Electrocatalytic properties of cobalt phosphides and pyrophosphates derived from phosphonate-based-MOFs

As a class of coordination polymers (CPs), metal phosphonates (MPs) are constructed by coordination bonds connecting metal sites and phosphonate (RPO32−) ligands, where the metal sites are dispersed uniformly at the atomic level. This feature facilitates the construction of metalphosphorous-based/nano-carbon composites by one-step pyrolysis, making them very attractive precursors of Non-Precious Metal Electrocatalysts (NPMCs) [1, 2] In this work, we report the synthesis, characterization and electrochemical properties of three cobalt(II) coordination polymers erived from the N,N-bis(phosphonomethyl)glycine (BPMGLY), Co(C4H9O8NP2·nH2O (n=2-4). These MPs, with different frameworks according to the crystallographic data, are used as precursors of new NPMCs by pyrolytic treatment under 5%-H2/Ar at different temperatures. The electrochemical behavior of the resulting compounds, mainly crystalline cobalt pyrophosphates and/or phosphides, is fully investigated regarding to the Oxygen Evolution and Reduction Reactions (OER and ORR, respectively) as well as Hydrogen Evolution Reaction (HER). In general, cobalt phosphides (CoP) derived from compound Co-BPMGLY-I (n=4), displayed better performances for the HER with an overpotential of 156 mVUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Synthesis, structural characterization and electrocatalytic properties of cobalt phosphides and pyrophosphates derived from glyphosine

Póster presentado en el XXX Simposio del GE3CMetal phosphonates (MPs), a subclass of coordination polymers, result from the bonding of phosphonic acids (RPO32-) with metal ions, giving rise to an uniformly dispersion of the metal sites at the atomic scale. This characteristic allows the preparation of metal-phosphorous-based nano-carbon composites by a simple one-step pyrolysis, what makes them very attractive precursors of Non-Precious Metal Catalysts (NPMCs). Herein, we report the synthesis, characterization and electrochemical properties of three cobalt(II) coordination polymers derived from the glycine-N,N-bis(methylenenphosphonic acid) (BPMGLY), with formula [Co(C4H9O8NP2(H2O)2]·nH2O (n=0, 2). In contrast with the zero-dimensional structure of [Co(C4H9O8NP2(H2O)2]·2H2O (Co-BPMGLY-I), the two new polymorphs synthesized, Co(C4H9O8NP2(H2O)2 (Co-BPMGLY-II and Co-BPMGLY-III), whose structures have been solved from powder diffraction data, show two-dimensional frameworks with different connectivity between the Co2+ ions and the ligand within the sheets. These MPs were used as precursors of NPMCs by pyrolyzing them under 5%-H2/Ar at different temperatures. The electrochemical behavior of the resulting compounds, mainly crystalline cobalt pyrophosphates and/or phosphides, is fully studied regarding to the Oxygen Evolution and Reduction Reactions (OER and ORR, respectively) as well as Hydrogen Evolution Reaction (HER). Cobalt phosphide (CoP) derived from Co-BPMGLY-I displayed the best results, showing an overpotential of 156 mV for HER.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. Proyectos nacionales MAT2016-77648-R y PID2019-110249RB-I0