Synthesis of phosphorous acid and its derivatives based on the reaction of elemental phosphorus (P<sub>4</sub>) and aqueous solution of choline in the presence of the hydroxides of earth alkali metals

Platova, Elena V.; Батыева, Э. С.; Kursheva, L. I.; Sinyashin, Оleg G.

doi:10.1002/hc.20472

Cited by 6 publications

(5 citation statements)

References 2 publications

(2 reference statements)

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“…This interaction is field independent. The measured scalar coupling constant, 1 J P−H is 704 Hz, in good agreement with previous report for this chemical [29]. By the way, no P 2 O 5 peak can be observed upon aging until 38 days.…”

Section: Resultssupporting

confidence: 92%

Degradation of black phosphorus: a real-time ³¹ P NMR study

et al. 2016

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Black phosphorus (BP) possesses several extraordinary physical properties, which include inplane anisotropy, thickness dependent direct bandgap and high carrier mobility. These physical properties make BP highly desirable from the point of view of fundamental science and modern optoelectronics applications. The excitement about this material has always been accompanied by unreserved skepticism due to its extraordinary degradation under ambient conditions. Here we show ambient degradation of exfoliated BP can be effectively suppressed using thin layer of hybrid metal organic chemical vapor deposition coating of boron nitride (BN) followed by atomic layer deposition coating of Al 2 O 3. We have extensively studied the time dependent surface, optical and electrical properties of BP encapsulated by BN and/or Al 2 O 3 using nanoscale infrared imaging and I-V characterizations. Our results show hybrid thin layer (∼5 nm) BN/Al 2 O 3 coated BP exfoliated on SiO 2 substrate is protected from degradation in ambient for over 6 months, much longer than those coated only by BN or Al 2 O 3 layers. Our theoretical modeling of the experimental degradation growth pattern shows that the influence of neighboring elements on the degradation of a given element is minimal for BP flakes with hybrid coating. Electrical characterization further confirms the effectiveness of BN/Al 2 O 3 as encapsulation layer and gate dielectrics with minor changes after several weeks.

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Section: Resultssupporting

confidence: 92%

Degradation of black phosphorus: a real-time ³¹ P NMR study

et al. 2016

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“… 74 This method led to a 34% isolated yield of phosphite (67% based on reactive P) in the form of a barium phosphite salt BaHPO 3 ·H 2 O ( SI section 4.5). Phosphorous acid solutions can be prepared by treatment of the barium phosphite salt with sulfuric acid, 75 and protocols for separation of phosphorous acid from phosphoric acid on an industrial scale are well-established. 76 − 79…”

mentioning

confidence: 99%

“…74 This method led to a 34% isolated yield of phosphite (67% based on reactive P) in the form of a barium phosphite salt BaHPO 3 •H 2 O (SI section 4.5). Phosphorous acid solutions can be prepared by treatment of the barium phosphite salt with sulfuric acid, 75 and protocols for separation of phosphorous acid from phosphoric acid on an industrial scale are well-established. 76−79 In biological systems, long-chain polyphosphate (polyP) is involved in ATP synthesis catalyzed by polyP kinases, in which polyP is the source of a third PO 3 − group leading to ATP.…”

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confidence: 99%

Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

et al. 2022

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In pursuit of a more sustainable production of phosphorous acid (H 3 PO 3 ), a versatile chemical with phosphorus in the +3 oxidation state, we herein report that condensed phosphates can be employed to phosphorylate hydride reagents under solvent-free mechanochemical conditions to furnish phosphite (HPO 3 2– ). Using potassium hydride as the hydride source, sodium trimetaphosphate (Na 3 P 3 O 9 ), triphosphate (Na 5 P 3 O 10 ), pyrophosphate (Na 4 P 2 O 7 ), fluorophosphate (Na 2 PO 3 F), and polyphosphate (“(NaPO 3 ) n ”) engendered phosphite in optimized yields of 44, 58, 44, 84, and 55% based on total P content, respectively. Formation of overreduced products including hypophosphite (H 2 PO 2 – ) was identified as a competing process, and mechanistic investigations revealed that hydride attack on in-situ-generated phosphorylated phosphite species is a potent pathway for overreduction. The phosphite generated from our method was easily isolated in the form of barium phosphite, a useful intermediate for production of phosphorous acid. This method circumvents the need to pass through white phosphorus (P 4 ) as a high-energy intermediate and mitigates involvement of environmentally hazardous chemicals. A bioproduced polyphosphate was found to be a viable starting material for the production of phosphite. These results demonstrate the possibility of accessing reduced phosphorus compounds in a more sustainable manner and, more importantly, a means to close the modern phosphorus cycle.

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“…58 This method led to a 34% isolated yield of phosphite (67% based on reactive P) in the form of a barium phosphite salt BaHPO3•H2O (see SI). Phosphorous acid solutions can be prepared by treatment of the barium phosphite salt with sulfuric acid, 59 and protocols for separation of phosphorous acid from phosphoric acid on an industrial scale are well established. [60][61][62][63] In biological systems, long-chain polyphosphate (polyP) is involved in ATP synthesis catalyzed by polyP kinases in which polyP is the source of a third PO3 − group leading to ATP.…”

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confidence: 99%

Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

Zhai

Xin

Geeson

et al. 2021

Preprint

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Phosphorus removal and recovery technologies have been implemented to tackle the anthropogenic eutrophication caused by phosphate runoff into waterways. In pursuit of a better utilization of the phosphates recovered from waste water treatment, we herein report that condensed phosphates can be employed to phosphorylate hydride reagents under solvent-free mechanochemical conditions to furnish phosphite (HPO3)2−, a versatile chemical with phosphorus in the +3 oxidation state. Hydride phosphorylation, as a two-electron one-proton reduction of a main group element oxide, constitutes a direct parallel with CO2 reduction to formate. Using potassium hydride as the hydride source, sodium trimetaphosphate (Na3P3O9 ), triphosphate (Na5P3O10), and pyrophosphate (Na4P2O7) engendered phosphite in 44, 58, and 44% yields based on total P content, respectively, under their optimal conditions. Formation of overreduced products including hypophosphite (H2PO2−) was identified as a competing process, and mechanistic investigation revealed that hydride attack on in situ generated phosphorylated phosphite species is a potent pathway for overreduction. The phosphite generated from our method could be easily isolated in the form of barium phosphite, a useful intermediate for production of phosphorous acid. This method circumvents the need to pass through white phosphorus (P4) as a high energy intermediate and mitigates involvement of environmentally hazardous chemicals. A bioproduced polyphosphate from baker’s yeast was demonstrated to be a viable starting material for the production of phosphite. This example demonstrates the possibility of accessing reduced phosphorus compounds in a more sustainable manner, and more importantly, closing the modern phosphorus cycle.

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Synthesis of phosphorous acid and its derivatives based on the reaction of elemental phosphorus (P₄) and aqueous solution of choline in the presence of the hydroxides of earth alkali metals

Cited by 6 publications

References 2 publications

Degradation of black phosphorus: a real-time ³¹ P NMR study

Degradation of black phosphorus: a real-time ³¹ P NMR study

Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

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Synthesis of phosphorous acid and its derivatives based on the reaction of elemental phosphorus (P4) and aqueous solution of choline in the presence of the hydroxides of earth alkali metals

Cited by 6 publications

References 2 publications

Degradation of black phosphorus: a real-time 31 P NMR study

Degradation of black phosphorus: a real-time 31 P NMR study

Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

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Synthesis of phosphorous acid and its derivatives based on the reaction of elemental phosphorus (P₄) and aqueous solution of choline in the presence of the hydroxides of earth alkali metals

Degradation of black phosphorus: a real-time ³¹ P NMR study

Degradation of black phosphorus: a real-time ³¹ P NMR study