A Theoretical Study of the Interaction of Ammonia with Silicon Trimer

Ratcliff, Lyn B.; Holme, Thomas A.

doi:10.1021/jp982089p

Cited by 3 publications

(3 citation statements)

References 33 publications

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“…Small silicon-based clusters have attracted continuing attention in part due to their abundant applications in various fields, especially in semiconductor industries and nanomaterial science. From the reactivity point of view, silicon clusters are different from the bulk silicon, as shown in both experimental and theoretical investigations. − Besides, the enhanced reactivity of noble metal clusters such as Au n with O 2 upon doping a silicon atom was reported . Because of their dangling bonds, bare silicon clusters are chemically too active and thus have limited applications.…”

Section: Introductionmentioning

confidence: 99%

Methanol Activation Catalyzed by Small Earth-Alkali Mixed Silicon Clusters Si_m–nM_n with M = Be, Mg, Ca and m = 3–4, n = 0–1

Hang

Nguyen

2016

J. Phys. Chem. C

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The methanol activation pathways occurring on small pure and mixed silicon clusters Si m−n M n with M = Be, Mg, Ca and m = 3−4, n = 0−1 were investigated using quantum chemical computations (density functional theory B3LYP/aug-cc-pVTZ and coupled-cluster theory CCSD(T)/CBS extrapolated from energies with the aug-cc-pVnZ basis sets, n = D, T, Q) to examine their thermodynamic and kinetic feasibilities. In all cases considered, the cleavage of the O−H bond is favored over that of the C−H bond. The O−H bond cleavage in the presence of the singlet Si 3 cluster is thermodynamically less preferred than on mixed Si 2 M clusters, even though it becomes more kinetically favored. Most importantly, the energy barriers for the O−H bond breaking on the singlet Si 3 , Si 2 Ca, and Si 3 Ca clusters are found to be lower than the previously reported results for metal clusters, catalytic metal surfaces, metal oxides, etc. The small mixed Si clusters thus appear to be good catalysts for methanol activation and most probably in other dehydrogenation processes from the X−H bonds of organic compounds. These findings suggest further extensive searches for doped silicon clusters as realistic catalysts that can experimentally be prepared, for methanol activation particularly and dehydrogenation processes generally.

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Section: Introductionmentioning

confidence: 99%

Methanol Activation Catalyzed by Small Earth-Alkali Mixed Silicon Clusters Si_m–nM_n with M = Be, Mg, Ca and m = 3–4, n = 0–1

Hang

Nguyen

2016

J. Phys. Chem. C

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“…The experimental and theoretical modeling of the surface reactions at the atomic−molecular level is particularly helpful in providing better insight into the mechanism of surface reactions, in which reactive intermediates might be involved. The interaction of ammonia with bulk silicon surfaces or silicon clusters has been the subject of many experimental and theoretical studies. − To our knowledge, there have been no reports on the reactions of atomic Si with ammonia molecules.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Atomic Silicon and Germanium with Ammonia: A Matrix-Isolation FTIR and Theoretical Study

Chen

Zheng

et al. 2002

J. Phys. Chem. A

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The reactions of Si atoms with NH3 molecules have been studied using matrix-isolation FTIR spectroscopy and density functional theoretical calculations. Silicon atoms reacted with NH3 to form the SiNH3 complex spontaneously in solid argon upon annealing. Mercury arc photolysis with a 290-nm long-wavelength pass filter destroyed the SiNH3 absorptions and produced HSiNH2 absorptions. Full-arc irradiation (250−580 nm) destroyed the HSiNH2 absorptions and produced SiNH absorptions. The potential energy surface along the reaction path leading to the observed products has also been calculated. Similar experiments with Ge gave spectra for the analogous product molecules.

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“…Of the many possible clusters as catalysts, small silicon-based clusters continues to attract great attention in part owing to their abundant applications in various fields. From the perspective of chemical reactivity, silicon clusters act differently from the bulk silicon, as indicated by both theoretical and experimental studies. − The reactivity of noble clusters such as Au n with O 2 was found to be enhanced upon doping of a silicon atom . Due to their dangling bonds, pure silicon clusters are, however, destabilizing, and hence have limited applications.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Study on Water Splitting Reactions by Small Silicon Clusters Si₃X, X = Si, Be, Mg, Ca

Hang

Nguyen

2018

J. Phys. Chem. A

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Interaction, dissociation, and dehydrogenation reactions of water monomer and dimer with pure and mixed tetrameric silicon clusters SiX with X = Si, Be, Mg, Ca were investigated using high accuracy quantum chemical calculations. While geometries were optimized using the DFT/B3LYP functional with the aug-cc-pVTZ basis set, reaction energy profiles were constructed making use of the coupled-cluster theory with extrapolation to complete basis set, CCSD(T)/CBS. Cleavage of the O-H bond in water dimer is found to be more favored than that of water monomer in the reaction with Si. The water acceptor monomer in water dimer performs as an internal catalyst facilitating H atom transfer to form H. Adsorption of water dimer on SiX clusters mostly takes place upon interaction of the donor water molecule with Si cluster. Water dimer adsorbs more strongly on SiM than on Si. The most stable complexes obtained upon interaction of water dimer with SiM mainly arise from M-O interaction in preference over a Si-O connection. Substitution of a Si atom in Si by an earth alkaline metal induces a substantial reduction of the energy barrier for the (rate-limiting) first O-H bond cleavage of water dimer. The most remarkable achievement upon doping is a disappearance of the overall energy barrier for the initial O-H bond cleavage in water dimer. Of the three binary SiM clusters considered, dehydrogenation of water dimer driven by SiBe is the most kinetically and thermodynamically favorable pathway. In comparison to another cluster such as Al and nanoparticles Ru, energy barriers for water dimer dissociation on SiM are much lower. The mixed clusters SiM turn out to be as efficient alternative reagents for O-H dissociation and hydrogen production from water dimer. This study proposes further searches for other mixed silicon clusters as realistic gas phase reagents for crucial dehydrogenation processes in such a way they can be prepared and conducted in experiment.

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A Theoretical Study of the Interaction of Ammonia with Silicon Trimer

Cited by 3 publications

References 33 publications

Methanol Activation Catalyzed by Small Earth-Alkali Mixed Silicon Clusters Si_m–nM_n with M = Be, Mg, Ca and m = 3–4, n = 0–1

Methanol Activation Catalyzed by Small Earth-Alkali Mixed Silicon Clusters Si_m–nM_n with M = Be, Mg, Ca and m = 3–4, n = 0–1

Reactions of Atomic Silicon and Germanium with Ammonia: A Matrix-Isolation FTIR and Theoretical Study

Mechanistic Study on Water Splitting Reactions by Small Silicon Clusters Si₃X, X = Si, Be, Mg, Ca

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A Theoretical Study of the Interaction of Ammonia with Silicon Trimer

Cited by 3 publications

References 33 publications

Methanol Activation Catalyzed by Small Earth-Alkali Mixed Silicon Clusters Sim–nMn with M = Be, Mg, Ca and m = 3–4, n = 0–1

Methanol Activation Catalyzed by Small Earth-Alkali Mixed Silicon Clusters Sim–nMn with M = Be, Mg, Ca and m = 3–4, n = 0–1

Reactions of Atomic Silicon and Germanium with Ammonia: A Matrix-Isolation FTIR and Theoretical Study

Mechanistic Study on Water Splitting Reactions by Small Silicon Clusters Si3X, X = Si, Be, Mg, Ca

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Methanol Activation Catalyzed by Small Earth-Alkali Mixed Silicon Clusters Si_m–nM_n with M = Be, Mg, Ca and m = 3–4, n = 0–1

Methanol Activation Catalyzed by Small Earth-Alkali Mixed Silicon Clusters Si_m–nM_n with M = Be, Mg, Ca and m = 3–4, n = 0–1

Mechanistic Study on Water Splitting Reactions by Small Silicon Clusters Si₃X, X = Si, Be, Mg, Ca