Mechanism of Selective Hydrogenation of α,β-Unsaturated Aldehydes on Silver Catalysts: A Density Functional Study | Sciact - CRIS-system of Boreskov Institute of Catalysis

Mechanism of Selective Hydrogenation of α,β-Unsaturated Aldehydes on Silver Catalysts: A Density Functional Study Full article

Journal

The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455

Output data

Year: 2009, Volume: 113, Number: 30, Pages: 13231-13240 Pages count : 10 DOI: 10.1021/jp902078c

Tags

SUBSURFACE OXYGEN; UNSATURATED ALDEHYDES; METHOXIDE DECOMPOSITION; DISSOCIATIVE ADSORPTION; SINGLE-CRYSTAL; MATERIALS GAP; ACROLEIN; Pt(111); SURFACE; Ag(111)

Authors

Lim Kok Hwa ^1,2 , Mohamed Amjad B. ¹ , Yudanov Ilya V. ^1,3 , Neyman Konstantin M. ^4,5 , Bron Michael ⁶ , Claus Peter ⁶ , Rösch Notker ¹

Affiliations

1	Department Chemie and Catalysis Research Center, Technische Universität München, 85747 Garching, Germany
2	School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637459
3	Boreskov Institute of Catalysis, Russian Academy of Sciences, 630090 Novosibirsk, Russia
4	Institució Catalana de Recerca i Estudis Avançats (ICREA), 08010 Barcelona, SpainDarmstadt, 64287 Darmstadt, Germany
5	Departament de Química Física i Institut de Química Teòrica i Computacional, Universitat de Barcelona, 08028 Barcelona, Spain
6	Ernst-Berl-Institut, Technische Chemie II, Technische Universität

Funding (3)

1	Ministry of Economic Affairs and Digital Transformation	FIS2008-02238
2	German Research Foundation
3	Verband der Chemischen Industrie

Supported silver catalysts exhibit a remarkably high selectivity in the industrially important hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols. We carried out density functional calculations to clarify factors that affect the catalytic function of silver in hydrogenating unsaturated aldehydes. We examined the activity and the selectivity of model silver catalysts for acrolein, the simplest, yet most difficult unsaturated aldehyde to be selectively hydrogenated. We focused on describing bulky catalyst particles, represented by sites on extended silver surfaces, on the regular clean Ag(110) surface and the surface Osub/Ag(111) with subsurface oxygen centers. On Ag(110) our results imply propanal, the undesired saturated aldehyde, to be the main product. In contrast, the calculations suggest a very high selectivity of Osub/Ag(111) for the corresponding unsaturated alcohol, allyl alcohol, although the activity of this system is lower than that of clean silver. At variance with Pt(111), where the selectivity to allyl alcohol is strongly reduced by the hindered desorption of the latter, allyl alcohol and propanal products are predicted to desorb easily from both Ag(110) and Osub/Ag(111) at common reaction temperatures. We also analyzed inherent limitations for an accurate description of the chemical regioselectivity by contemporary computational methods.

Lim K.H. , Mohamed A.B. , Yudanov I.V. , Neyman K.M. , Bron M. , Claus P. , Rösch N.
Mechanism of Selective Hydrogenation of α,β-Unsaturated Aldehydes on Silver Catalysts: A Density Functional Study
The Journal of Physical Chemistry C. 2009. V.113. N30. P.13231-13240. DOI: 10.1021/jp902078c WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Mar 7, 2009
Accepted:	May 26, 2009
Published online:	Jul 7, 2009
Published print:	Jul 30, 2009

Web of science:	WOS:000268233800049
Scopus:	2-s2.0-68349117185
Elibrary:	13614394
Chemical Abstracts:	2009:819712
Chemical Abstracts (print):	151:100750
OpenAlex:	W2031618374

DB	Citing
Web of science	43
Scopus	47
Elibrary	46
OpenAlex	53