<i>Ab initio</i>density-functional theory study of<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mi mathvariant="normal">N</mml:mi><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math>dehydrogenation and reverse reactions on the Rh(111) surface

Popa, Cristina; Offermans, WK Willy; Santen, van Ra Rutger; Jansen, Apj Tonek

doi:10.1103/physrevb.74.155428

Cited by 41 publications

(20 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…NH 3 decomposition over Ir(1 0 0),22 Ir(1 1 0),23 Pt(1 1 1)24 and Rh(1 1 1)19, 20 have been theoretically investigated base on DFT calculations, and several points can be drawn by comparing these systems with Ir(1 1 1). For the direct decomposition of NH x ( x =1–3), reactions start with NH 3 at a top site on Ir(1 0 0), Ir(1 1 0), Rh(1 1 1),19 and Pt(1 1 1) surfaces, similar to our work on Ir(1 1 1). This can be ascribed to the interaction of the non‐bonding lone pair of NH 3 with one of the substrate metal atoms.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Mechanistic Insight into Catalytic Oxidation of Ammonia on Clean, O‐ and OH‐Assisted Ir(1 1 1) Surfaces

Deng

Chau

et al. 2013

ChemCatChem

View full text Add to dashboard Cite

Periodic DFT calculations have been performed to systematically investigate the catalytic mechanisms of ammonia (NH3) decomposition on clean, O‐ and OH‐assisted Ir(1 1 1) surfaces. The adsorption configurations, reaction energies and barriers, and elementary steps were elaborated. Our results show that the NHx (x=1–3) decomposition prefers to proceed by means of the O‐ and OH‐assisted reaction mechanisms, NH3+O→NH2+OH, NH2+OH→NH+H2O, and NH+OH→N+H2O, rather than the direct NHx decomposition of NH3→NH2→NH→N as a result of the high energy barriers involved. The promotion effect of the O‐ and OH‐oxidizing agents are then discussed using energy barrier analysis. The relationships between the selectivity toward the final product and coverage, O to N coverage, and reaction temperature are elucidated. Finally, we compare our results with analogous investigations of NH3 decomposition on Pt, Rh, and Ir surfaces.

show abstract

Section: Resultsmentioning

confidence: 99%

“…DFT investigations have been successfully applied to reveal the microscopic catalytic oxidation mechanism of amines with clean d ‐band metals, such as Rh,19, 20 Ir,21–23 Pt,6, 24–26 Au,27, 28 Co,29, 30 and Cu 31. Offermans et al.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insight into Catalytic Oxidation of Ammonia on Clean, O‐ and OH‐Assisted Ir(1 1 1) Surfaces

Deng

Chau

et al. 2013

ChemCatChem

View full text Add to dashboard Cite

show abstract

“…[2][3][4] It has a high hydrogen content (17.7 wt%), so NH 3 provides a promising mode for the transfer and storage of hydrogen for its on-site generation. [5][6][7] In recent years, the catalytic dehydrogenation of ammonia on metals, [8][9][10][11][12][13][14] alloys, 15 and metal oxides 16,17 has been an object of the most extensive investigation. Thus, the decomposition of ammonia became of great importance for the industry and economy.…”

Section: Introductionmentioning

confidence: 99%

Computational investigation of NH₃adsorption and dehydrogenation on a W-modified Fe(111) surface

Hsiao

Liu

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Hydrogen gas will play an important role in the future since it could be a replacement for gasoline, heating oil, natural gas, and other fuels. In previous reports ammonia (NH3), which has a high hydrogen content, provides a promising mode for the transferring and storing of hydrogen for its on-site generation. Therefore, the dehydrogenation of NH3 on a metal surface has been studied widely in the last few decades. In our study, we employed monolayer tungsten metal to modify the Fe(111) surface, denoted as W@Fe(111), and calculated the adsorption and dehydrogenation behaviors of NH3 on W@Fe(111) surface via first-principles calculations based on density functional theory (DFT). The three adsorption sites of the surface, top (T), 3-fold-shallow (S), and 3-fold-deep (D) were considered. The most stable structure of the NHx (x = 0-3) species on the surface of W@Fe(111) have been predicted. The calculated activation energies for NHx (x = 1-3) dehydrogenations are 19.29 kcal mol(-1) (for H2N-H bond activation), 29.17 kcal mol(-1) (for HN-H bond activation) and 27.94 kcal mol(-1) (for N-H bond activation), and the entire process is exothermic by 33.05 kcal mol(-1). To gain detailed knowledge of the catalytic processes of the NH3 molecule on the W@Fe(111) surface, the physical insights between the adsorbate/substrate interaction and interface morphology were subjected to a detailed electronic analysis.

show abstract

“…18 Many reports describe the decomposition and oxidation of NH 3 . [19][20][21][22][23][24][25] In addition, the reduction of N 2 to yield NH 3 (so-called "nitrogen fixation") is one of most important topics in chemistry and biology. [26][27][28] In biological systems, N 2 fixation is mediated under ambient conditions by the enzyme nitrogenase.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Theory Study of NH_x (x = 0−3) and N₂ Adsorption on IrO₂(110) Surfaces

2010

View full text Add to dashboard Cite

The oxidation of ammonia (NH 3 ) and the reduction of nitrogen (N 2 ) are two important processes in chemistry. In this study, we used density functional theory calculations to investigate the adsorptions of NH x (x ) 0-3) and N 2 on IrO 2 (110) surfaces, with density of states (DOS) analysis providing information relating to bond character and state interactions. These adsorbates have higher binding energies on the IrO 2 (110) surface than on the RuO 2 (110) surface because the former forms stronger σ bonds with the adsorbed molecules. The surface adsorptions of NH 2 and NH on the IrO 2 (110) surface proceed with similar binding energies and similar hybridizations of the nitrogen atoms. In addition, the orientations of NH 2 and NH adsorbed on the IrO 2 (110) surface are governed by lateral interactions with surface oxygen atoms (O cus or O br ), rather than by hydrogen bonding. We calculated the binding energy for the adsorption of N 2 on the IrO 2 (110) surface to be 1.10 eV. The weakening of the NtN triple bond was evident from our DOS results; strong bonding forces, including σ-and π-type interactions, exist between the N 2 molecule and the surface, suggesting that N 2 molecules are moderately activated by IrO 2 (110) surfaces.

show abstract

Ab initiodensity-functional theory study ofNHxdehydrogenation and reverse reactions on the Rh(111) surface

Cited by 41 publications

References 42 publications

Mechanistic Insight into Catalytic Oxidation of Ammonia on Clean, O‐ and OH‐Assisted Ir(1 1 1) Surfaces

Mechanistic Insight into Catalytic Oxidation of Ammonia on Clean, O‐ and OH‐Assisted Ir(1 1 1) Surfaces

Computational investigation of NH₃adsorption and dehydrogenation on a W-modified Fe(111) surface

Density Functional Theory Study of NH_x (x = 0−3) and N₂ Adsorption on IrO₂(110) Surfaces

Contact Info

Product

Resources

About

Ab initiodensity-functional theory study ofNHxdehydrogenation and reverse reactions on the Rh(111) surface

Cited by 41 publications

References 42 publications

Mechanistic Insight into Catalytic Oxidation of Ammonia on Clean, O‐ and OH‐Assisted Ir(1 1 1) Surfaces

Mechanistic Insight into Catalytic Oxidation of Ammonia on Clean, O‐ and OH‐Assisted Ir(1 1 1) Surfaces

Computational investigation of NH3adsorption and dehydrogenation on a W-modified Fe(111) surface

Density Functional Theory Study of NHx (x = 0−3) and N2 Adsorption on IrO2(110) Surfaces

Contact Info

Product

Resources

About

Computational investigation of NH₃adsorption and dehydrogenation on a W-modified Fe(111) surface

Density Functional Theory Study of NH_x (x = 0−3) and N₂ Adsorption on IrO₂(110) Surfaces