Promotion of Hydrogenation of Organic Molecules by Incorporating Iron into Platinum Nanoparticle Catalysts: Displacement of Inactive Reaction Intermediates

We characterize the surface chemical states of reactants and catalysts under reaction conditions to elucidate the composition effect of platinum–iron bimetallic nanoparticles on catalytic hydrogenation of organic molecules. The catalytic hydrogenation of ethylene is drastically accelerated on the surface of 2 nm PtFe bimetallic nanoparticles as compared to pure Pt. Sum frequency generation (SFG) vibrational spectroscopy indicates that incorporation of Fe into Pt nanoparticle catalysts weakens the adsorption of ethylidyne, an inactive spectator species, on the catalyst surface. Similarly, the turnover frequency of cyclohexene hydrogenation is also significantly enhanced by incorporating Fe into Pt nanoparticle catalysts. Ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) reveals the surface composition and oxidation states of the PtFe nanoparticles under reaction conditions. The oxidation state distribution of Fe responded to the gas atmosphere and the probing depth, whereas the Pt remained largely...

[1]  K. Tam,et al.  Synthesis and Fabrication of a Thin Film Containing Silica‐Encapsulated Face‐Centered Tetragonal FePt Nanoparticles , 2006 .

[2]  Jingguang G. Chen,et al.  Review of Pt-based bimetallic catalysis: from model surfaces to supported catalysts. , 2012, Chemical reviews.

[3]  Peidong Yang,et al.  Sub-10 nm platinum nanocrystals with size and shape control: catalytic study for ethylene and pyrrole hydrogenation. , 2009, Journal of the American Chemical Society.

[4]  Longwei Yin,et al.  Well-dispersed and size-tuned bimetallic PtFex nanoparticle catalysts supported on ordered mesoporous carbon for enhanced electrocatalytic activity in direct methanol fuel cells , 2012 .

[5]  G. Somorjai,et al.  Cyclohexene dehydrogenation and hydrogenation on Pt(111) monitored by SFG surface vibrational spectroscopy: different reaction mechanisms at high pressures and in vacuum , 1998 .

[6]  G. Somorjai,et al.  Evolution of structure and chemistry of bimetallic nanoparticle catalysts under reaction conditions. , 2010, Journal of the American Chemical Society.

[7]  G. Somorjai,et al.  Intrinsic relation between catalytic activity of CO oxidation on Ru nanoparticles and Ru oxides uncovered with ambient pressure XPS. , 2012, Nano letters.

[8]  James L. Gole,et al.  Interactive metal ion–silicon oxidation/reduction processes on fumed silica , 2012 .

[9]  A S Bondarenko,et al.  Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. , 2009, Nature chemistry.

[10]  Q. Fu,et al.  Highly active Pt–Fe bicomponent catalysts for CO oxidation in the presence and absence of H2 , 2012 .

[11]  Vadim V. Guliants,et al.  Recent developments in catalysis using nanostructured materials , 2009 .

[12]  Zhi Liu,et al.  Easy synthesis of bimetal PtFe-containing ordered mesoporous carbons and their use as catalysts for selective cinnamaldehyde hydrogenation , 2013 .

[13]  Tao Zhang,et al.  Novel Alumina-Supported PtFe Alloy Nanoparticles for Preferential Oxidation of Carbon Monoxide in Hydrogen , 2008 .

[14]  Lin-wang Wang,et al.  Furfuraldehyde hydrogenation on titanium oxide-supported platinum nanoparticles studied by sum frequency generation vibrational spectroscopy: acid-base catalysis explains the molecular origin of strong metal-support interactions. , 2012, Journal of the American Chemical Society.

[15]  Z. Hussain,et al.  New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2. , 2010, The Review of scientific instruments.

[16]  G. Somorjai,et al.  High-surface-area catalyst design: Synthesis, characterization, and reaction studies of platinum nanoparticles in mesoporous SBA-15 silica. , 2005, The journal of physical chemistry. B.

[17]  Xiaomin Wang,et al.  Carbon nanotube-supported Pt-based bimetallic catalysts prepared by a microwave-assisted polyol reduction method and their catalytic applications in the selective hydrogenation , 2010 .

[18]  C. Powell,et al.  Elastic photoelectron-scattering effects in quantitative X-ray photoelectron spectroscopy , 2012 .

[19]  M. Koyanagi,et al.  Investigation of the effect of in situ annealing of FePt nanodots under high vacuum on the chemical states of Fe and Pt by x-ray photoelectron spectroscopy , 2008 .

[20]  Ya‐Wen Zhang,et al.  Shape control of bimetallic nanocatalysts through well-designed colloidal chemistry approaches. , 2012, Chemical Society reviews.

[21]  Feng Tao,et al.  Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles , 2008, Science.

[22]  M. S. Hegde,et al.  Hydrogen Spillover on CeO2/Pt: Enhanced Storage of Active Hydrogen , 2007 .

[23]  W. Schirmer,et al.  Introduction to Surface Chemistry and Catalysis , 1995 .

[24]  K. Komvopoulos,et al.  High-Pressure Adsorption of Ethylene on Cubic Pt Nanoparticles and Pt(100) Single Crystals Probed by in Situ Sum Frequency Generation Vibrational Spectroscopy , 2012 .

[25]  E. Morallón,et al.  Highly dispersed platinum nanoparticles on carbon nanocoils and their electrocatalytic performance for fuel cell reactions , 2009 .

[26]  Jian Xu,et al.  Effect of Pt Impregnation on a Precipitated Iron-based Fischer–Tropsch Synthesis Catalyst , 2008 .

[27]  Mostafa A. El-Sayed,et al.  Shape-Dependent Catalytic Activity of Platinum Nanoparticles in Colloidal Solution , 2004 .

[28]  D. Blowes,et al.  Spectroscopic study of precipitates formed during removal of selenium from mine drainage spiked with selenate using permeable reactive materials , 2008 .

[29]  G. Somorjai,et al.  Nanoscale advances in catalysis and energy applications. , 2010, Nano letters.

[30]  G. Somorjai,et al.  Ethylene Hydrogenation on Pt(111) Monitored in Situ at High Pressures Using Sum Frequency Generation , 1996 .

[31]  Dingsheng Wang,et al.  Bimetallic Nanocrystals: Liquid‐Phase Synthesis and Catalytic Applications , 2011, Advanced materials.

[32]  Shouheng Sun,et al.  Recent Advances in Chemical Synthesis, Self‐Assembly, and Applications of FePt Nanoparticles , 2006 .

[33]  G. Somorjai,et al.  Size and Shape Dependence on Pt Nanoparticles for the Methylcyclopentane/Hydrogen Ring Opening/Ring Enlargement Reaction , 2011 .

[34]  J. Kuhn Effect of Organic Capping Layers over Monodisperse Platinum Nanoparticles upon Activity for Ethylene Hydrogenation and Carbon Monoxide Oxidation , 2009 .

[35]  G. Somorjai,et al.  The surface chemistry of 1,3-cyclohexadiene and 1,4-cyclohexadiene on Pt(111) studied by surface vibrational spectroscopy with sum frequency generation , 1997 .

[36]  G. Somorjai,et al.  Influence of Particle Size on Reaction Selectivity in Cyclohexene Hydrogenation and Dehydrogenation over Silica-Supported Monodisperse Pt Particles , 2008 .

[37]  T. Yamashita,et al.  Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials , 2008 .

[38]  K. Komvopoulos,et al.  Sum Frequency Generation Vibrational Spectroscopy of Colloidal Platinum Nanoparticle Catalysts: Disordering versus Removal of Organic Capping , 2012 .