Ni- and Co-struvites: Revealing crystallization mechanisms and crystal engineering towards applicational use of transition metal phosphates

TL;DR

This study elucidates the crystallization mechanisms of Ni- and Co-struvites, optimizing their synthesis for potential use in metal recovery and transition metal phosphate applications, with insights into morphology control and reaction kinetics.

Contribution

It provides new synthesis routes and mechanistic understanding of transition metal struvites, enabling tailored crystal engineering for environmental and industrial applications.

Findings

Ni-struvite is stable across various conditions.

Co-struvite forms only at low M/P ratios.

Crystallization involves intermediate colloidal phases.

Abstract

Industrial and agricultural waste streams, which contain high concentrations of NH4+, PO43- and transition metals are environmentally harmful and toxic pollutants. At the same time phosphorous and transition metals constitute highly valuable resources. Typically, separate pathways have been considered to extract hazardous transition metals or phosphate, independently from each other. Investigations on the simultaneous removal of multiple components have been studied only to a limited extent. Here, we report the synthesis routes for Co- and Ni-struvites (NH4MPO4.6H2O, M = Ni2+, Co2+ ), which allow for P, ammonia and metal co precipitation. By evaluating different reaction parameters, the phase and stability of transition metal struvites, as well as their crystal morphologies, and sizes could be optimized. Ni-struvite is stable in a wide reactant concentration range and at different metal/phosphorus (M/P) ratios, whereas Co-struvite only forms at low M/P ratios. Detailed investigations of the precipitation process using ex situ and in situ techniques provided insights into the crystallization mechanisms/crystal engineering of these materials. M-struvites crystallize via intermediate colloidal nanophases, which subsequently aggregate and condense to final crystals after extended reaction times. However, the exact reaction kinetics of the formation of a final crystalline product varies significantly depending on the metal cation involved in the precipitation process: several seconds (Mg) to minutes (Ni) to hours (Co). The achieved level of control over the morphology and size, makes precipitation of metal struvites a promising method for direct metal recovery and binding them in the form of valuable phosphate raw materials. Under this paradigm, the crystals can be potentially upcycled as precursor powders for electrochemical applications, which require transition metal phosphates (TMPs).