Dehydrogenation of methanol on Pd(100): comparison with the results of Pd(111)

Jiang, Ruibin; Guo, Wenyue; Li, Ming; Lu, Xiaoqing; Yuan, Jianye; Shan, Honghong

doi:10.1039/b927050g

Cited by 33 publications

(37 citation statements)

References 63 publications

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“…On Rh and Au, the first dehydrogenation of CH 3 OH competitively proceeds through O-H or C-H bond cleavages. These results are consistent with previous theoretical studies [34][35][36][37], which have investigated the reaction pathways for CH 3 OH dehydrogenation.…”

Section: Microkinetic Modelingsupporting

confidence: 95%

Using microkinetic analysis to search for novel anhydrous formaldehyde production catalysts

Lausche

Peterson

et al. 2015

Surface Science

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a b s t r a c tDirect dehydrogenation of methanol to produce anhydrous formaldehyde is investigated using periodic density functional theory (DFT) and combining the microkinetic model to estimate rates and selectivities on stepped (211) surfaces under a desired reaction condition. Binding energies of reaction intermediates and transition state energies for each elementary reaction can be accurately scaled with CHO and OH binding energies as the only descriptors. Based on these two descriptors, a steady-state microkinetic model is constructed with a piecewise adsorbate-adsorbate interaction model that explicitly includes the effects of adsorbate coverage on the rates and selectivities as well as the volcano plots are obtained. Our results show that most of the stepped (211) puremetallic surfaces such as Au, Pt, Pd, Rh, Ru, Ni, Fe, and Co are located in a region of low activity and selectivity toward CH 2 O production due to higher rate for CH 2 O dehydrogenation than CH 2 O desorption. The selectivities toward CH 2 O production on Zn, Cu, and Ag surfaces are located on the boundary between the high and low selectivity regions. To find suitable catalysts for anhydrous CH 2 O production, a large number of A 3 B-type transition metal alloys are screened based on their predicted rates and selectivities, as well as their estimated stabilities and prices. We finally propose several promising candidates for the dehydrogenation of CH 3 OH.Published by Elsevier B.V.

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Section: Microkinetic Modelingsupporting

confidence: 95%

Using microkinetic analysis to search for novel anhydrous formaldehyde production catalysts

Lausche

Peterson

et al. 2015

Surface Science

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“…3f), the carbon atom exhibited a three-fold site with the oxygen atom located directly above it, which was in agreement with previous results [53,62]. Three CePt bond lengths were much shorter than 2.120 Å on Pd(111) [57]. The calculated value of CeOeH angle was 111.4 .…”

Section: Hydroxymethylidyne (Coh)supporting

confidence: 90%

“…The scission of CeH bond in TS4 was accompanied by a rotation of the CeO axis to a position almost perpendicular to the PtPd 3 (111) surface. The CeO bond was shortened from 1.206 Å in the formyl (IS4) to 1.159 Å in TS4, which was almost similar to the product CO (1.198 Å ) [57]. The CeH bond was elongated from 1.112 Å in IS4 to 1.501 Å in TS4, and finally to 3.271 Å in the adsorption complex (FS4), indicating the formation of the final product CO*.…”

Section: Reaction Pathways Of Methanol Dehydrogenationmentioning

confidence: 96%

“…7), COH strongly adsorbed at the fcc site with H atom pointing to an upper tilt. Since H atom was far away from the surface, COH would dehydrogenate with a higher energy barrier of 1.312 eV [57], indicating this dehydrogenation step was much more difficult to occur, compared with CHO / CO þ H (energy barrier: 0.813 eV). The corresponding back energy barrier was 1.816 eV, suggesting that this pathway was exothermic.…”

Section: Reaction Pathways Of Methanol Dehydrogenationmentioning

confidence: 99%

“…3d) with the adsorption energy of 0.333 eV ( Table 2). This adsorption mode was generally accepted as the stable configuration [57,58], in which the carbon located on top of Pt atom and the oxygen situated over adjacent Pt atom. The closed-shell electronic configuration of CH 2 O resulted in a weak interaction with PtPd 3 (111) [27,59].…”

Section: Formaldehyde (Ch 2 O)mentioning

confidence: 99%

See 2 more Smart Citations

A density functional theory study of methanol dehydrogenation on the PtPd 3 (111) surface

Wang

Chen

2015

International Journal of Hydrogen Energy

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Comparative DFT study of methanol decomposition on Mo2C(001) and Mo2C(101) surfaces

Shi

2023

J Mol Model

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In this study, the complete reaction mechanism of methanol decomposition on metallic Mo 2 C(001) and Mo/C-mixed Mo 2 C(101) hexagonal Mo 2 C crystalline phases was systematically investigated using planewave-based periodic density functional theory (DFT). The main reaction route for Mo 2 C(001) is as follows: CH 3 OH → CH 3 O + H → CH 2 O + 2H → CHO + 3H → CO + 4H → C + O + 4H. Hence, C,O, and H are the main products. It was found that the energy barrier for CO dissociation was low. Therefore, it was concluded that the Mo 2 C(001) surface was too active to be easily oxidized or carburized. The optimal reaction pathway for Mo 2 C(101) is as follows:Therefore, CH 4 is the major product. The hydrogenation of CH 3 leading to CH 4 showed the highest energy barrier and the lowest rate constant and should be the rate-determining step. In addition, the formation of CO + 2H 2 was competitive on Mo 2 C(101), and the optimal path was CH 3 OH →The computed energy barrier and rate constant indicate that the rate-determining step is the last step in CO formation. In agreement with the experimental observations, the results provide insights into the Mo 2 C-catalyzed decomposition of methanol and other side reactions.suitable dehydrogenation pathway was CH 3 OH → CH 2 OH → CH 2 O → CHO → CO. On Pd(100), it was found that the dissociation of C-H is easier in the cases of CH 3 OH and CH 2 OH, and the cleavage of O-H is more favorable for CHOH. 10 It was concluded that the predominant pathway is CH 3 OH → CH 3 O → CH 2 O → CHO → CO on Rh(100) and Rh(110). 11 Recently, bimetallic catalysts, such as CuPd, 25,26 PtNi, [27][28][29] and RuPt, 30,31 have also been used in the reactions of methanol. Damte et al. 30 studied the decomposition of methanol on a Ru-Pt/boron-doped graphene surface and found that the lowest energy pathway was CH 3 OH → CH 3 O → CH 2 O → CHO → CO; they concluded that the initial O-H dissociation of methanol was more favorable than its desorption at 0.95 eV.Recently, carbides, especially molybdenum carbide, have attracted immense research attention as a new type of catalytic material. Molybdenum carbide is widely used in reactions involving hydrogen, such as MSR [32][33][34][35] and MD, 36-39 hydrodeoxygenation (HDO), [40][41][42] and hydrodesulfurization (HDS). [43][44][45] This is due to its noble metal properties, such as its strong ability to dissociate and absorb hydrogen, high stability, low price, and good catalytic performance. Koós et al. 32 explored MSR and MD on a K-promoted Mo 2 C/C catalyst exhibiting high thermal stability and found that the selectivity of H 2 reached 97-98% at 723 K. The results of Ma et al. 33 revealed that Ni-modi ed Mo 2 C showed high stability and catalytic activity for MSR. Széchenyi et al. 39 studied the decomposition of methanol and ethanol on unsupported Mo 2 C catalysts and found that an important feature of Mo 2 C catalysts is their high thermal stability at 573-723 K, and the main product of MD was H 2 , along with a small amount of CH 4 . The conversion of methanol reac...

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Dehydrogenation of methanol on Pd(100): comparison with the results of Pd(111)

Cited by 33 publications

References 63 publications

Using microkinetic analysis to search for novel anhydrous formaldehyde production catalysts

Using microkinetic analysis to search for novel anhydrous formaldehyde production catalysts

A density functional theory study of methanol dehydrogenation on the PtPd 3 (111) surface

Comparative DFT study of methanol decomposition on Mo2C(001) and Mo2C(101) surfaces

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