Template-free synthesis of mesoporous and amorphous transition metal phosphate materials

Abstract

We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves the transformation of a precursor metal phosphate phase, called M-struvite (NH₄MPO₄·6H₂O, M = Mg²⁺, Ni²⁺, Co²⁺, Ni_xCo_1−x²⁺). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms during degassing of NH₃ and H₂O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed by in situ and ex situ scattering and diffraction, as well as X-ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on the metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and Ni_xCo_1−x-struvites exhibit high surface areas and pore volumes (240 m² g⁻¹ and 0.32 cm⁻³ g⁻¹ for Mg and 90 m² g⁻¹ and 0.13 cm⁻³ g⁻¹ for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further application, for instance in (electro)catalysis.