Synthesis of Petitjeanite Bi3O(OH)(PO4)2 Photocatalytic Microparticles: Effect of Synthetic Conditions on the Crystal Structure and Activity toward Degradation of Aqueous Perfluorooctanoic Acid (PFOA)

Abstract

The discovery of synthetic Bi₃O(OH)(PO₄)₂ [BOHP] and its application toward photocatalytic oxidation of the water contaminant perfluorooctanoic acid (PFOA) have prompted further interest in development. Despite its high activity toward PFOA degradation, the scarce appearance in the literature and lack of research have left a knowledge gap in the understanding of BOHP synthesis, formation, and photocatalytic activity. Herein, we explore the crystallization of BOHP microparticles via hydrothermal syntheses, focusing on the influence of ions and organics present in the reaction solution when using different hydroxide amendments (NaOH, NH₄OH, NMe₄OH, and NEt₄OH). To better understand the unique structure-activity aspects of BOHP, the related bismuth oxy phosphate (BOP) structural family was also explored, including A-BOP (A = Na⁺ and K⁺) and M-BOP derivatives (M = Ca²⁺, Sr²⁺, and Pb²⁺). Results from materials characterization, including X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy, indicated that the crystal structure, morphology, and atomic composition were significantly influenced by solution pH, inorganic metal cations (Na⁺, K⁺, Ca²⁺, Sr²⁺, and Pb²⁺), and organic amines. Experiments involving ultraviolet photocatalytic destruction of PFOA by a BOHP suspension revealed that catalytic activity was influenced by the choice of reagents and their variable effect on surface facet growth and crystal defects in the resulting microparticles. Together, this work provides a strategy for crystal facet and surface defect engineering with the potential to expand to other metal oxides within the hydrothermal system.

Keywords: facet engineering; photocatalysis; pollution remediation; post-transition metal oxides; surface engineering.