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The Phosphorus Cycle

The Phosphorus Cycle

Unlike carbon, water, and nitrogen, phosphorus is not present in the atmosphere as a gas. Instead, most phosphorus in the ecosystem exists as compounds, such as phosphate ions (PO43-), found in soil, water, sediment and rocks. Phosphorus is often a limiting nutrient (i.e., in short supply). Consequently, phosphorus is added to most agricultural fertilizers, which can cause environmental problems related to runoff in aquatic ecosystems.

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Unexpected nanoscale CeO₂ structural transformations induced by ecologically relevant phosphate species.

Tatiana V Plakhova¹, Maria A Vyshegorodtseva¹, Irina F Seregina¹

¹Lomonosov Moscow State University, Department of Chemistry, Leninskie Gory 1/3, 119991, Moscow, Russia.

|November 3, 2024

Summary

Cerium dioxide nanoparticles (CeO2 NPs) transform into sodium-cerium double phosphate in phosphate solutions. This phosphate-induced transformation alters nanoparticle speciation and microstructure.

Keywords:

Ageing Cerium dioxide Cerium(IV) phosphate Nanoparticles Phase changes

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Area of Science:

Environmental Science
Materials Science
Nanotechnology

Background:

Cerium dioxide nanoparticles (CeO2 NPs) are increasingly used in various applications.
Understanding the environmental fate and transformation of CeO2 NPs is crucial.
Phosphate is a common component in natural and engineered environments.

Purpose of the Study:

To investigate the dissolution and microstructural transformation of CeO2 NPs in phosphate-containing solutions.
To elucidate the chemical speciation and structural changes of CeO2 NPs upon interaction with phosphate.
To provide insights into the environmental behavior of CeO2 NPs.

Main Methods:

Synchrotron X-ray diffraction (XRD) analysis
X-ray absorption spectroscopy (XAS)
Scanning and transmission electron microscopy (SEM/TEM)
Pair distribution function (PDF) analysis

Main Results:

Dissolution of 2 nm and 5 nm CeO2 NPs in phosphate buffer solutions differs significantly from NaClO4 solutions.
CeO2 NPs transform into sodium-cerium double phosphate (Na-Ce(IV) phosphate) with cerium primarily in the Ce(IV) state.
The Na-Ce(IV) phosphate forms spindle-like aggregates of nanocrystalline rods with a 3D framework structure similar to NaTh2(PO4)3.
Disordered sodium atoms are observed within large channels along the c-axis of the Na-Ce(IV) phosphate structure.

Conclusions:

This study provides the first detailed analysis of phosphate-induced speciation and microstructural transformation of CeO2 NPs.
The formation of Ce(IV) phosphate represents a significant transformation pathway for CeO2 NPs in phosphate-rich environments.
Similar transformation processes may occur in natural ecosystems, impacting the environmental fate and effects of CeO2 NPs.