Correlation of H2 heat of adsorption and ethylene hydrogenation activity for supported Re@Pd overlayer catalysts

Latusek, Michael P.; Spigarelli, Brett P.; Heimerl, Rebecca M.; Holles, Joseph H.

doi:10.1016/j.jcat.2009.02.022

Cited by 26 publications

(46 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reactivity studies were conducted using an ethylene hydrogenation descriptor reaction and is described in detail by Latusek et al [12]. The activity of the various catalyst samples was studied as a function of different ethylene concentrations and flow rates.…”

Section: Ethylene Hydrogenation Reactivity Experimentsmentioning

confidence: 99%

“…Rhenium data was collected in transmission mode. Due to the low palladium loadings (shown in Table 1) [12], palladium data was collected in fluorescence mode [16]. Transmission catalyst samples were pressed into a thin wafer inside a six sample, steel transmission sample holder supplied at the beamline which held the sample perpendicular to the incident X-ray beam.…”

Section: Xas Experimentsmentioning

confidence: 99%

“…Latusek et al extended these computational studies by synthesizing Re@Pd catalysts for ethylene hydrogenation and hydrogen heat of adsorption studies [12]. In this work, the same catalysts previously published [12,13] were analyzed via X-ray absorption spectroscopy (XAS) to analyze their electronic and structural properties.…”

Section: Introductionmentioning

confidence: 99%

“…In this work, the same catalysts previously published [12,13] were analyzed via X-ray absorption spectroscopy (XAS) to analyze their electronic and structural properties. In addition to the catalysts synthesized by Latusek et al catalysts synthesized and published by Skoglund et al were also studied via XAS to continue their work in determining that the formation of an overlayer dominates reactivity over particle size effects [4].…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Particle Size or Electronic Effect? An XAS Study of Re@Pd Overlayer Catalysts

2015

Self Cite

View full text Add to dashboard Cite

Re@Pd (core@overlayer) catalysts are analyzed via X-ray absorption spectroscopy to correlate structural and electronic properties with previous reactivity results. The ethylene hydrogenation turnover frequency of the Re-Pd bimetallic and the Re@Pd catalysts is much lower than that of the pure Pd. A reduction of activity agrees with the computationally predicted properties of the overlayer catalysts and indicates that the overlayer catalysts have been synthesized. The FEFF fitted EXAFS yields a Pd-Pd inter-atomic distance in the Re@Pd SD small particle (2.7 nm) catalyst of 2.79 Å and in the Re@Pd SD large particle (6.3 nm) catalyst of 2.76 Å . The fitted Pd-Pd inter-atomic distance of Pd foil is 2.74 Å . The small particle overlayer Re@Pd SD catalyst is also longer than the Pd-Pd inter-atomic distance seen in the, as synthesized, structureless bimetallic Re-Pd (2.73 Å ). The disparity in calculated inter-atomic distances indicates an electronic effect is being exerted upon the disperse Pd atoms by the larger Re crystals and vice versa. The Pd K-edge and Re L III -edge white line data also show the electronic interaction between the Pd overlayer and the core Re atoms. The Pd white line of the overlayer catalysts shifted up relative to Pd foil indicating Pd d-band broadening as a result of the interaction of Pd with Re. The Re d-band of the overlayer catalysts narrowed, which is evidenced by the decreased white line absorption relative to Re foil. These observed changes in the Pd and Re d-band are consistent with computational predictions for catalysts with overlayer structures. Graphical Abstract

show abstract

Section: Ethylene Hydrogenation Reactivity Experimentsmentioning

confidence: 99%

Section: Xas Experimentsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Particle Size or Electronic Effect? An XAS Study of Re@Pd Overlayer Catalysts

2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…Catalyst preparation methods have been devised that promote Pd-Re interactions and minimize Re-support interactions. These include catalytic reduction, wherein chemisorbed H on the surface of Pd particles reduces perrhenate ions adsorbed from solution [25][26][27], and the directed deposition technique, wherein a Pd precursor is deposited on reduced Re particles [28][29][30]. Both of these methods, however, require preparation and handling of air-sensitive samples under an inert atmosphere, and the loading of Re (or Pd) is restricted based on the metal surface area of the parent catalyst.…”

Section: Introductionmentioning

confidence: 99%

Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH3)4](ReO4)2 on γ-Al2O3

Thompson

Lamb

2017

Journal of Catalysis

View full text Add to dashboard Cite

a b s t r a c tThe double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH 3 ) 4 ](ReO 4 ) 2 on c-Al 2 O 3 in flowing H 2 at 400°C yields bimetallic nanoparticles 1-2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of b-PdH x formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re L III edges (PdARe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH 3 ) 4 ](ReO 4 ) 2 on c-Al 2 O 3 at 350°C in air and subsequent reduction in H 2 at 400°C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and c-Al 2 O 3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO 4 and [Pd(NH 3 ) 4 ](NO 3 ) 2 has a similar morphology.The catalyst derived by direct reduction of [Pd(NH 3 ) 4 ](ReO 4 ) 2 on c-Al 2 O 3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150°C and 1 atm. Suppression of H 2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.

show abstract

Kinetics of Furfural Hydrogenation over Bimetallic Overlayer Catalysts and the Effect of Oxygen Vacancy Concentration on Product Selectivity

et al. 2019

View full text Add to dashboard Cite

Furfural hydrogenation over silica‐supported Co@Pd and Cu@Pd bimetallic overlayer catalysts was studied in this work. Both overlayer catalysts showed enhanced reactivity compared to pure Pd in furfural hydrogenation. Langmuir‐Hinshelwood kinetic study revealed that this enhanced reactivity could be attributed to the decreased hydrogen surface coverage on catalyst surface of overlayer catalysts compared to pure Pd during reaction, releasing more available active sites for surface reaction or furfural adsorption to take place. The effect of oxygen vacancy concentration on furfural hydrogenation product selectivity was also studied. It is proposed that oxygen vacancies were crucial for both furfural hydrodeoxygenation and aromatic ring hydrogenation, depending on the concentration of oxygen vacancies. This work provides new perspective for tuning the furfural hydrogenation product selectivity by altering the oxygen vacancy concentration.

show abstract

Correlation of H2 heat of adsorption and ethylene hydrogenation activity for supported Re@Pd overlayer catalysts

Cited by 26 publications

References 35 publications

Particle Size or Electronic Effect? An XAS Study of Re@Pd Overlayer Catalysts

Particle Size or Electronic Effect? An XAS Study of Re@Pd Overlayer Catalysts

Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH3)4](ReO4)2 on γ-Al2O3

Kinetics of Furfural Hydrogenation over Bimetallic Overlayer Catalysts and the Effect of Oxygen Vacancy Concentration on Product Selectivity

Contact Info

Product

Resources

About