Efficient Electrosynthesis of White Phosphorus from Molten Condensed Phosphate Salts

Elemental white phosphorus (P4) is a crucial feedstock for the entire phosphorus-derived chemicals industry, spanning everything from herbicides to food additives. Currently, industrial P4 production is gated by the infrastructurally demanding reduction of phosphate rock by carbon coke in an arc furnace at temperatures of up to 1500 °C. The electrochemical reduction of phosphate salts could enable the sustainable, point-of-use manufacture of white phosphorus; however, such P4 electrosynthesis requires the rapid activation of strong P—O bonds. Herein, we show that the intrinsic oxide-accepting character of phosphoryl anhydride linkages in molten condensed phosphate salts promotes the reduction of phosphate to white phosphorus at high electron and energy efficiencies. These findings could enable an efficient, low-carbon alternative to legacy carbothermal synthesis of P4.

Did Cyclic Metaphosphates Have a Role in the Origin of Life?

How life began still eludes science life, the initial progenote in the context presented herein, being a chemical aggregate of primordial inorganic and organic molecules capable of self-replication and evolution into ever increasingly complex forms and functions.Presented is a hypothesis that a mineral scaffold generated by geological processes and containing polymerized phosphate units was present in primordial seas that provided the initiating factor responsible for the sequestration and organization of primordial life’s constituents. Unlike previous hypotheses proposing phosphates as the essential initiating factor, the key phosphate described here is not a polynucleotide or just any condensed phosphate but a large (in the range of at least 1 kilo-phosphate subunits), water soluble, cyclic metaphosphate, which is a closed loop chain of polymerized inorganic phosphate residues containing only phosphate middle groups. The chain forms an intrinsic 4-phosphate helix analogous to its structure in Na Kurrol’s salt, and as with DNA, very large metaphosphates may fold into hairpin structures. Using a Holliday-junction-like scrambling mechanism, also analogous to DNA, rings may be manipulated (increased, decreased, exchanged) easily with little to no need for additional energy, the reaction being essentially an isomerization.A literature review is presented describing findings that support the above hypothesis. Reviewed is condensed phosphate inorganic chemistry including its geological origins, biological occurrence, enzymes and their genetics through eukaryotes, polyphosphate functions, circular polynucleotides and the role of the Holliday junction, previous biogenesis hypotheses, and an Eoarchean Era timeline.