Decomposition of P(CH3)3 on Ru(0001): comparison with PH3 and PCl3

Tao, H.-S.; Diebold, Ulrike; Shinn, Neal D.; Madey, T. E.

doi:10.1016/s0039-6028(96)01280-0

Cited by 18 publications

(13 citation statements)

References 18 publications

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“…Before hydrotreating, as shown in Figures (a) and (b), peaks for P 2p 1/2 (130.2 eV) and P 2p 3/2 (129.6 eV), with an electron binding energy (ΔBE) of 0.6 eV, and the characteristic peaks for Co 2p [BE (Co 2p 1/2 ) = 778.2 eV; BE (Co 2p 3/2 ) = 793.8 eV] are observed; these values are very similar to those reported for Co 2 P . Interestingly, after the hydrotreating process, a new peak at 129.3 eV in the spectrum of P 2p [Figure (c)] is observed, which is assigned to P–H bonding, again very close to the value reported in the literature (129.1 eV) , . So it can be concluded that P–H bonds form after hydrotreating.…”

Section: Resultssupporting

confidence: 77%

Intracell Hydrogen Adsorption–Transmission in a Co₂P Solid Hydrogen‐Storage Material

Bao

Gao

et al. 2016

Eur J Inorg Chem

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Co 2 P nanoparticles, obtained by a simple mechanical ball-milling treatment, have been shown to undergo a new hydrogen adsorption-transmission process called intracell Kubas-enhanced adsorption, which results in an improved hydrogen-storage capacity. It is found that in this intracell Kubas-enhanced adsorption process hydrogen is firstly adsorbed by the Co atoms in Co 2 P through a Co···H interaction and acti- [a]

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Section: Resultssupporting

confidence: 77%

Intracell Hydrogen Adsorption–Transmission in a Co₂P Solid Hydrogen‐Storage Material

Bao

Gao

et al. 2016

Eur J Inorg Chem

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“…The phosphorus-modified Ru(0001) surface is prepared by exposing Ru(0001) to 2.5 Langmuirs (1 Langmuir = 10 –6 Torr s) of PH 3 (Sigma-Aldrich, 99.9995%) at 300 K followed by annealing the crystal to 1400 K at 5 K s –1 . , The atomic ratio of phosphorus to ruthenium (P/Ru) at the surface is determined with AES (3 keV, 1 mA emission) by comparing the peak to peak intensity at 120 eV for P to that at 273 eV for Ru and using published Auger sensitivity factors . The preparation method produces samples with a surface P/Ru ratio of ∼0.4, which are denoted as P 0.4 –Ru(0001).…”

Section: Experimental Methods and Catalyst Characterizationmentioning

confidence: 99%

Catalytic Hydrogen Transfer and Decarbonylation of Aromatic Aldehydes on Ru and Ru Phosphide Model Catalysts

2018

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Transition-metal and metal phosphide nanoparticles catalyze hydrogen-transfer steps that reduce biomass-derived aldehydes using either gaseous H2 or organic hydrogen donors (e.g., alcohols) and produce valuable chemicals and fuels to replace petroleum derivatives. Here, we study reactions of aromatic aldehydes (furfural, benzaldehyde) on Ru(0001) and P0.4–Ru(0001), a surface representative of the (0001) facet of Ru2P, to determine how the addition of phosphorus influences activation barriers and flux along competing reaction pathways. Although Ru(0001) entirely decomposes furfural to CO, H2, and surface carbon, P0.4–Ru(0001) primarily decarbonylates furfural to form CO and furan. Similarly, benzaldehyde decarbonylates to benzene with a selectivity that is 7-fold greater over P0.4–Ru(0001) than on Ru(0001). These observations are consistent with weaker interactions between adsorbates and P0.4–Ru(0001) than on Ru(0001) that reflect charge transfer from Ru to P that in turn reduces electron back donation from Ru to the adsorbates and leads to selective decarbonylation of aromatic aldehydes over P0.4–Ru(0001). The distribution of product isotopologues from temperature-programmed reactions of selectively deuterated forms of furfural on P0.4–Ru(0001) shows that furan forms by catalytic transfer hydrogenation (CTH) on P0.4–Ru(0001). The rate-determining step that forms furan from a furanyl surface species involves hydrogen transfer, but H atoms transfer directly from either the aldehydic group or the decomposed aromatic ring of the parent molecule and not from H* atoms chemisorbed to Ru. These findings show that modifying Ru with phosphorus results in the selective rupture of C–C bond required for decarbonylation while facilitating CTH of reactive intermediates from aromatic aldehydes in the absence of an external hydrogen source.

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“…P x -Ru(0001) Catalyst Synthesis. P x -Ru(0001) surfaces are prepared by sequential cycles of saturation exposures (2.5 langmuirs) of PH 3 (Sigma-Aldrich, 99.9995%) gas onto Ru(0001) surface at 300 K followed by heating at 5 K s −1 to 1300 K. 30,31 The resulting atomic P:Ru ratio is determined using the ratio of the AES peak to peak intensities at 120 eV for P MVV to 273 eV for Ru MNN (Figure 2) and using published Auger sensitivity factors. 32 Surfaces with atomic P:Ru ratios ranging from 0 to 0.43 were produced.…”

Section: Methodsmentioning

confidence: 99%

Mechanistic Study of Formic Acid Decomposition over Ru(0001) and P_x-Ru(0001): Effects of Phosphorus on C–H and C–O Bond Rupture

Chang

Flaherty

2016

J. Phys. Chem. C

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Transition metal phosphide (TMP) catalysts are selective and active toward C–O bond rupture in hydrodeoxygenation reactions; however, the manner in which C–O bond rupture mechanisms and intrinsic energy barriers differ between transition metals and TMP is not well understood. In this study, we characterize the chemical and structural properties of phosphorus (P) modified Ru(0001) surface using Auger electron spectroscopy, low-energy electron diffraction, and temperature-programmed desorption (TPD) of CO and NH3. The decomposition pathways for formic acid and the differences between the associated barriers were studied using temperature-programmed reaction (TPR) and reactive molecular beam scattering (RMBS) of DCOOH on pristine and P-modified Ru(0001) surfaces. TPR and TPD results suggest that P atoms introduce an electronic (and perhaps a geometric) effect that decreases the extent of electron exchange between Ru atoms and adsorbates, which decreases desorption energies and increases barriers for C–O and C–H/D bond rupture. RMBS of DCOOH (measured from 500 to 800 K) shows the addition of P atoms enhances C–O bond over C–D bond rupture. These findings provide useful information for the rational design of TMP catalysts to enhance C–O bond rupture, which will increase biomass conversion efficiency to platform chemicals.

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Decomposition of P(CH3)3 on Ru(0001): comparison with PH3 and PCl3

Cited by 18 publications

References 18 publications

Intracell Hydrogen Adsorption–Transmission in a Co₂P Solid Hydrogen‐Storage Material

Intracell Hydrogen Adsorption–Transmission in a Co₂P Solid Hydrogen‐Storage Material

Catalytic Hydrogen Transfer and Decarbonylation of Aromatic Aldehydes on Ru and Ru Phosphide Model Catalysts

Mechanistic Study of Formic Acid Decomposition over Ru(0001) and P_x-Ru(0001): Effects of Phosphorus on C–H and C–O Bond Rupture

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Decomposition of P(CH3)3 on Ru(0001): comparison with PH3 and PCl3

Cited by 18 publications

References 18 publications

Intracell Hydrogen Adsorption–Transmission in a Co2P Solid Hydrogen‐Storage Material

Intracell Hydrogen Adsorption–Transmission in a Co2P Solid Hydrogen‐Storage Material

Catalytic Hydrogen Transfer and Decarbonylation of Aromatic Aldehydes on Ru and Ru Phosphide Model Catalysts

Mechanistic Study of Formic Acid Decomposition over Ru(0001) and Px-Ru(0001): Effects of Phosphorus on C–H and C–O Bond Rupture

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Intracell Hydrogen Adsorption–Transmission in a Co₂P Solid Hydrogen‐Storage Material

Intracell Hydrogen Adsorption–Transmission in a Co₂P Solid Hydrogen‐Storage Material

Mechanistic Study of Formic Acid Decomposition over Ru(0001) and P_x-Ru(0001): Effects of Phosphorus on C–H and C–O Bond Rupture