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

Antonio, Mark R.; Bera, Mrinal K.

doi:10.1002/ejic.201801165

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

Abstract

Keggin phosphotungstate heteropolyanions (HPA), PW ₁₂ O 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 provides 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 ₁₂ O ₄₀ ³⁻ anion at pH = 0 and the monovacant lacunary PW ₁₁ O 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 momentummore »« less

Authors:

^[1];

^[2]

Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Chicago, IL (United States)

Publication Date:: Sun Dec 09 00:00:00 EST 2018

Research Org.:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); 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:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 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.

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                    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.  https://doi.org/10.1002/ejic.201801165

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                    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.  https://doi.org/10.1002/ejic.201801165.  https://www.osti.gov/servlets/purl/1494561.

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@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 = {Keggin phosphotungstate heteropolyanions (HPA), PW 12 O 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 provides 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 12 O 40 3− anion at pH = 0 and the monovacant lacunary PW 11 O 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, whereas at pH = 4.7 the repulsive interactions dominate, thereby eliminating the peak near Q = 0 Å −1 . The experimental results 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         = {Sun Dec 09 00:00:00 EST 2018},

  month        = {Sun Dec 09 00:00:00 EST 2018}

}

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

Abstract

Citation Formats

Cluster formation in fluids with competing short-range and long-range interactions journal, March 2014

An analytic structure factor for macroion solutions journal, January 1981

In situ measurement of the Preyssler polyoxometalate morphology upon electrochemical reduction: A redox system with Born electrostatic ion solvation behavior journal, February 2009

Are Keggin’s POMs Charged Nanocolloids or Multicharged Anions? journal, January 2018

Ramanspektroskopische und Ultrazentrifugen-Messungen zur Untersuchung der Hydrolyse der Dodekawolframatophosphors�ure journal, September 1977

Joint use of small-angle X-ray and neutron scattering to study biological macromolecules in solution journal, April 2006

Polyoxometalates in the Hofmeister series journal, January 2018

Crystallization of Keggin Heteropolyanions via a Two-Step Process in Aqueous Solutions journal, June 2016

Sectroscopic study of stability and molecular species of 12-tungstophosphoric acid in aqueous solution journal, October 2008

Intermediate range order and structure in colloidal dispersions with competing interactions journal, October 2013

The Chaotropic Effect as an Assembly Motif in Chemistry journal, September 2018

SASfit : a tool for small-angle scattering data analysis using a library of analytical expressions journal, September 2015

Aggregation of Heteropolyanions in Aqueous Solutions Exhibiting Short-Range Attractions and Long-Range Repulsions journal, December 2015

The stability of 12-molybdosilicic, 12-tungstosilicic, 12-molybdophosphoric and 12-tungstophosphoric acids in aqueous solution at various pH journal, March 1995

pH-controlled hydrogen-bonding (Short Communication) journal, December 1974

Small-angle scattering studies of biological macromolecules in solution journal, September 2003

Nanometer-Size Polyoxometalate Anions Adsorb Strongly on Neutral Soft Surfaces journal, August 2015

Acidity Measurements on a Heteropolyacid Hydrate in Acetic Acid Solution: A Case of Three Hydrons Ionizing Independently, Rather Than Consecutively journal, March 1995

Ion aggregation in concentrated aqueous and methanol solutions of polyoxometallates Keggin anions: the effect of counterions investigated by molecular dynamics simulations journal, January 2008

Spectroscopic identification of molecular species of 12-tungstophosphoric acid in methanol/water solutions journal, March 2012

Structural aspects of heteropolyacid microemulsions journal, January 2014

Dodecatungstophosphoric acid hexahydrate, (H5O2+)3(PW12O403−). The true structure of Keggin's `pentahydrate' from single-crystal X-ray and neutron diffraction data journal, April 1977

Stability investigation of some heteropolyoxotungstate and heteropolyoxomolybdate salts in buffer solutions journal, October 2012

Small-angle scattering. Information content and error analysis journal, April 1980

Polyoxometalates in the Hofmeister series text, January 2018

Cluster formation in fluids with competing short-range and long-range interactions
journal, March 2014

An analytic structure factor for macroion solutions
journal, January 1981

In situ measurement of the Preyssler polyoxometalate morphology upon electrochemical reduction: A redox system with Born electrostatic ion solvation behavior
journal, February 2009

Are Keggin’s POMs Charged Nanocolloids or Multicharged Anions?
journal, January 2018

Ramanspektroskopische und Ultrazentrifugen-Messungen zur Untersuchung der Hydrolyse der Dodekawolframatophosphors�ure
journal, September 1977

Joint use of small-angle X-ray and neutron scattering to study biological macromolecules in solution
journal, April 2006

Polyoxometalates in the Hofmeister series
journal, January 2018

Crystallization of Keggin Heteropolyanions via a Two-Step Process in Aqueous Solutions
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Sectroscopic study of stability and molecular species of 12-tungstophosphoric acid in aqueous solution
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journal, September 2018

SASfit : a tool for small-angle scattering data analysis using a library of analytical expressions
journal, September 2015

Aggregation of Heteropolyanions in Aqueous Solutions Exhibiting Short-Range Attractions and Long-Range Repulsions
journal, December 2015

The stability of 12-molybdosilicic, 12-tungstosilicic, 12-molybdophosphoric and 12-tungstophosphoric acids in aqueous solution at various pH
journal, March 1995

pH-controlled hydrogen-bonding (Short Communication)
journal, December 1974

Small-angle scattering studies of biological macromolecules in solution
journal, September 2003

Nanometer-Size Polyoxometalate Anions Adsorb Strongly on Neutral Soft Surfaces
journal, August 2015

Acidity Measurements on a Heteropolyacid Hydrate in Acetic Acid Solution: A Case of Three Hydrons Ionizing Independently, Rather Than Consecutively
journal, March 1995

Ion aggregation in concentrated aqueous and methanol solutions of polyoxometallates Keggin anions: the effect of counterions investigated by molecular dynamics simulations
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journal, March 2012

Structural aspects of heteropolyacid microemulsions
journal, January 2014

Dodecatungstophosphoric acid hexahydrate, (H5O2+)3(PW12O403−). The true structure of Keggin's `pentahydrate' from single-crystal X-ray and neutron diffraction data
journal, April 1977

Stability investigation of some heteropolyoxotungstate and heteropolyoxomolybdate salts in buffer solutions
journal, October 2012

Small-angle scattering. Information content and error analysis
journal, April 1980

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