Adsorption and Subsequent Reaction of a Water Molecule on Silicate and Silica Cluster Anions

Masashi Arakawa; Tsubasa Omoda; Akira Terasaki

doi:10.1021/acs.jpcc.6b11689

Adsorption and Subsequent Reaction of a Water Molecule on Silicate and Silica Cluster Anions

Masashi Arakawa, Tsubasa Omoda, Akira Terasaki

Physical Chemistry

Research output: Contribution to journal › Article › peer-review

5 Citations (Scopus)

Abstract

We present reactions of size-selected free silicate, Mg_lSiO_m^-, and silica, Si_nO_m^-, cluster anions with a H₂O molecule focusing on H₂O adsorption. It was found that H₂O adsorption to Mg_lSiO_m^- with l = 2 and 3 (m = 4-6) is always followed by molecular oxygen release, whereas reactivity of the clusters with l = 1 (m = 3-5) was found to be much lower. On the contrary, in the reaction of Si_nO_m^- (n = 3-8, 2n - 1 ≤ m ≤ 2n + 2), a H₂O adduct is observed as a major reaction product. Larger and oxygen-rich clusters tend to exhibit higher reactivity; the rate constants of the adsorption reaction are 2 orders of magnitude larger than those of CO adsorption previously reported. DFT calculations revealed that H₂O is dissociatively adsorbed on Si_nO_m^- to form two SiO₃(OH) tetrahedra. The site selectivity of H₂O adsorption is governed by the location of the singly occupied molecular orbital (SOMO) on Si_nO_m^-. The present findings give molecular-level insights into H₂O adsorption on silica and silicate species in the interstellar environment.

Original language	English
Pages (from-to)	10790-10795
Number of pages	6
Journal	Journal of Physical Chemistry C
Volume	121
Issue number	20
DOIs	https://doi.org/10.1021/acs.jpcc.6b11689
Publication status	Published - May 25 2017

All Science Journal Classification (ASJC) codes

Electronic, Optical and Magnetic Materials
Energy(all)
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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@article{64b4ea25c44345aa9cd5933d80c66b2b,

title = "Adsorption and Subsequent Reaction of a Water Molecule on Silicate and Silica Cluster Anions",

abstract = "We present reactions of size-selected free silicate, MglSiOm-, and silica, SinOm-, cluster anions with a H2O molecule focusing on H2O adsorption. It was found that H2O adsorption to MglSiOm- with l = 2 and 3 (m = 4-6) is always followed by molecular oxygen release, whereas reactivity of the clusters with l = 1 (m = 3-5) was found to be much lower. On the contrary, in the reaction of SinOm- (n = 3-8, 2n - 1 ≤ m ≤ 2n + 2), a H2O adduct is observed as a major reaction product. Larger and oxygen-rich clusters tend to exhibit higher reactivity; the rate constants of the adsorption reaction are 2 orders of magnitude larger than those of CO adsorption previously reported. DFT calculations revealed that H2O is dissociatively adsorbed on SinOm- to form two SiO3(OH) tetrahedra. The site selectivity of H2O adsorption is governed by the location of the singly occupied molecular orbital (SOMO) on SinOm-. The present findings give molecular-level insights into H2O adsorption on silica and silicate species in the interstellar environment.",

author = "Masashi Arakawa and Tsubasa Omoda and Akira Terasaki",

note = "Funding Information: The present study was supported by Grants-in-Aid for Scientific Research on Innovative Areas (26108510 and 16H00938) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Grant-in-Aid for Young Scientists (B) (26870431) from the Japan Society for Promotion of Science (JSPS), and Kurita Water and Environment Foundation (14D047). The computations were mainly performed using a computing system at the Research Institute for Information Technology, Kyushu University.",

year = "2017",

month = may,

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doi = "10.1021/acs.jpcc.6b11689",

language = "English",

volume = "121",

pages = "10790--10795",

journal = "Journal of Physical Chemistry C",

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publisher = "American Chemical Society",

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T1 - Adsorption and Subsequent Reaction of a Water Molecule on Silicate and Silica Cluster Anions

AU - Arakawa, Masashi

AU - Omoda, Tsubasa

AU - Terasaki, Akira

N1 - Funding Information: The present study was supported by Grants-in-Aid for Scientific Research on Innovative Areas (26108510 and 16H00938) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Grant-in-Aid for Young Scientists (B) (26870431) from the Japan Society for Promotion of Science (JSPS), and Kurita Water and Environment Foundation (14D047). The computations were mainly performed using a computing system at the Research Institute for Information Technology, Kyushu University.

PY - 2017/5/25

Y1 - 2017/5/25

N2 - We present reactions of size-selected free silicate, MglSiOm-, and silica, SinOm-, cluster anions with a H2O molecule focusing on H2O adsorption. It was found that H2O adsorption to MglSiOm- with l = 2 and 3 (m = 4-6) is always followed by molecular oxygen release, whereas reactivity of the clusters with l = 1 (m = 3-5) was found to be much lower. On the contrary, in the reaction of SinOm- (n = 3-8, 2n - 1 ≤ m ≤ 2n + 2), a H2O adduct is observed as a major reaction product. Larger and oxygen-rich clusters tend to exhibit higher reactivity; the rate constants of the adsorption reaction are 2 orders of magnitude larger than those of CO adsorption previously reported. DFT calculations revealed that H2O is dissociatively adsorbed on SinOm- to form two SiO3(OH) tetrahedra. The site selectivity of H2O adsorption is governed by the location of the singly occupied molecular orbital (SOMO) on SinOm-. The present findings give molecular-level insights into H2O adsorption on silica and silicate species in the interstellar environment.

AB - We present reactions of size-selected free silicate, MglSiOm-, and silica, SinOm-, cluster anions with a H2O molecule focusing on H2O adsorption. It was found that H2O adsorption to MglSiOm- with l = 2 and 3 (m = 4-6) is always followed by molecular oxygen release, whereas reactivity of the clusters with l = 1 (m = 3-5) was found to be much lower. On the contrary, in the reaction of SinOm- (n = 3-8, 2n - 1 ≤ m ≤ 2n + 2), a H2O adduct is observed as a major reaction product. Larger and oxygen-rich clusters tend to exhibit higher reactivity; the rate constants of the adsorption reaction are 2 orders of magnitude larger than those of CO adsorption previously reported. DFT calculations revealed that H2O is dissociatively adsorbed on SinOm- to form two SiO3(OH) tetrahedra. The site selectivity of H2O adsorption is governed by the location of the singly occupied molecular orbital (SOMO) on SinOm-. The present findings give molecular-level insights into H2O adsorption on silica and silicate species in the interstellar environment.

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