Can Cu+-Exchanged Zeolites Store Molecular Hydrogen? An Ab-Initio Periodic Study Compared with Low-Temperature FTIR | Sciact - CRIS-система Института катализа

Can Cu+-Exchanged Zeolites Store Molecular Hydrogen? An Ab-Initio Periodic Study Compared with Low-Temperature FTIR Научная публикация

Журнал

The Journal of Physical Chemistry B
ISSN: 1520-6106 , E-ISSN: 1520-5207

Вых. Данные

Год: 2004, Том: 108, Номер: 24, Страницы: 8278-8286 Страниц : 9 DOI: 10.1021/jp0486651

Ключевые слова

Absorption; Charge transfer; Electronic structure; Fourier transform infrared spectroscopy; Hamiltonians; Hydrogen; Ion exchange; Personal computers; Polarization

Авторы

Solans-Monfort Xavier ¹ , Branchadell Vicenç ¹ , Sodupe Mariona ¹ , Zicovich-Wilson Claudio M. ² , Gribov Evgueny ³ , Spoto Giuseppe ³ , Busco Claudia ³ , Ugliengo Piero ³

Организации

1	Departament de Química, Universitat Autònoma de Barcelona, Bellaterra 08193, Spain, Facultad de Ciencias
2	Universidad Autonoma del Estado de Morelos, Av. Universidad 1001, Col. Chamilpa, 62210 Cuernavaca (Morelos), Mexico
3	Dipartimento di Chimica IFM, Università di Torino, Via P. Giuria, 7, 10125 Torino, Italy

Cu+-exchanged Si/Al 11:1 chabazite has been studied ab initio using the periodic CRYSTAL03 computer code with Hartree−Fock and the hybrid B3LYP Hamiltonians to characterize the structures and energetics of the Cu+ ion sitting preference and its interaction with H2. Two sites (I and IV) have been found to be stable for Cu+ ion: site I, the most stable one, envisaging coordination in a six-membered zeolite ring and site IV in which the Cu+ ion sits in the largest eight-membered ring. Interaction of H2 gives adsorption energies at B3LYP of −13 and −56 kJ/mol for sites I and IV, respectively. The B3LYP bathochromic harmonic H2 frequency shifts are 847 and 957 cm-1 for adsorption at sites I and IV, respectively, in good agreement with the shifts measured (1030 and 1081 cm-1) in the Cu−ZSM-5 system in which Cu+ ion is, respectively, three and bi-coordinated by the oxygen atoms of the zeolite framework. Analysis of the components of the adsorption energy, carried out within the cluster approach, revealed that charge transfer from the Cu(3dπ) orbital through the antibonding H2(σu) and orbital polarization play a significant role in the H2 adsorption energy, and cause the large bathochromic H2 frequency shift.

Solans-Monfort X. , Branchadell V. , Sodupe M. , Zicovich-Wilson C.M. , Gribov E. , Spoto G. , Busco C. , Ugliengo P.
Can Cu+-Exchanged Zeolites Store Molecular Hydrogen? An Ab-Initio Periodic Study Compared with Low-Temperature FTIR
The Journal of Physical Chemistry B. 2004. V.108. N24. P.8278-8286. DOI: 10.1021/jp0486651 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	25 мар. 2004 г.
Опубликована online:	25 мая 2004 г.
Опубликована в печати:	1 июн. 2004 г.

Web of science:	WOS:000221965400028
Scopus:	2-s2.0-3042691610
РИНЦ:	14514268
Chemical Abstracts:	2004:431810
Chemical Abstracts (print):	141:28948
OpenAlex:	W1997080269

БД	Цитирований
Web of science	89
Scopus	89
OpenAlex	94