First Row Transition Metal Phosphides

Whitmire, Kenton H.; Caudell, Jacob B.

doi:10.1002/9781119951438.eibc2160

Cited by 4 publications

(3 citation statements)

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“…This structural variety is attributed to the bonding flexibility of phosphorus, which may be present as individual anions, dumbbells, or larger networks . Because metal phosphides feature diverse structural motifs and compositional ranges, they can display a wide range of magnetic, catalytic, and transport properties. ,− Furthermore, they often boast high thermal stability and corrosion resistance. As a result, transition metal phosphides have been considered for a number of applications.…”

Section: Introductionmentioning

confidence: 99%

NiP₂: A Story of Two Divergent Polymorphic Multifunctional Materials

Owens‐Baird

Petrovykh

et al. 2019

Chem. Mater.

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In this paper, we explore the drastic differences in transport properties and catalytic activities for two structural polymorphs of NiP 2 : cubic (Pa3; No. 205) and monoclinic NiP 2 (C2/c; No. 15). The former one has been long assumed to be the high-pressure metastable phase, as it had been originally synthesized through high-pressure methods. Synthetic and in situ synchrotron X-ray diffraction studies unambiguously show that the cubic polymorph can be synthesized at ambient pressure but irreversibly transforms into the monoclinic structure above 876 K. Band structure calculations and transport measurements show that cubic NiP 2 is a semimetal, while the monoclinic polymorph is an ntype direct band gap semiconductor. Both compounds exhibit low thermal conductivities, with cubic NiP 2 exhibiting a value of 1.7 W•m −1 K −1 at 300 K. The bulk structure of the phosphides may affect the surface-related properties. Unlike the monoclinic polymorph, cubic NiP 2 excels in both half-cell HER and OER measurements. In alkaline half-cell OER, cubic NiP 2 outperforms the RuO 2 standard. More importantly, HER tests in a PEM electrolysis single cell showed high promise for cubic NiP 2 , which requires only 13% higher overpotentials when compared to state-of-the-art Pt/IrRuO x -based assemblies, far surpassing any reported properties of metal pnictide or chalcogenide full cells.

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Section: Introductionmentioning

confidence: 99%

NiP₂: A Story of Two Divergent Polymorphic Multifunctional Materials

Owens‐Baird

Petrovykh

et al. 2019

Chem. Mater.

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“…For example, Ni 12 P 5 and Ni 3 P possess a tetragonal structure, whereas Ni 5 P 4 , Ni 5 P 2 , and Ni 2 P possess a hexagonal structure. Ni 7 P 3 and NiP 3 have a cubic structure, whereas Ni 8 P 3 , NiP, and NiP 2 retain trigonal, orthorhombic, and monoclinic structures, respectively [51] (shown in Figure 1). One should note that the NiP 2 also has a cubic phase [52].…”

Section: Crystal Structures Of Ni X P Ymentioning

confidence: 99%

A Review of the Structure–Property Relationship of Nickel Phosphides in Hydrogen Production

Chen,

Wei

2024

Energies

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Hydrogen, one of the most promising forms of new energy sources, due to its high energy density, low emissions, and potential to decarbonize various sectors, has attracted significant research attention. It is known that electrocatalytic hydrogen production is one of the most widely investigated research directions due to its high efficiency in the conversion of electricity to H2 gas. However, given the limited reserves and high cost of precious metals, the search for non-precious metal-based catalysts has been widely explored, for example, transition metal phosphides, oxides, and sulfides. Despite this interest, a detailed survey unveils that the surface and internal structures of the alternative catalysts, including their surface reconstruction, composition, and electronic structure, are poorly studied. As a result, a disconnection in the structure–property relationship severely hinders the rational design of efficient and reliable non-precious metal-based catalysts. In this review, by focusing on Ni5P4, a bifunctional catalyst for water splitting, we systematically summarize the material motifs pertaining to the different synthetic methods, surface characteristics, and hydrolysis properties. It is believed that a cascaded correlation may provide insights toward understanding the fundamental catalytic mechanism and design of robust alternative catalysts for hydrogen production.

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“…A major thrust of research in our laboratory has been the development of single-source precursors (SSPs) for complex binary and ternary metal pnictides, systems in which multiple phases are possible for a given combination of elements. In contrast to systems like those of cadmium sulfide and cadmium selenide where only one phase for the combination of elements exists, iron phosphide has multiple combinatory mixtures possible: FeP 4 , FeP 2 , FeP, Fe 2 P, and Fe 3 P, each with discrete phases and structures . These compositional and structural differences create a diverse and attractive set of properties unique to each combinatory mixture.…”

Section: Introductionmentioning

confidence: 99%

Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et₄N]₂[HAs{Fe(CO)₄}₃] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials

2016

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The chemistry of [Et 4 N] 2 [HAs{Fe(CO) 4 } 3 ] ([Et 4 N] 2 [I]) has been explored with the goal of preparing heterometallic compounds for use as single-source precursors to metal pnictide phases. Reaction of AgPF 6 with [Et 4 N] 2 [I] in THF produces [Et 4 N][HAs{Fe 2 (CO) 6 (μ-CO)(μ-H)}{Fe-(CO) 4 }] in 12% yield, but the yield is improved to 71% if the reaction is carried out with added [Et 4 N][HFe(CO) 4 ]. The structure possesses rare As−H and {Fe 2 (CO) 6 (μ-CO)(μ-H)} fragments. The addition of [CPh 3 ][BF 4 ] to [Et 4 N] 2 [I] in THF gives [Et 4 N][Fe 3 (CO) 9 (μ-CO){μ 3 -AsFe(CO) 4 }] in 45% yield. This compound is also obtained as a minor product from oxidation of [Et 4 N] 2 [I] with 1 equiv of AgPF 6, AsCl 3, SbCl 3 , or BiCl 3 in THF. The cluster consists of an Fe 3 As tetrahedron with an isolated Fe(CO) 4 unit bound to the arsenic in a spikedtetrahedral arrangement. Refluxing [Et 4 N] 2 [I] with 1 equiv of AgPF 6 in THF produces [Et 4 N][(μ-H) 2 Fe 3 (CO) 9 ){μ 3 -AsFe(CO) 4 }]. This cluster is similar to [Et 4 N][Fe 3 (CO) 9 (μ-CO){μ 3 -AsFe(CO) 4 }] with the bridging CO being replaced by two bridging hydride ligands. Treatment of [Et 4 N] 2 [I] with 1 equiv of Mn(CO) 5 Br in THF gives the spirocyclic compound [Et 4 N][{FeMn(CO) 8 }(μ 4 -As){Fe 2 (CO) 6 (μ-CO)(μ-H)}] in 52% yield. Refluxing this cluster in the presence of triethylamine and an additional 1.8 equiv of Mn(CO) 5 Br gives [Et 4 N][Fe 3 (CO) 9 (μ-CO){μ 3 -AsMn(CO) 4 Br-cis}] in low yield. Alternatively, treating [Et 4 N][{FeMn(CO) 8 }(μ 4 -As){Fe 2 (CO) 6 (μ-CO)(μ-H)}] with triflic acid or an oxidant ([Ox] = Cu + , Ag + , Cu 2+ , CPh 3 + ) in dichloromethane produces the two neutral compounds (μ-H) 2 Fe 3 (CO) 9 {μ 3 -AsMn(CO) 5 } and {FeMn(CO) 8 }(μ 4 -As){Fe 2 (CO) 8 } in trace amounts and high yield, respectively. The former could be removed by treatment with base in nonpolar solvents. Neutral {FeMn(CO) 8 }(μ 4 -As){Fe 2 (CO) 8 } can then be isolated by filtration and evaporation in 74% yield. An improved synthesis of the known [Fe 3 (CO) 9 (μ-CO){μ 3 -PFe(CO) 4 }] − as its tetraethylammonium salt is also included. All compounds were characterized by spectroscopy, by ESI-mass spectrometry, and by single-crystal X-ray diffraction.

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First Row Transition Metal Phosphides

Cited by 4 publications

References 166 publications

NiP₂: A Story of Two Divergent Polymorphic Multifunctional Materials

NiP₂: A Story of Two Divergent Polymorphic Multifunctional Materials

A Review of the Structure–Property Relationship of Nickel Phosphides in Hydrogen Production

Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et₄N]₂[HAs{Fe(CO)₄}₃] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials

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First Row Transition Metal Phosphides

Cited by 4 publications

References 166 publications

NiP2: A Story of Two Divergent Polymorphic Multifunctional Materials

NiP2: A Story of Two Divergent Polymorphic Multifunctional Materials

A Review of the Structure–Property Relationship of Nickel Phosphides in Hydrogen Production

Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et4N]2[HAs{Fe(CO)4}3] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials

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NiP₂: A Story of Two Divergent Polymorphic Multifunctional Materials

NiP₂: A Story of Two Divergent Polymorphic Multifunctional Materials

Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et₄N]₂[HAs{Fe(CO)₄}₃] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials