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Title: pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions: pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions

Abstract

Previously, Keggin phosphotungstate heteropolyanions (HPA), PW 12O 40 3–, are known to interact via short-range attraction and long-range repulsion (SALR) at moderate and high solution concentrations and low-pH (pH = 1). These interactions were identified through the observation of structure factor peaks in small-angle X-ray scattering (SAXS) data reported previously (J. Phys. Chem. C 2016, 120, 1317). Here we describe the interactions between the same heteropolyanions with extremely low concentrations at low (pH = 0) and high pH (pH = 4.7) conditions. The solution chemistry of Keggin heteropolyanions at these two pH values offers a unique way to change the charge of the cluster anions without changing the structure (from the perspective of SAXS) and, at the same time, changing the hydrogen bonding interactions. The structure factors obtained from concentration dependent SAXS data reveal that the change in pH changes the nature of SALR interactions, consistent with the presence of the plenary PW 12O 40 3– anion at pH = 0 and the monovacant lacunary PW 11O 39 7– anion at pH = 4.7. At the low pH condition, the attractive interactions dominate to provide a peak near Q = 0 Å –1 momentum transfer in the structure factors, whereasmore » at pH = 4.7 the repulsive interactions dominate, thereby eliminating the peak near Q = 0 Å –1. The experimental findings presented here are in agreement with the recent liquid state theory and computer simulation predictions on SALR interactions.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1494561
Alternate Identifier(s):
OSTI ID: 1488961
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2019; Journal Issue: 3-4; Journal ID: ISSN 1434-1948
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
Baxter model; Guinier analysis; Polyoxometalate; SALR, short-range attraction long-range repulsion; SAXS, small-angle X-ray scattering

Citation Formats

Antonio, Mark R., and Bera, Mrinal K. pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions: pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions. United States: N. p., 2018. Web. doi:10.1002/ejic.201801165.
Antonio, Mark R., & Bera, Mrinal K. pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions: pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions. United States. doi:10.1002/ejic.201801165.
Antonio, Mark R., and Bera, Mrinal K. Sun . "pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions: pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions". United States. doi:10.1002/ejic.201801165. https://www.osti.gov/servlets/purl/1494561.
@article{osti_1494561,
title = {pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions: pH-Dependent Interactions between Keggin Heteropolyanions in Dilute Solutions},
author = {Antonio, Mark R. and Bera, Mrinal K.},
abstractNote = {Previously, Keggin phosphotungstate heteropolyanions (HPA), PW12O403–, are known to interact via short-range attraction and long-range repulsion (SALR) at moderate and high solution concentrations and low-pH (pH = 1). These interactions were identified through the observation of structure factor peaks in small-angle X-ray scattering (SAXS) data reported previously (J. Phys. Chem. C 2016, 120, 1317). Here we describe the interactions between the same heteropolyanions with extremely low concentrations at low (pH = 0) and high pH (pH = 4.7) conditions. The solution chemistry of Keggin heteropolyanions at these two pH values offers a unique way to change the charge of the cluster anions without changing the structure (from the perspective of SAXS) and, at the same time, changing the hydrogen bonding interactions. The structure factors obtained from concentration dependent SAXS data reveal that the change in pH changes the nature of SALR interactions, consistent with the presence of the plenary PW12O403– anion at pH = 0 and the monovacant lacunary PW11O397– anion at pH = 4.7. At the low pH condition, the attractive interactions dominate to provide a peak near Q = 0 Å–1 momentum transfer in the structure factors, whereas at pH = 4.7 the repulsive interactions dominate, thereby eliminating the peak near Q = 0 Å–1. The experimental findings presented here are in agreement with the recent liquid state theory and computer simulation predictions on SALR interactions.},
doi = {10.1002/ejic.201801165},
journal = {European Journal of Inorganic Chemistry},
number = 3-4,
volume = 2019,
place = {United States},
year = {2018},
month = {12}
}

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