Evidence for non-electrostatic interactions between a pyrophosphate-functionalized uranyl peroxide nanocluster and iron (hydr)oxide minerals

Luke R. Sadergaski; Samuel N. Perry; Luke R. Tholen; Amy E. Hixon

doi:10.1039/c9em00139e

Evidence for non-electrostatic interactions between a pyrophosphate-functionalized uranyl peroxide nanocluster and iron (hydr)oxide minerals

Luke R. Sadergaski, Samuel N. Perry, Luke R. Tholen, Amy E. Hixon

Research output: Contribution to journal › Article › peer-review

Abstract

The terminal oxygen atoms of the pyrophosphate groups in the uranyl peroxide nanocluster U₂₄Pp₁₂ ([(UO₂)₂₄(O₂)₂₄(P₂O₇)₁₂]^48-) are not fully satisfied by bond valence considerations and can become protonated. This functionality could allow for specific interactions with mineral surfaces, as opposed to the electrostatically-driven interactions observed between non-functionalized uranyl peroxide nanoclusters and mineral surfaces. The sorption of U₂₄Pp₁₂ to goethite and hematite was studied using batch sorption experiments as a function of U₂₄Pp₁₂ concentration, mineral concentration, and pH. A suite of spectroscopic techniques, scanning electron microscopy, and electrophoretic mobility measurements were used to examine the minerals before and after reaction with U₂₄Pp₁₂, leading to a proposed conceptual model for U₂₄Pp₁₂ interactions with goethite. The governing rate laws were determined and compared to those previously determined for a non-functionalized uranyl peroxide nanocluster. The rate of uranyl peroxide nanocluster sorption depends on the charge density and functionalized component of the uranyl peroxide cage. Electrophoretic mobility and attenuated total reflectance Fourier transform infrared spectroscopy analyses show that an inner-sphere complex forms between the U₂₄Pp₁₂ cluster and the goethite surface through the terminal pyrophosphate groups, leading to a proposed conceptual model in which U₂₄Pp₁₂ interacts with the triply-coordinated reactive sites on the (110) plane of goethite. These results demonstrate that the behavior of U₂₄Pp₁₂ at the iron (hydr)oxide-water interface is unique relative to interactions of the uranyl ion and non-functionalized uranyl peroxide nanoclusters.

Original language	English
Pages (from-to)	1174-1183
Number of pages	10
Journal	Environmental Science: Processes and Impacts
Volume	21
Issue number	7
DOIs	https://doi.org/10.1039/c9em00139e
State	Published - Jul 2019
Externally published	Yes

Funding

This material is based on work supported by the U.S. Department of Energy, National Nuclear Security Administration as part of the Actinide Center of Excellence under Award Number DE-NA0003763. The authors thank Dr Allen G. Oliver for helpful discussions regarding ATR-FTIR and Mercury analyses. The following centers and facilities at the University of Notre Dame provided access to instrumentation used in this research study: the Center for Environmental Science and Technology (BET, ICP-OES), the Mass Spectrometry and Proteomics Facility (ESI-MS), and the Center for Sustainable Energy's Materials Characterization Facility (powder X-ray diffraction, Raman, XPS). This material is based on work supported by the U.S. Department of Energy, National Nuclear Security Administration as part of the Actinide Center of Excellence under Award Number DE-NA0003763. The authors thank Dr Allen G. Oliver for helpful discussions regarding ATR-FTIR and Mercury analyses. The following centers and facilities at the University of Notre Dame provided access to instrumentation used in this research study: the Center for Environmental Science and Technology (BET, ICP-OES), the Mass Spectrometry and Proteomics Facility (ESIMS), and the Center for Sustainable Energy's Materials Characterization Facility (powder X-ray diffraction, Raman, XPS).

Funders	Funder number
BET
Center for Environmental Science and Technology
Center for Sustainable Energy's Materials Characterization Facility
ESIMS
Mass Spectrometry and Proteomics Facility
U.S. Department of Energy
National Nuclear Security Administration	DE-NA0003763
University of Notre Dame

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title = "Evidence for non-electrostatic interactions between a pyrophosphate-functionalized uranyl peroxide nanocluster and iron (hydr)oxide minerals",

abstract = "The terminal oxygen atoms of the pyrophosphate groups in the uranyl peroxide nanocluster U24Pp12 ([(UO2)24(O2)24(P2O7)12]48-) are not fully satisfied by bond valence considerations and can become protonated. This functionality could allow for specific interactions with mineral surfaces, as opposed to the electrostatically-driven interactions observed between non-functionalized uranyl peroxide nanoclusters and mineral surfaces. The sorption of U24Pp12 to goethite and hematite was studied using batch sorption experiments as a function of U24Pp12 concentration, mineral concentration, and pH. A suite of spectroscopic techniques, scanning electron microscopy, and electrophoretic mobility measurements were used to examine the minerals before and after reaction with U24Pp12, leading to a proposed conceptual model for U24Pp12 interactions with goethite. The governing rate laws were determined and compared to those previously determined for a non-functionalized uranyl peroxide nanocluster. The rate of uranyl peroxide nanocluster sorption depends on the charge density and functionalized component of the uranyl peroxide cage. Electrophoretic mobility and attenuated total reflectance Fourier transform infrared spectroscopy analyses show that an inner-sphere complex forms between the U24Pp12 cluster and the goethite surface through the terminal pyrophosphate groups, leading to a proposed conceptual model in which U24Pp12 interacts with the triply-coordinated reactive sites on the (110) plane of goethite. These results demonstrate that the behavior of U24Pp12 at the iron (hydr)oxide-water interface is unique relative to interactions of the uranyl ion and non-functionalized uranyl peroxide nanoclusters.",

author = "Sadergaski, {Luke R.} and Perry, {Samuel N.} and Tholen, {Luke R.} and Hixon, {Amy E.}",

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doi = "10.1039/c9em00139e",

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AU - Hixon, Amy E.

PY - 2019/7

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N2 - The terminal oxygen atoms of the pyrophosphate groups in the uranyl peroxide nanocluster U24Pp12 ([(UO2)24(O2)24(P2O7)12]48-) are not fully satisfied by bond valence considerations and can become protonated. This functionality could allow for specific interactions with mineral surfaces, as opposed to the electrostatically-driven interactions observed between non-functionalized uranyl peroxide nanoclusters and mineral surfaces. The sorption of U24Pp12 to goethite and hematite was studied using batch sorption experiments as a function of U24Pp12 concentration, mineral concentration, and pH. A suite of spectroscopic techniques, scanning electron microscopy, and electrophoretic mobility measurements were used to examine the minerals before and after reaction with U24Pp12, leading to a proposed conceptual model for U24Pp12 interactions with goethite. The governing rate laws were determined and compared to those previously determined for a non-functionalized uranyl peroxide nanocluster. The rate of uranyl peroxide nanocluster sorption depends on the charge density and functionalized component of the uranyl peroxide cage. Electrophoretic mobility and attenuated total reflectance Fourier transform infrared spectroscopy analyses show that an inner-sphere complex forms between the U24Pp12 cluster and the goethite surface through the terminal pyrophosphate groups, leading to a proposed conceptual model in which U24Pp12 interacts with the triply-coordinated reactive sites on the (110) plane of goethite. These results demonstrate that the behavior of U24Pp12 at the iron (hydr)oxide-water interface is unique relative to interactions of the uranyl ion and non-functionalized uranyl peroxide nanoclusters.

AB - The terminal oxygen atoms of the pyrophosphate groups in the uranyl peroxide nanocluster U24Pp12 ([(UO2)24(O2)24(P2O7)12]48-) are not fully satisfied by bond valence considerations and can become protonated. This functionality could allow for specific interactions with mineral surfaces, as opposed to the electrostatically-driven interactions observed between non-functionalized uranyl peroxide nanoclusters and mineral surfaces. The sorption of U24Pp12 to goethite and hematite was studied using batch sorption experiments as a function of U24Pp12 concentration, mineral concentration, and pH. A suite of spectroscopic techniques, scanning electron microscopy, and electrophoretic mobility measurements were used to examine the minerals before and after reaction with U24Pp12, leading to a proposed conceptual model for U24Pp12 interactions with goethite. The governing rate laws were determined and compared to those previously determined for a non-functionalized uranyl peroxide nanocluster. The rate of uranyl peroxide nanocluster sorption depends on the charge density and functionalized component of the uranyl peroxide cage. Electrophoretic mobility and attenuated total reflectance Fourier transform infrared spectroscopy analyses show that an inner-sphere complex forms between the U24Pp12 cluster and the goethite surface through the terminal pyrophosphate groups, leading to a proposed conceptual model in which U24Pp12 interacts with the triply-coordinated reactive sites on the (110) plane of goethite. These results demonstrate that the behavior of U24Pp12 at the iron (hydr)oxide-water interface is unique relative to interactions of the uranyl ion and non-functionalized uranyl peroxide nanoclusters.

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Evidence for non-electrostatic interactions between a pyrophosphate-functionalized uranyl peroxide nanocluster and iron (hydr)oxide minerals

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