Water Dissociation in the Presence of Metal Ions

Coskuner, Orkid; Jarvis, Emily; Allison, Thomas C.

doi:10.1002/anie.200701617

Cited by 31 publications

(51 citation statements)

References 31 publications

(28 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Hydrogen is gaining more and more attention because it is regarded as an important future fuel [23,24]. Water is recommended as the ideal source for the generation of hydrogen.…”

Section: Hydrogen Production From Water Splittingmentioning

confidence: 99%

Catalytic Membrane Reactors – Chemical Upgrading and Pollution Control

Czuprat

Jiang

2011

Chemie Ingenieur Technik

View full text Add to dashboard Cite

This article presents an overview on oxygen permeation, oxidative activation of light hydrocarbons and splitting of various molecules (H 2 O, N 2 O, NO x ) containing oxygen in a hollow fiber catalytic membrane reactor made of BaCo x Fe y Zr z O 3-d (BCFZ, x+y+z = 1) which is used to separate oxygen from oxygen containing gases. Innovative reactor concepts are introduced and performances for the various applications are discussed. A detailed view is also given on the thermodynamic and kinetic background with regard to the above mentioned reactions. The potentials in terms of product intensification and energy saving by usage of the BCFZ hollow fibers as reaction vessels are evaluated. However, there are still technological challenges that prevent the described processes from being practiced on commercial scale by now.

show abstract

“…Hydrogen is gaining more and more attention because it is regarded as an important future fuel [23,24]. Water is recommended as the ideal source for the generation of hydrogen.…”

Section: Hydrogen Production From Water Splittingmentioning

confidence: 99%

Catalytic Membrane Reactors – Chemical Upgrading and Pollution Control

Czuprat

Jiang

2011

Chemie Ingenieur Technik

View full text Add to dashboard Cite

show abstract

“…重视, 这使得许多实验研究有困难的问题在理论上却得到了很好的阐释 [7,[18][19][20][21] . 不久前,Neumark研究小组 [19] 利用阴离子光电子谱测得 N1鄄位脱氢胸腺嘧啶的电子亲合势为 3.250 依0.015eV, 这一结果与 Schaefer 理论小组 [22] 早些时候对该体系电子亲合势的理论计算值 (…”

Section: 随着计算方法的不断更新和计算精度的不断提高化学中的理论手段正越来越得到研究人员的unclassified

Molecular Geometries and Electronic Structures of Adducts between 2’-Deoxycytidine-5’-monophosphate Acid and Hydroxyl Radical

Hou¹,

Li²,

Yi³

2009

Acta Physico-Chimica Sinica

View full text Add to dashboard Cite

“…Extensive efforts have been devoted to exploring the self and forced hydrolysis reactions of Al 3+ (aq) in aqueous solution that form various monomeric and polymeric hydrolytic Al species . Unlike the self‐hydrolysis of Al 3+ (aq) in acidic solutions whose detailed reaction steps have been carefully studied using both experimental and theoretical methods, the microscopic reaction kinetics for the forced hydrolysis of Al 3+ (aq) under elevated pH conditions such as base titration is rarely considered, and the role of hydroxyl in the formation mechanisms of the hydrolytic Al species remains poorly understood. This has hindered the precision studies of the hydrolysis‐polymerization mechanisms of Al species.…”

Section: Introductionmentioning

confidence: 99%

Density functional theory studies on the external OH⁻‐induced barrierless proton dissociation mechanism for the forced hydrolysis reaction of Al³⁺(aq)

Dong

Shi

Zhang

et al. 2018

Int J of Quantum Chemistry

View full text Add to dashboard Cite

The forced hydrolysis reaction of aqueous aluminum ion (Al 3+ ) is of critical importance in Al chemistry, but its microscopic mechanism has long been neglected. Herein, density functional calculations reveal an external OH − -induced barrierless proton dissociation mechanism for the forced hydrolysis of Al 3+ (aq). Dynamic reaction pathway modeling results show that the barrierless deprotonations induced by the second-or third-shell external OH − proceed via the concerted proton transfer through H-bond wires connected to the coordinated waters, and the inducing ability of the external OH − decreases with increasing hydration layers between Al(H 2 O) 6 3+ and the external OH − . The OH − -induced forced hydrolysis mechanism of Al 3+ (aq) is quite different from its self-hydrolysis mechanism without OH − . The inducing ability is a unique characteristic of OH − , rather than other anions such as F − or Cl − .aluminium ion, barrierless proton dissociation, density functional theory, forced hydrolysis,The hydrolysis chemistry of aluminum (Al) is central to environmental science, human health and industry activities. [1][2][3] Extensive efforts have been devoted to exploring the self and forced hydrolysis reactions of Al 3+ (aq) in aqueous solution that form various monomeric and polymeric hydrolytic Al species. [4] Unlike the self-hydrolysis of Al 3+ (aq) in acidic solutions whose detailed reaction steps have been carefully studied using both experimental [5,6] and theoretical [7][8][9][10][11] methods, the microscopic reaction kinetics for the forced hydrolysis of Al 3+ (aq) under elevated pH conditions such as base titration is rarely considered, and the role of hydroxyl in the formation mechanisms of the hydrolytic Al species remains poorly understood. This has hindered the precision studies of the hydrolysis-polymerization mechanisms of Al species.Conventionally, the self-hydrolysis of Al 3+ (aq) is viewed as the spontaneous proton removal on Al 3+ inner-shell coordinated waters with the assistance of adjacent solvent water molecules, [12] while the forced hydrolysis of Al 3+ (aq) involves the participation of external OH − . The firstorder forced hydrolysis of Al 3+ (aq), which acts as the first reaction step in forming polymeric hydroxyl Al species upon base titration, is usually expressed as: [13,14] Al 3 + + OH − ! AlðOHÞ 2 +AlðH 2 OÞ 6 3 + + OH − ! AlðOHÞðH 2 OÞ 5 2 + + H 2 O:In aqueous solution, the Al 3+ ion exists mainly in the hydrated form of Al(H 2 O) 6 3+ rather than the naked Al 3+ , thus, Equation (2) is more suitable to describe the reaction in aqueous solution. The reaction may proceed via the pathway that a proton on an Al(H 2 O) 6 3+ inner-shell coordinated water dissociates and moves into OH − , or in other words, the external OH − captures the proton. Herein, this possible reaction pathway is modeled using the density functional theory-quantum chemical cluster model (DFT-CM) method, [15,16] in order to elucidate the molecular mechanism of the forced hydrolysis reaction of Al 3+ (aq) in aqueou...

show abstract

Water Dissociation in the Presence of Metal Ions

Abstract: With or without the metal: Recently, the Grotthuss mechanism of proton transfer in water has been described in detail. A similar mechanism has been found in the vicinity of transition‐metal ions, which leads to the formation of Zundel and Eigen complexes (see picture).

Cited by 31 publications

References 31 publications

Catalytic Membrane Reactors – Chemical Upgrading and Pollution Control

Catalytic Membrane Reactors – Chemical Upgrading and Pollution Control

Molecular Geometries and Electronic Structures of Adducts between 2’-Deoxycytidine-5’-monophosphate Acid and Hydroxyl Radical

Density functional theory studies on the external OH⁻‐induced barrierless proton dissociation mechanism for the forced hydrolysis reaction of Al³⁺(aq)

Contact Info

Product

Resources

About

Water Dissociation in the Presence of Metal Ions

Abstract: With or without the metal: Recently, the Grotthuss mechanism of proton transfer in water has been described in detail. A similar mechanism has been found in the vicinity of transition‐metal ions, which leads to the formation of Zundel and Eigen complexes (see picture).

Cited by 31 publications

References 31 publications

Catalytic Membrane Reactors – Chemical Upgrading and Pollution Control

Catalytic Membrane Reactors – Chemical Upgrading and Pollution Control

Molecular Geometries and Electronic Structures of Adducts between 2’-Deoxycytidine-5’-monophosphate Acid and Hydroxyl Radical

Density functional theory studies on the external OH−‐induced barrierless proton dissociation mechanism for the forced hydrolysis reaction of Al3+(aq)

Contact Info

Product

Resources

About

Density functional theory studies on the external OH⁻‐induced barrierless proton dissociation mechanism for the forced hydrolysis reaction of Al³⁺(aq)