Newsome DS.The water-gas shift reaction.Catal Rev Sci Eng1980;21:275-318.
[20]Zhai YP,Pierre D,Si R,et al.Alkali-stabilized Pt-OHxspecies catalyze lowtemperature water-gas shift reactions.Science 2010;329:1633-6.
[21]Yang M,Li S,Wang Y,et al.Catalytically active Au-O(OH)x-species stabilized by alkali ions on zeolites and mesoporous oxides.Science 2014;346:1498-501.
[22]Zugic B,Zhang SR,Bell DC,et al.Probing the low-temperature water-gas shift activity of alkali-promoted platinum catalysts stabilized on carbon supports.JAm Chem Soc 2014;136:3238-45.
[23]Laine RM,Rinker RG,Ford PC,et al.Homogeneous catalysis by ruthenium carbonyl in alkaline solution:the water gas shift reaction.J Am Chem Soc1977;99:252-3.
[24]Yang M,Liu JL,Lee S,et al.A common single-site Pt(II)-O(OH)x-species stabilized by sodium on‘‘active”and‘‘inert”supports catalyzes the water-gas shift reaction.J Am Chem Soc 2015;137:3470-3.
[25]Bunluesin T,Gorte RJ,Graham GW,et al.Studies of the water-gas-shift reaction on ceria-supported Pt,Pd,and Rh:implications for oxygen-storage properties.Appl Catal B Environ 1998;15:107-14.
[26]Yao SY,Zhang X,Zhou W,et al.Atomic-layered Au clusters on a-MoC as catalysts for the low-temperature water-gas shift reaction.Science2017;357:389-93.
[27]Si R,Flytzani-Stephanopoulos M.Shape and crystal-plane effects of nanoscale ceria on the activity of Au-CeO2catalysts for the water-gas shift reaction.Angew Chem Int Ed 2008;47:2884-7.
[28]Xie J,Zhang QH,Gu L,et al.Ruthenium-platinum core-shell nanocatalysts with substantially enhanced activity and durability towards methanol oxidation.Nano Energy 2016;21:247-57.
[29]Sulaiman JE,Zhu SQ,Xing ZL,et al.Pt-Ni octahedra as electrocatalysts for the ethanol electro-oxidation reaction.ACS Catal 2017;7:5134-41.
[2]Ratnasamy C,Wagner JP.Water gas shift catalysis.Catal Rev 2009;51:325-440.
[3]Stere CE,Anderson JA,Chansai S,et al.Non-thermal plasma activation of goldbased catalysts for low-temperature water-gas shift catalysis.Angew Chem Int Ed 2017;56:5579-83.
[4]Sun Y,Hla SS,Duffy GJ,et al.A comparative study of CeO2-La2O3-based Cu catalysts for the production of hydrogen from simulated coal-derived syngas.Appl Catal A Gen 2010;390:201-9.
[5]Kalamaras CM,Dionysiou DD,Efstathiou AM,et al.Mechanistic studies of the water-gas shift reaction over Pt/CexZr1-xO2catalysts:the effect of Pt particle size and Zr dopant.ACS Catal 2012;2:2729-42.
[6]Bussche KMV,Froment GF.A steady-state kinetic model for methanol synthesis and the water gas shift reaction on a commercial Cu/ZnO/Al2O3catalyst.J Catal 1996;161:1-10.
[7]Yang M,Allard LF,Flytzani-Stephanopoulos M,et al.Atomically dispersed Au-(OH)xspecies bound on titania catalyze the low-temperature water-gas shift reaction.J Am Chem Soc 2013;135:3768-71.
[8]Fu Q,Saltsburg H,Flytzani-Stephanopoulos M,et al.Active nonmetallic Au and Pt species on ceria-based water-gas shift catalysts.Science 2003;301:935-8.
[9]Rodriguez JA,Ma S,Liu P,et al.Activity of CeOxand TiOxnanoparticles grown on Au(1 1 1)in the water-gas shift reaction.Science 2007;318:1757-60.
[10]Qiao BT,Wang AQ,Yang XF,et al.Single-atom catalysis of CO oxidation using Pt1/FeOx.Nat Chem 2011;3:634-41.
[11]Shang L,Bian T,Zhang B,et al.Graphene-supported ultrafine metal nanoparticles encapsulated by mesoporous silica:robust catalysts for oxidation and reduction reactions.Angew Chem Int Ed 2014;53:250-4.
[12]Miao DY,Goldbach A,Xu HY,et al.Platinum/apatite water-gas shift catalysts.ACS Catal 2016;6:775-83.
[13]Casado-Rivera E,Volpe DJ,Alden L,et al.Electrocatalytic activity of ordered intermetallic phases for fuel cell applications.J Am Chem Soc2004;126:4043-9.
[14]Huang YY,Cai JD,Liu MY,et al.Fabrication of a novel PtPbBi/C catalyst for ethanol electro-oxidation in alkaline medium.Electrochim Acta 2012;83:1-6.
[15]Feng YG,Bu LZ,Guo SJ,et al.3D platinum-lead nanowire networks as highly efficient ethylene glycol oxidation electrocatalysts.Small 2016;12:4464-70.
[16]Gilroy KD,Ruditskiy A,Peng HC,et al.Bimetallic nanocrystals:syntheses,properties,and applications.Chem Rev 2016;116:10414-72.
[17]Wang D,Li Y.Bimetallic nanocrystals:liquid-phase synthesis and catalytic applications.Adv Mater 2011;23:1044-60.
[18]Khan MU,Wang LB,Liu Z,et al.Pt3Co octapods as superior catalysts of CO2hydrogenation.Angew Chem Int Ed 2016;55:9548-52.
[19]Newsome DS.The water-gas shift reaction.Catal Rev Sci Eng1980;21:275-318.
[20]Zhai YP,Pierre D,Si R,et al.Alkali-stabilized Pt-OHxspecies catalyze lowtemperature water-gas shift reactions.Science 2010;329:1633-6.
[21]Yang M,Li S,Wang Y,et al.Catalytically active Au-O(OH)x-species stabilized by alkali ions on zeolites and mesoporous oxides.Science 2014;346:1498-501.
[22]Zugic B,Zhang SR,Bell DC,et al.Probing the low-temperature water-gas shift activity of alkali-promoted platinum catalysts stabilized on carbon supports.JAm Chem Soc 2014;136:3238-45.
[23]Laine RM,Rinker RG,Ford PC,et al.Homogeneous catalysis by ruthenium carbonyl in alkaline solution:the water gas shift reaction.J Am Chem Soc1977;99:252-3.
[24]Yang M,Liu JL,Lee S,et al.A common single-site Pt(II)-O(OH)x-species stabilized by sodium on‘‘active”and‘‘inert”supports catalyzes the water-gas shift reaction.J Am Chem Soc 2015;137:3470-3.
[25]Bunluesin T,Gorte RJ,Graham GW,et al.Studies of the water-gas-shift reaction on ceria-supported Pt,Pd,and Rh:implications for oxygen-storage properties.Appl Catal B Environ 1998;15:107-14.
[26]Yao SY,Zhang X,Zhou W,et al.Atomic-layered Au clusters on a-MoC as catalysts for the low-temperature water-gas shift reaction.Science2017;357:389-93.
[27]Si R,Flytzani-Stephanopoulos M.Shape and crystal-plane effects of nanoscale ceria on the activity of Au-CeO2catalysts for the water-gas shift reaction.Angew Chem Int Ed 2008;47:2884-7.
[28]Xie J,Zhang QH,Gu L,et al.Ruthenium-platinum core-shell nanocatalysts with substantially enhanced activity and durability towards methanol oxidation.Nano Energy 2016;21:247-57.
[29]Sulaiman JE,Zhu SQ,Xing ZL,et al.Pt-Ni octahedra as electrocatalysts for the ethanol electro-oxidation reaction.ACS Catal 2017;7:5134-41.