Tepora Su’a, Mikaylah N. Poli and Stephanie L. Brock*,
{"title":"通过前体调节的多金属磷酸盐的均匀纳米颗粒:三元和四元M2P相(M=Fe,Co,Ni)","authors":"Tepora Su’a, Mikaylah N. Poli and Stephanie L. Brock*, ","doi":"10.1021/acsnanoscienceau.2c00025","DOIUrl":null,"url":null,"abstract":"<p >Transition metal phosphides (TMPs) are a highly investigated class of nanomaterials due to their unique magnetic and catalytic properties. Although robust and reproducible synthetic routes to narrow polydispersity monometallic phosphide nanoparticles (M<sub>2</sub>P; M = Fe, Co, Ni) have been established, the preparation of multimetallic nanoparticle phases (M<sub>2–<i>x</i></sub>M′<sub><i>x</i></sub>P; M, M′ = Fe, Co, Ni) remains a significant challenge. Colloidal syntheses employ zero-valent metal carbonyl or multivalent acetylacetonate salt precursors in combination with trioctylphosphine as the source of phosphorus, oleylamine as the reducing agent, and additional solvents such as octadecene or octyl ether as “noncoordinating” cosolvents. Understanding how these different metal precursors behave in identical reaction environments is critical to assessing the role the relative reactivity of the metal precursor plays in synthesizing complex, homogeneous multimetallic TMP phases. In this study, phosphorus incorporation as a function of temperature and time was evaluated to probe how the relative rate of phosphidation of organometallic carbonyl and acetylacetonate salt precursors influences the homogeneous formation of bimetallic phosphide phases (M<sub>2–<i>x</i></sub>M′<sub><i>x</i></sub>P; M, M′ = Fe, Co, Ni). From the relative rate of phosphidation studies, we found that where reactivity with TOP for the various metal precursors differs significantly, prealloying steps are necessary to isolate the desired bimetallic phosphide phase. These insights were then translated to establish streamlined synthetic protocols for the formation of new trimetallic Fe<sub>2–<i>x</i>–<i>y</i></sub>Ni<sub><i>x</i></sub>Co<sub><i>y</i></sub>P phases.</p>","PeriodicalId":29799,"journal":{"name":"ACS Nanoscience Au","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2022-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsnanoscienceau.2c00025","citationCount":"2","resultStr":"{\"title\":\"Homogeneous Nanoparticles of Multimetallic Phosphides via Precursor Tuning: Ternary and Quaternary M2P Phases (M = Fe, Co, Ni)\",\"authors\":\"Tepora Su’a, Mikaylah N. Poli and Stephanie L. Brock*, \",\"doi\":\"10.1021/acsnanoscienceau.2c00025\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Transition metal phosphides (TMPs) are a highly investigated class of nanomaterials due to their unique magnetic and catalytic properties. Although robust and reproducible synthetic routes to narrow polydispersity monometallic phosphide nanoparticles (M<sub>2</sub>P; M = Fe, Co, Ni) have been established, the preparation of multimetallic nanoparticle phases (M<sub>2–<i>x</i></sub>M′<sub><i>x</i></sub>P; M, M′ = Fe, Co, Ni) remains a significant challenge. Colloidal syntheses employ zero-valent metal carbonyl or multivalent acetylacetonate salt precursors in combination with trioctylphosphine as the source of phosphorus, oleylamine as the reducing agent, and additional solvents such as octadecene or octyl ether as “noncoordinating” cosolvents. Understanding how these different metal precursors behave in identical reaction environments is critical to assessing the role the relative reactivity of the metal precursor plays in synthesizing complex, homogeneous multimetallic TMP phases. In this study, phosphorus incorporation as a function of temperature and time was evaluated to probe how the relative rate of phosphidation of organometallic carbonyl and acetylacetonate salt precursors influences the homogeneous formation of bimetallic phosphide phases (M<sub>2–<i>x</i></sub>M′<sub><i>x</i></sub>P; M, M′ = Fe, Co, Ni). From the relative rate of phosphidation studies, we found that where reactivity with TOP for the various metal precursors differs significantly, prealloying steps are necessary to isolate the desired bimetallic phosphide phase. 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Homogeneous Nanoparticles of Multimetallic Phosphides via Precursor Tuning: Ternary and Quaternary M2P Phases (M = Fe, Co, Ni)
Transition metal phosphides (TMPs) are a highly investigated class of nanomaterials due to their unique magnetic and catalytic properties. Although robust and reproducible synthetic routes to narrow polydispersity monometallic phosphide nanoparticles (M2P; M = Fe, Co, Ni) have been established, the preparation of multimetallic nanoparticle phases (M2–xM′xP; M, M′ = Fe, Co, Ni) remains a significant challenge. Colloidal syntheses employ zero-valent metal carbonyl or multivalent acetylacetonate salt precursors in combination with trioctylphosphine as the source of phosphorus, oleylamine as the reducing agent, and additional solvents such as octadecene or octyl ether as “noncoordinating” cosolvents. Understanding how these different metal precursors behave in identical reaction environments is critical to assessing the role the relative reactivity of the metal precursor plays in synthesizing complex, homogeneous multimetallic TMP phases. In this study, phosphorus incorporation as a function of temperature and time was evaluated to probe how the relative rate of phosphidation of organometallic carbonyl and acetylacetonate salt precursors influences the homogeneous formation of bimetallic phosphide phases (M2–xM′xP; M, M′ = Fe, Co, Ni). From the relative rate of phosphidation studies, we found that where reactivity with TOP for the various metal precursors differs significantly, prealloying steps are necessary to isolate the desired bimetallic phosphide phase. These insights were then translated to establish streamlined synthetic protocols for the formation of new trimetallic Fe2–x–yNixCoyP phases.
期刊介绍:
ACS Nanoscience Au is an open access journal that publishes original fundamental and applied research on nanoscience and nanotechnology research at the interfaces of chemistry biology medicine materials science physics and engineering.The journal publishes short letters comprehensive articles reviews and perspectives on all aspects of nanoscience and nanotechnology:synthesis assembly characterization theory modeling and simulation of nanostructures nanomaterials and nanoscale devicesdesign fabrication and applications of organic inorganic polymer hybrid and biological nanostructuresexperimental and theoretical studies of nanoscale chemical physical and biological phenomenamethods and tools for nanoscience and nanotechnologyself- and directed-assemblyzero- one- and two-dimensional materialsnanostructures and nano-engineered devices with advanced performancenanobiotechnologynanomedicine and nanotoxicologyACS Nanoscience Au also publishes original experimental and theoretical research of an applied nature that integrates knowledge in the areas of materials engineering physics bioscience and chemistry into important applications of nanomaterials.