Low-Temperature Solvothermal Synthesis of Phosphorus-Rich Transition-Metal Phosphides

Barry, Brian M.; Gillan, Edward G.

doi:10.1021/cm703095z

Cited by 65 publications

(50 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[5,6] In recent years, considerable efforts have been devoted to the synthesis of nanostructured transition-metal phosphides. For instance, Co 2 P nanoparticles supported on silica were synthesized by thermal treatment of [Co 2 (CO) 6 [7] Nanostructured Co 2 P, Ni 2 P, CoP, FeP, and MnP were prepared by hydrothermal and solvothermal methods using yellow phosphorus (P 4 ) [8,9] and by a desilylation strategy using tris(trimethylsilyl)phosphine (PA C H T U N G T R E N N U N G (SiMe 3 ) 3 ). [10] Moreover, Fe 2 P, FeP, Co 2 P, CoP, Ni 2 P, and MnP nanocrystals were also made by solution-phase methods using trioctylphosphine (TOP), metal phosphine complexes, long-chain alkylphosphonic acids, and single-source molecular precursors containing elemental metal and phosphorus.…”

Section: Introductionmentioning

confidence: 99%

Phase‐Controlled Synthesis of Transition‐Metal Phosphide Nanowires by Ullmann‐Type Reactions

Wang

Yang

Zhang

et al. 2010

Chemistry A European J

105

View full text Add to dashboard Cite

Transition-metal phosphide nanowires were facilely synthesized by Ullmann-type reactions between transition metals and triphenylphosphine in vacuum-sealed tubes at 350-400 degrees C. The phase (stoichiometry) of the phosphide products is controllable by tuning the metal/PPh(3) molar ratio and concentration, reaction temperature and time, and heating rate. Six classes of iron, cobalt, and nickel phosphide (Fe(2)P, FeP, Co(2)P, CoP, Ni(2)P, and NiP(2)) nanostructures were prepared to demonstrate the general applicability of this new method. The resulting phosphide nanostructures exhibit interesting phase- and composition-dependent magnetic properties, and magnetic measurements suggested that the Co(2)P nanowires with anti-PbCl(2) structure show a ferromagnetic-paramagnetic transition at 6 K, while the MnP-structured CoP nanowires are paramagnetic with Curie-Weiss behavior. Moreover, GC-MS analyses of organic byproducts of the reaction revealed that thermally generated phenyl radicals promoted the formation of transition-metal phosphides under synthetic conditions. Our work offers a general method for preparing one-dimensional nanoscale transition-metal phosphides that are promising for magnetic and electronic applications.

show abstract

Section: Introductionmentioning

confidence: 99%

Phase‐Controlled Synthesis of Transition‐Metal Phosphide Nanowires by Ullmann‐Type Reactions

Wang

Yang

Zhang

et al. 2010

Chemistry A European J

105

View full text Add to dashboard Cite

show abstract

“…[15][16] Barry et al reported an anhydrous solvothermal route to prepare phosphorous-rich transition metal phosphides without using an excess of phosphorous. 17 Perera et al used P(SiMe 3 3 to react with iron(III) acetylacetonate and manganese(III) acetylacetonate to prepare FeP and MnP nanoparticles. 18 Liu's group and Brock's group noted that trioctylphosphine (TOP) can be used as a phosphorous source in replace of very reactive P(SiMe 3 3 to form metal phosphides.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Anisotropic Transition Metal Phosphide Nanocrystals: The Case of Nickel Phosphide Nanoplatelets, Nanorods, and Nanowires

She¹,

Chen²,

Luo³

et al. 2010

J. Nanosci. Nanotech.

View full text Add to dashboard Cite

We have synthesized anisotropic nickel phosphide nanocrystals, including triangular/hexagonal nanoplatelets, nanorods and nanowires, via a solution-phase synthetic method that uses nickel(II) acetylacetonate as a metal precursor and trioctylphosphine as a phosphorus source. Nickel phosphide nanoplatelets have been prepared from a one-pot reaction, and their dimensions in the length mostly vary from 20 to 50 nm, while their thicknesses are in a narrow range of 7-9 nm. Nickel phosphide nanorods with a width of approximately 6 nm and a typical length of 25-32 nm can be synthesized from either the one-pot reaction or the multi-injection approach, although the latter can generate nanorods with a much higher uniformity. A continuous injection approach has been used to synthesize nanowires that have a typical width of approximately 6 nm and a length ranging from tens of nanometers up to several hundred nanometers. Major factors that influence the growth of nickel phosphide nanocrystals have been investigated, and a multi-surfactant system is found to be essential for the formation of anisotropic nanostructure. Magnetic studies have revealed paramagnetic characteristics for all the synthesized samples.

show abstract

“…[1] Cobaltrelated materials, including metallic cobalt, [2] cobalt oxide, [3] cobalt alloy, [4] and cobalt phosphide, [5] have been used in magnetic materials, aerospace engineering, and energy storage. With the development of modern nanoelectronic technology and the increasing demand for nanostructured materials, [6] the preparation of nanostructured inorganic cobaltcontaining materials has become a crucial technological challenge.…”

mentioning

confidence: 99%

Charged Metallopolymers as Universal Precursors for Versatile Cobalt Materials

et al. 2013

View full text Add to dashboard Cite

Inorganic metal-based materials have been widely utilized in catalytic chemistry, life sciences, and engineering. [1] Cobaltrelated materials, including metallic cobalt, [2] cobalt oxide, [3] cobalt alloy, [4] and cobalt phosphide, [5] have been used in magnetic materials, aerospace engineering, and energy storage. With the development of modern nanoelectronic technology and the increasing demand for nanostructured materials, [6] the preparation of nanostructured inorganic cobaltcontaining materials has become a crucial technological challenge. Various methods have been developed to prepare nanoscale inorganic cobalt-containing materials, including electrodeposition, [7] polymeric precursor synthesis, [8] solvothermal/hydrothermal methods, [5b, 9] and sol-gel precipitation. [10] Among them, the utilization of metal-containing polymer precursors to prepare nanostructured cobalt-based materials has been used in particular, for such reasons as controlled molecular weight and architectures offered by well-established controlled/living synthetic methods, various morphologies from polymer self-assembly, [11] and facile manipulation of polymers. [12] As a result, a myriad of metalcontaining polymer precursors in the form of thin films, micelles, or fibers have been designed and utilized for preparation of functional inorganic materials. [8] However, metal-containing polyelectrolytes or charged metallopolymers have been much less studied as precursors to prepare inorganic metal-based materials. [13] Compared with neutral metal-containing polymers, the existence of counterions in charged metallopolymers has several advantages as novel precursors, such as ion-dependent solubility [14] and ioninduced self-assembly. [15] Thus these polyelectrolytes could be universal precursors for access to multifunctional inorganic materials. Unfortunately, it is challenging to perform facile exchange of counterions for charged metallopolymers. Most studies have been limited to specific systems (usually small molecules [16] or super-macromolecules [17] ), thus severely restricting the diversity of charged metallopolymers.Phase transfer has been applied in various organic reactions [18] and utilized in applications such as ionic selfassembly, [19] heterogeneous catalysts, [18,20] and ionic liquids. [21] However, the utilization of phase transfer to tune metalassociated counterions for charged metallopolymers is much less explored. [15, 19b] We have recently demonstrated ion exchange between hexafluorophosphate (PF 6 À ) and tetraphenyl borate (BPh 4 À ) ions in cationic cobaltocenium-containing monomers/polymers, which was clearly a phase transfer-driven reaction. [14b, 22] But this specific reaction was only limited for BPh 4 À anions. It is still challenging to apply a powerful technique to access other types of counterions for cobaltocenium-containing polymers.Herein, we report a facile phase-transfer ion-exchange method to prepare cationic cobaltocenium-containing polyelectrolytes with diverse counterions by the use of tetrabutylam...

show abstract

Low-Temperature Solvothermal Synthesis of Phosphorus-Rich Transition-Metal Phosphides

Cited by 65 publications

References 39 publications

Phase‐Controlled Synthesis of Transition‐Metal Phosphide Nanowires by Ullmann‐Type Reactions

Phase‐Controlled Synthesis of Transition‐Metal Phosphide Nanowires by Ullmann‐Type Reactions

Preparation of Anisotropic Transition Metal Phosphide Nanocrystals: The Case of Nickel Phosphide Nanoplatelets, Nanorods, and Nanowires

Charged Metallopolymers as Universal Precursors for Versatile Cobalt Materials

Contact Info

Product

Resources

About