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1. Effect of nickel phosphide phase on the photo-thermal catalytic hydrogenation of carbon dioxide

   https://doi.org/10.1016/j.cattod.2025.115185  

   Hennig, Hannah K; Schare, Jacob R; Lynch, Reilly P; Bullock, Alex; Baldwin, Michael S; Bussell, Mark E (April 2025, Catalysis Today)

   Khatib, Sheima J; Groppo, Elena (Ed.)

   The CO2 hydrogenation (HYD) reaction was investigated over Ni phosphide (Ni3P, Ni12P5, Ni2P) catalysts to probe the effect of the NixPy phase on photo-thermal catalytic properties in comparison to Ni metal. The light absorption properties of 2.5 wt% NixPy/SiO2 catalysts differ substantially, with the extent of light absorption decreasing as the P/Ni molar ratio of the Ni phosphide phase increases. This finding directly impacts the photo-thermal catalytic properties as the photo-enhancement (light activity / dark activity) correlates linearly with the extent of light absorption. For comparison purposes, 2.5 wt% Ni/SiO2 catalysts were also investigated and showed high activity but suffered from low CO selectivity (57-68%). A Ni3P/SiO2 catalyst was the most active of the Ni phosphides with high CO selectivity (>95%), while Ni12P5/SiO2 and Ni2P/SiO2 catalysts had lower CO2 HYD activities but CO selectivities above 98%. Upon light exposure, the NixPy/SiO2 (and Ni/SiO2) catalysts exhibited significant rises of temperature (~200 K increase from room temperature), indicating the importance of photothermal heating in increasing the CO2 HYD rate. The findings highlight how a non-metal element (i.e., P) plays a crucial role in tailoring the photo-thermal catalytic properties of earth abundant nickel metal. 

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2. Computational screen of M ₂ P metal phosphides for catalytic ethane dehydrogenation

   https://doi.org/10.1039/D2CY00602B  

   Ko, Jeonghyun; Schneider, William F. (September 2022, Catalysis Science & Technology)

   Metal phosphides are promising catalysts for hydrocarbon transformations, but computational screening is complicated by their diverse structures and compositions. To disentangle structural from compositional contributions, here we explore the metal-rich M 2 P (M = Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, Pt) series in hexagonal and orthorhombic structures that are common to a subset of these materials, using supercell density functional theory (DFT). To understand the contribution of metal choice to utility for catalytic ethane dehydrogenation (EDH), we compute and compare the adsorption of key EDH intermediates across low-index surface terminations. These materials expose both metal and phosphide sites. Calculations show that binding energies at metal sites correlate with the bulk metals, with P incorporation either enhancing or suppressing binding. Phosphide sites compete with metal sites for adsorbates and tend to suppress overactivation by destabilizing highly dehydrogenated species engaging in C–H bond breaking. Results are generally insensitive to bulk structure and surface facet. Results suggest metal-rich Pd phosphides to have favorable adsorption characteristics for catalytic dehydrogenation, consistent with recent observations. 

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3. In situ synthesis and in operando NMR studies of a high-performance Ni ₅ P ₄ -nanosheet anode

   https://doi.org/10.1039/C8TA05433A  

   Feng, Xuyong; Tang, Mingxue; O'Neill, Sean; Hu, Yan-Yan (November 2018, Journal of Materials Chemistry A)

   Nickel phosphide (Ni 5 P 4 ) nanosheets are synthesized using in situ chemical vapor deposition of P on Ni foam. The thickness of the as-synthesized Ni 5 P 4 film is determined to be ∼5 nm, using atomic force microscopy (AFM). The small thickness shortens the diffusion path of Li ions and results in fast ion transport. In addition, the 2D Ni 5 P 4 nanosheets seamlessly connect to the Ni foam, which facilitates electron transfer between Ni 5 P 4 and the Ni current collector. Therefore, the binder/carbon free-nickel supported Ni 5 P 4 shows fast rate performance as an anode for lithium-ion batteries (LIBs). The specific capacity of 2D Ni 5 P 4 is obtained as 600 mA h g −1 at a cycling rate of 0.1C, approaching the theoretical capacity of 768 mA h g −1 . Even at a rate of 0.5C, the capacity remains as 450 mA h g −1 over 100 cycles. A capacity >100 mA h g −1 is retained at a very high rate of 20C. Ni 5 P 4 also exhibits a low voltage of ∼0.5 V with respect to Li metal, which makes it a suitable negative electrode for LIBs. In operando 31 P NMR and 7 Li NMR are employed to probe the lithiation and de-lithiation mechanisms upon electrochemical cycling. 

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4. Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation

   https://doi.org/10.1039/c7cc06841g  

   Joost, Maximilian; Transue, Wesley J.; Cummins, Christopher C. (January 2017, Chemical Communications)

   Tungsten( iv ) tetrakis(2,6-diisopropylphenoxide) ( 1 ) has been demonstrated to be a competent platform for decarbonylative formation of anionic terminal pnictide complexes upon treatment with pnictaethynolate anions: cyanate, 2-phosphaethynolate, and 2-arsaethynolate. These transformations constitute the first examples of terminal phosphide and arsenide complex formation at a transition metal center from OCP − and OCAs − , respectively. The phosphide and arsenide complexes are also the first to be isolated in a tetragonal, all-oxygen ligand environment. The scalar NMR coupling constants between tungsten-183 and nitrogen-15 or phosphorus-31 have been measured and contextualized using natural bond orbital (NBO) methods in terms of s orbital character in the σ bonding orbital and pnictide lone pair. 

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5. Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity

   https://doi.org/10.1002/anie.201808307  

   Buss, Joshua A.; Hirahara, Masanari; Ueda, Yohei; Agapie, Theodor (November 2018, Angewandte Chemie International Edition)

   Abstract A new series of low‐valent dinuclear molybdenum complexes bearing phosphido or phosphinidene bridging ligands was synthesized as a structural model of heterogeneous metal phosphide catalysts. Addition of acid to a monocationic Mo₂‐μ‐P complex results in phosphide protonation, affording a dicationic Mo₂‐μ‐PH species. Alternatively, reaction of an isoelectronic Mo₂‐μ‐P precursor with LiBEt₃H gives a Mo₂H‐μ‐P complex. Mixing these species, one bearing a Mo−H and the other a P−H bond, results in facile H₂production at room temperature. 

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