Why do zeolites induce an unprecedented electronic state on exchanged metal ions?
Literature Information
Takahiro Ohkubo, Takashi Yumura, Hisayoshi Kobayashi, Yasushige Kuroda
Understanding the exact position and the detailed role of the Al array in zeolites is essential for elucidating the origin of unique properties that can be derived from the metal-ion exchanged in zeolite samples and for designing zeolite materials with high efficiency in catalytic and adsorption processes. In this work, we investigate, for the first time, the important role of the Al array in the reactivity observed on the metal-ion exchanged in zeolites on the basis of the calculation method by utilizing the spontaneous heterolytic cleavage of H2 observed experimentally on the Zn2+-ion exchanged in MFI-type zeolites (Zn2+-MFI) as the model reaction. In the case of calculation, two main types of models for considering the Al positions in MFI-type zeolites were adopted: in the first type, the Al atoms with appropriate distances are aligned in the circumferential direction of the straight channel (abbreviated as a circumferentially arrayed Al–Al site); in the second type, the nearest neighbouring Al atoms with appropriate distances are directed toward the straight channel axis (abbreviated as a channel directionally arrayed Al–Al site). Results indicated that the Al-array direction governs the reactivity of Zn2+-MFI. The former type of array well explains the experimental fact that spontaneous and irreversible heterolysis of H2 takes place on Zn2+-MFI, even at room temperature, whereas the latter type of array is less reactive; high activation energy is required for the heterolytic cleavage of H2 (ca. >70 kJ mol−1). A detailed analysis of the geometric and electronic structures of a series of Zn2+-MFI models with various Al-array directions clarified the following facts: the circumferentially arrayed Al–Al site induces an inevitable environment around the Zn2+ site, with the simultaneous existence of both a Lewis acid point (coordinatively unsaturated and distorted Zn2+) and a Lewis base point (the lattice oxygen atom juxtaposed with exchanged Zn2+, which participates in the activation of H2: OjL). It is the circumferentially arrayed Al–Al atoms that confer acidic and basic nature on the metal ion and the lattice oxygen atom (OjL), and ultimately trigger the heterolytic dissociation of H2, even at 300 K.
Related Literature
The role of solvation models on the computed absorption and emission spectra: the case of fireflies oxyluciferin
Cristina García-Iriepa, Madjid Zemmouche, Isabelle Navizet
DOI: 10.1039/C8CP07352J
Using nanotubes to study the phonon spectrum of two-dimensional materials
Jesús Carrete, Vu Ngoc Tuoc, Georg K. H. Madsen
DOI: 10.1039/C9CP00052F
Thousand-atom ab initio calculations of excited states at organic/organic interfaces: toward first-principles investigations of charge photogeneration
Takatoshi Fujita, Md. Khorshed Alam, Takeo Hoshi
DOI: 10.1039/C8CP05574B
Liquid–liquid phase separation and evaporation of a laser-trapped organic–organic airborne droplet using temporal spatial-resolved Raman spectroscopy
Aimable Kalume, Chuji Wang, Joshua Santarpia, Yong-Le Pan
DOI: 10.1039/C8CP02372G
Infrared spectroscopic characterization of phosphate binding at the goethite–water interface
Stella Gypser, Peter Leinweber, Dirk Freese
DOI: 10.1039/C8CP07168C
An ab initio study of sensing applications of MoB2 monolayer: a potential gas sensor
Amreen Bano, Jyoti Krishna, Devendra K. Pandey, N. K. Gaur
DOI: 10.1039/C8CP07038E
Infrared photodissociation spectroscopy of cold cationic trimethylamine complexes
Xiangtao Kong, Zhi Zhao, Dongxu Dai, Xueming Yang, Ling Jiang
DOI: 10.1039/C8CP03672A
Three-dimensional pulsed field gradient NMR measurements of self-diffusion in anisotropic materials for energy storage applications
L. E. Marbella, N. M. Trease, M. De Volder, C. P. Grey
DOI: 10.1039/C8CP07776B
Vertical vs. adiabatic ionization energies in solution and gas-phase: probing ionization-induced reorganization in conformationally-mobile bichromophoric actuators using photoelectron spectroscopy, electrochemistry and theory
Maxim V. Ivanov, Denan Wang, Depeng Zhang, Rajendra Rathore, Scott A. Reid
DOI: 10.1039/C8CP02936A
Molecular and dissociative O2 adsorption on the Cu2O(111) surface
Xiaohu Yu, Caibin Zhao, Tianlei Zhang, Zhong Liu
DOI: 10.1039/C8CP03035A
You might also like
Is 6-(3-Fluorophenyl)picolinic acid (CAS: 887982-40-3) safe?
6-(3-Fluorophenyl)picolinic acid is generally considered safe for laboratory use...
What industries use (3R)-3-Pyrrolidinol (CAS: 2799-21-5)?
(3R)-3-Pyrrolidinol is used in the pharmaceutical industry as a precursor for dr...
What precautions should be taken when handling (4R,5R)-4,5-Diethoxycarbonyl-2,2-dimethyldioxolane (CAS: 59779-75-8)?
When handling (4R,5R)-4,5-Diethoxycarbonyl-2,2-dimethyldioxolane (CAS: 59779-75-...
How is 1-(6-Chloroimidazo[1,2-b]pyridazin-3-yl)ethanone (CAS: 90734-71-7) typically synthesized?
1-(6-Chloroimidazo[1,2-b]pyridazin-3-yl)ethanone is often synthesized via a mult...
What is the market or research trend for N-Ethyl-3,4-dimethylbenzylamine (CAS: 39180-83-1)?
The market for N-Ethyl-3,4-dimethylbenzylamine (CAS: 39180-83-1) remains steady,...
What is Tert-butyl 3-(pyrrolidin-1-yl)azetidine-1-carboxylate (CAS: 1019008-21-9)?
Tert-butyl 3-(pyrrolidin-1-yl)azetidine-1-carboxylate is a chemical compound wit...
What regulatory guidelines apply to 1-Bromo-3-chloro-2,4-dimethoxybenzene (CAS: 1228956-93-1)?
1-Bromo-3-chloro-2,4-dimethoxybenzene (CAS: 1228956-93-1) falls under the classi...
Is 8-Bromo-2-methyl-3,4-dihydroisoquinolin-1(2H)-one (CAS: 1368622-07-4) safe?
The safety of 8-Bromo-2-methyl-3,4-dihydroisoquinolin-1(2H)-one (CAS: 1368622-07...
Is Benzyl [(3S)-2,6-dioxo-3-piperidinyl]carbamate (CAS: 22785-43-9) safe?
Benzyl [(3S)-2,6-dioxo-3-piperidinyl]carbamate is generally safe when handled wi...
How should 1-{[4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]sulfonyl}pyrrolidine (CAS: 928657-21-0) be stored?
1-{[4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]sulfonyl}pyrrolidine s...
Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










![(2E)-4-[(1R,2S,8R,19S,21R)-14-Hydroxy-11-isopropenyl-8,23,23-trimethyl-5-(3-methyl-2-buten-1-yl)-16,20-dioxo-3,7,22-trioxaheptacyclo[17.4.1.1~8,12~.0~2,17~.0~2,21~.0~4,15~.0~6,13~]pentacosa-4(15),5,13
,17-tetraen-21-yl]-2-methyl-2-butenoic acid structure (2E)-4-[(1R,2S,8R,19S,21R)-14-Hydroxy-11-isopropenyl-8,23,23-trimethyl-5-(3-methyl-2-buten-1-yl)-16,20-dioxo-3,7,22-trioxaheptacyclo[17.4.1.1~8,12~.0~2,17~.0~2,21~.0~4,15~.0~6,13~]pentacosa-4(15),5,13
,17-tetraen-21-yl]-2-methyl-2-butenoic acid structure](https://static.chemtradehub.com/structs/173/173867-04-4-d2d3.webp)



