Phosphorus Nitride Research Articles

Phosphorus nitride dot-activated ferrate (VI) with enhanced singlet oxygen mediating chemiluminescence for pyroquilon determination

Phosphorus nitride dot-activated ferrate (VI) with enhanced singlet oxygen mediating chemiluminescence for pyroquilon determination

ZnH2P4N8: Case Study on Topochemical Imidonitridophosphate High-Pressure Synthesis.

Nitridophosphates are subject of current research, as they have a broad spectrum of properties and potential applications, such as ion conductors or luminescent materials. Yet, the subclass of imidonitridophosphates has been studied less extensively. The primary reason is that the controlled N-H functionalization of nitridophosphates is not straight forward, making targeted synthesis more challenging. Inspired by the high-pressure (HP) post-synthetic modification of nitridophosphates, we present the topochemical HP deprotonation of phosphorus nitride imides using the high-pressure polymorph β-PN(NH) as an example. Additional incorporation of Zn2+ results in the first quaternary transition metal imidonitridophosphate ZnH2P4N8. The crystal structure was elucidated by single-crystal X-ray diffraction (SCXRD), energy-dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (PXRD) and solid-state magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). In addition, the presence of H as part of an imide group was confirmed by IR spectroscopy. The potential of this defunctionalization approach for controlling the N-H content is demonstrated by the preparation of partially deprotonated intermediates ZnxH4-2xP4N8 (x≈0.5, 0.85). This topochemical high-pressure reaction represents a promising way to prepare, control and manipulate new imide-based materials without altering their overall anionic framework.

Covalently anchoring phosphorus nitride imide on carbon nanotubes for efficient electrochemical extraction of uranium

The electrochemical extraction technique is an emerging approach for the recovery of uranium. However, the ultra-high salinity and the coexistence of many competitive ions seriously reduce the electrochemical extraction performance of uranium. Phosphorus nitride imide (PN) demonstrates high efficiency and selectivity as a uranium adsorbent. However, its low conductivity adversely affects its electrochemical performance. In this work, the covalent grafting strategy has been employed to anchor PN onto carbon nanotubes (PN@CNT) toward efficient electrochemical extraction of uranium (EEU). CNTs not only serve as an optimal carrier for the dispersion of PN, but also establish a three-dimensional conductive network for PN, thereby facilitating the fixation and reduction of uranium ions. This ingenious structural design enables outstanding EEU performance: PN@CNT demonstrates an extremely high uranium adsorption capacity (1006.9 mg/g), excellent anti-interference and satisfactory cycle stability. PN@CNT reduced uranium-spiked groundwater from 5 mg/L to 15 μg L−1 within 12 h which meets the drinking water standard (30 μg L−1). This study offers a potential material for the EEU, while also serving as a reference for the development of electrodes in the electrochemical recovery of other heavy metals.

Observations of phosphorus-bearing molecules in the interstellar medium

The chemistry of phosphorus (31P) in space is particularly significant due to the key role it plays in biochemistry on Earth. Utilising radio and infrared spectroscopic observations, several key phosphorus-containing molecules have been detected in interstellar clouds, circumstellar shells, and even extragalactic sources. Among these, phosphorus nitride (PN) was the first P-bearing molecule detected in space, and still is the species detected in the largest number of sources. Phosphorus oxide (PO) and phosphine (PH3) were also crucial species due to their role both in chemical networks and in forming biogenic compounds. The still limited high-angular resolution observations performed so far are shading light on the geometrical distribution of these molecules, which represent crucial insights on their formation processes. Observations have also highlighted the challenges and complexities associated with detecting and understanding phosphorus chemistry in space, owing to the low elemental abundance of P relative to other elements. This review article provides a state-of-art picture of the observational results obtained so far on phosphorus compounds in the interstellar medium. Special attention is given to star-forming regions, and to their implications for our understanding of prebiotic chemistry and the potential for life beyond Earth. Our knowledge of the dominant formation and destruction pathways of the most abundant species has improved, but critical questions remain open, among which: what is (are) the main phosphorus carrier(s) in space? Upcoming new facilities are expected to contribute significantly to this field, offering opportunities to both detect new phosphorus-bearing molecules and enlarge the number of sources in which the chemistry of P can be studied. The synergy between observations, theoretical models, laboratory experiments, and computational chemistry is mandatory to significantly progress in our comprehension of the chemistry of this important but poorly studied chemical element.

Phosphorus Nitride Imide Nanotubes for Uranium Capture from Seawater.

Nuclear power plays a pivotal role in the global energy supply. The adsorption-based extraction of uranium from seawater is crucial for the rapid advancement of nuclear power. The phosphorus nitride imide (PN) nanotubes were synthesized in this study using a solvothermal method, resulting in chemically stable cross-linked tubular hollow structures that draw inspiration from the intricate snowflake fractal pattern. Detailed characterization showed that these nanotubes possess a uniformly distributed five-coordinated nanopocket, which exhibited great selectivity and efficiency in binding uranium. PN nanotubes captured 97.34% uranium from the low U-spiked natural seawater (∼355 μg L-1) and showed a high adsorption capacity (435.58 mg g-1), along with a distribution coefficient, KdU > 8.71 × 107 mL g-1. In addition, PN nanotubes showed a high adsorption capacity of 7.01 mg g-1 in natural seawater. The facile and scalable production of PN nanotubes presented in this study holds implications for advancing their large-scale implementation in the selective extraction of uranium from seawater.

Out-of-Plane Single-Copper-Site Catalysts for Room-Temperature Benzene Oxidation.

Crafting single-atom catalysts (SACs) that possess "just right" modulated electronic and geometric structures, granting accessible active sites for direct room-temperature benzene oxidation is a coveted objective. However, achieving this goal remains a formidable challenge. Here, we introduce an innovative in situ phosphorus-immitting strategy using a new phosphorus source (phosphorus nitride, P3N5) to construct the phosphorus-rich copper (Cu) SACs, designated as Cu/NPC. These catalysts feature locally protruding metal sites on a nitrogen (N)-phosphorus (P)-carbon (C) support (NPC). Rigorous analyses, including X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS), validate the coordinated bonding of nitrogen and phosphorus with atomically dispersed Cu sites on NPC. Crucially, systematic first-principles calculations, coupled with the climbing image nudged-elastic-band (CI-NEB) method, provide a comprehensive understanding of the structure-property-activity relationship of the distorted Cu-N2P2 centers in Cu/NPC for selective oxidation of benzene to phenol production. Interestingly, Cu/NPC has shown more energetically favorable C-H bond activation compared to the benchmark Cu/NC SACs in the direct oxidation of benzene, resulting in outstanding benzene conversion (50.3 %) and phenol selectivity (99.3 %) at room temperature. Furthermore, Cu/NPC achieves a remarkable turnover frequency of 263 h-1 and mass-specific activity of 35.2 mmol g-1 h-1, surpassing the state-of-the-art benzene-to-phenol conversion catalysts to date.

Out‐of‐Plane Single‐Copper‐Site Catalysts for Room‐Temperature Benzene Oxidation

AbstractCrafting single‐atom catalysts (SACs) that possess “just right” modulated electronic and geometric structures, granting accessible active sites for direct room‐temperature benzene oxidation is a coveted objective. However, achieving this goal remains a formidable challenge. Here, we introduce an innovative in situ phosphorus‐immitting strategy using a new phosphorus source (phosphorus nitride, P3N5) to construct the phosphorus‐rich copper (Cu) SACs, designated as Cu/NPC. These catalysts feature locally protruding metal sites on a nitrogen (N)‐phosphorus (P)‐carbon (C) support (NPC). Rigorous analyses, including X‐ray absorption spectroscopy (XAS) and X‐ray photoelectron spectroscopy (XPS), validate the coordinated bonding of nitrogen and phosphorus with atomically dispersed Cu sites on NPC. Crucially, systematic first‐principles calculations, coupled with the climbing image nudged‐elastic‐band (CI‐NEB) method, provide a comprehensive understanding of the structure‐property‐activity relationship of the distorted Cu−N2P2 centers in Cu/NPC for selective oxidation of benzene to phenol production. Interestingly, Cu/NPC has shown more energetically favorable C−H bond activation compared to the benchmark Cu/NC SACs in the direct oxidation of benzene, resulting in outstanding benzene conversion (50.3 %) and phenol selectivity (99.3 %) at room temperature. Furthermore, Cu/NPC achieves a remarkable turnover frequency of 263 h−1 and mass‐specific activity of 35.2 mmol g−1 h−1, surpassing the state‐of‐the‐art benzene‐to‐phenol conversion catalysts to date.

Electronic, Elastic, Piezoelectric, and Infrared Properties of 2D Phosphorus Oxynitride by First Principles

Bulk phosphorus oxynitride (PON), isoelectronic with SiO2, is confirmed to have many polymorphs as the latter. However, its 2D counterparts have not been studied. In this work, crystal structure exploration and property study are performed on 2D PON with the help of first‐principle calculation. Three 2D PON sheets are found with thermal, dynamical, and mechanical stability and all of them can be viewed as oxygen‐doped known 2D γ phosphorus nitride (γ‐PN). In the studies, it is indicated that they are indirect bandgap materials with gap values larger than 3 eV. The situations of orbital hybridization are discussed and their bonding properties are analyzed. Infrared vibrational spectra of these 2D materials are simulated and the vibrational modes at the Brillouin center are assigned by the factor group analysis. The reasons for the disappearance of some infrared peaks in the simulated spectra are revealed based on the calculated Born effective charges and vibrational eigenvectors. Their piezoelectric stress tensors are computed via density‐functional perturbation method and the piezoelectric strain tensors are also deduced via the calculated elastic constants. In the results, it is uncovered that these 2D PON sheets have considerably greater piezoelectric coefficients than the primitive 2D γ‐PN, which make them promising for nanopiezoelectric use.

Nitride Synthesis under High-Pressure, High-Temperature Conditions: Unprecedented In Situ Insight into the Reaction.

High-pressure, high-temperature (HP/HT) syntheses are essential for modern high-performance materials. Phosphorus nitride, nitridophosphate, and more generally nitride syntheses benefit greatly from HP/HT conditions. In this contribution, we present the first systematic in situ investigation of a nitridophosphate HP/HT synthesis using the reaction of zinc nitride Zn3N2 and phosphorus(V) nitride P3N5 to the nitride semiconductor Zn2PN3 as a case study. At a pressure of 8 GPa and temperatures up to 1300 °C, the reaction was monitored by energy-dispersive powder X-ray diffraction (ED-PXRD) in a large-volume press at beamline P61B at DESY. The experiments investigate the general behavior of the starting materials under extreme conditions and give insight into the reaction. During cold compression and subsequent heating, the starting materials remain crystalline above their ambient-pressure decomposition points, until a sufficient minimum temperature is reached and the reaction starts. The reaction proceeds via ion diffusion at grain boundaries with an exponential decay in the reaction rate. Raising the temperature above the minimum required value quickly completes the reaction and initiates single-crystal growth. After cooling and decompression, which did not influence the resulting product, the recovered sample was analyzed by energy-dispersive X-ray (EDX) spectroscopy.

Phosphorous nitride dots induced efficient advanced oxidation with intrinsic chemiluminescence for organic pollutant degradation.

In this work, we introduced new metal-free catalysts, phosphorus nitride dots (PNDs), into an environmentally friendly H2O2-SO32- system to generate abundant reactive oxygen species (O2˙-, ˙OH and SO4˙-) with strong intrinsic chemiluminescence (CL). The excellent catalytic ability of PNDs not only improved the degradation efficiency of organic pollutants, but also provided a promising prospect for deeply probing the mechanism of advanced oxidation processes (AOPs) by combining with CL.

ACA observation and chemical modeling of phosphorus nitride towards hot molecular cores G10.47$$\varvec {+}$$0.03 and G31.41$$\varvec {+}$$0.31

ACA observation and chemical modeling of phosphorus nitride towards hot molecular cores G10.47$$\varvec {+}$$0.03 and G31.41$$\varvec {+}$$0.31

Carbon and Oxygen-Doped Phosphorus Nitride (COPN) for Continuous Selective and Stable H2O2 Production

Carbon and Oxygen-Doped Phosphorus Nitride (COPN) for Continuous Selective and Stable H₂O₂ Production

First‐Principles Study of the C‐ and Si‐Doped Buckled Honeycomb PN Monolayer

AbstractIn this work, the effects of doping with carbon (C) and silicon (Si) on the electronic and magnetic properties of phosphorus nitride (PN) monolayer are investigated. PN monolayer is stable, exhibiting the semiconductor nature with indirect band gap of 1.81(2.89) eV calculated by standard Perdew–Burke–Ernzerhof (hybrid HSE06) functional. C and Si impurities prefer doping at N and P sublattices, respectively. PN monolayer is slightly magnetized by doping with 25% of C with total magnetic moment of 0.20 . The magnetization is stronger in the remaining cases with total magnetic moments of 1.00 . Magnetic properties are produced mainly by C and Si impurities. In addition, C and Si codoping is also investigated, in which the magnetization depends strongly on the interatomic distance between impurities. Specifically, the inter‐dopant interactions preserve the non‐magnetic nature of PN monolayer, but significantly reduce the energy gap. However, further separating these dopants leads to the emergence of magnetism with total magnetic moment of up to 1.97 . Results may introduce doping‐based effective method to induce feature‐rich electronic and magnetic properties in buckled honeycomb PN monolayer. Such that, the C‐ and Si‐doped PN sheets are recommended for spintronic applications considering their magnetic semiconductor nature.

Detonation of high explosives containing phosphorus(V) nitride, P3N5

AbstractComposition A4 (RDX/wax, 94/6 wt %) modified with additional phosphorus(V) nitride, P3N5 (CAS‐No.: [12136‐91‐3]) and aluminum does not show increased detonation velocity, Gurney energy or blast pressure when compared with the baseline formulation. The general failure of P3N5 to contribute to the detonation performance is understood to result from the low negative enthalpy of formation of P3N5 that makes this compound a “heat sink” in the detonation and post detonation zone. A formulation containing both P3N5 and Al (RDX/P3N5/Al/wax: 50.76/36/10/3.24 wt %) shows superior luminosity and temperature of the post detonation fireball when compared with both Comp A4 and even aluminized Comp A4 (Hexal=RDX/Al/wax: 65.8/30/4.2 wt %). The superior luminosity is understood to be due to formation of aluminum phosphate, AlPO4 a material with high optical emissivity which however, decomposes above T=1600 °C.

Improved potential-energy and dipole-moment functions of the ground electronic state of phosphorus nitride

Ab initio calculations of the PN potential and electric dipole moment in the X1Σ+ ground electronic state were performed at short bond lengths, r=0.2–0.8 Å, and semi-empirical analytical potential-energy and dipole-moment functions were constructed based on all available experimental and theoretical information. The analytical forms for the potential-energy functions include the Extended Morse Oscillator and the Extended Hulburt-Hirshfelder potential. The dipole-moment function of PN was presented by our irregular and rational functions previously used for CO. The potential-energy and dipole-moment model functions were fitted simultaneously to the experimental line positions and permanent dipoles at v=0-2, as well as to the ab initio data from our present and previous studies. With these new functions, the improved line list for the ground electronic state of 31P14N was calculated. We show that the new analytic representations of the potential and dipole moment functions help significantly reduce the numerical noise in the intensities of high overtones as well as the associated saturation at high wavenumbers leading to the so-called “overtone plateaus” in spectra of diatomic molecules (see Medvedev et al., J. Mol. Spectrosc., 330, 36 (2016)) and thus provide reliable transition intensities at very high transition frequencies. The 3-0 band is identified as vibrational anomaly, and rotational anomalies inside this and some other bands are found.

Subtraction by addition: Chalcogen-oxidation induced N[sbnd]C bond scissions in bis(amido)cyclodiphosphazane chelates of the group 15 elements

The phosphorus-nitrogen heterocycle cis-[(tBuNH)P(μNtBu)2P(NHtBu)], A, is readily oxidized at phosphorus with chalcogens to yield the corresponding dichalcogenide cis-[(tBuNH)Ch=P(μNtBu)2P=Ch(NHtBu)], B. Both A and B can be deprotonated to yield dianionic ligands, but while A encapsulates metals and nonmetals as a desirable chelating N, N’ diamide, B forms the less desirable N, Ch chelates, which are less reactive. Here we report on the post-chelation oxidation of Group 15 chelates of B in which the ligand functions as the desired N, N’ diamide. Chelates of P, As, and Sb, each bearing the monodentate ligands Cl, Ph, and N3 were oxidized to mono- and dichalcogenides with elemental sulfur and selenium. The nature of the monodentate ligands had only minor effects on the rate of oxidation, but selenium was always the much faster oxidant. At elevated temperatures the chelated phosphorus atom was oxidized to yield tri-chalcogenides, but chelated As and Sb were never oxidized. At sufficiently high temperature even the loss of tert-butyl groups and of Cl from the chelates was observed to furnish a phosphorus nitride. The solid-state structures of most products were studied and are discussed.

Improved Potential-Energy and Dipole-Moment Functions of the Ground Electronic State of Phosphorus Nitride

Improved Potential-Energy and Dipole-Moment Functions of the Ground Electronic State of Phosphorus Nitride

Destruction of phosphorus nitride through the N(4S) + PN(1Σ+) → N2(1Σ+) + P(4S) reaction

ABSTRACT The study of reactions involving phosphorus bearing species (PBS) in star-forming regions as well as in circumstellar envelopes are important to elucidate the mechanisms in which this element is formed and destroyed, and perhaps, lead to important pre-biotic molecules. Phosphorus nitride (PN) is the most easily detected PBS in the interstellar medium (ISM), and is considered as one of the major reservoirs of this element in the ISM. However, only a few of its reactions have been analysed experimentally or computationally. Therefore, modelling PN chemistry and interpretation of the observations suffer uncertainties, affecting our astrochemical understanding of this species. In this work, we perform explicitly correlated multireference configuration interaction (MRCI+Q/AVTZ+d//CAS/AVTZ+d) calculations on the destruction of PN through the N(4S) + PN(1Σ+) reaction. We have also performed DFT (M06-2X) and CCSD(T) calculations for benchmark purposes. Rate coefficients over a large range of temperatures were computed using standard transition state theory (TST), canonical variational TST (CVT), and also incorporating tunneling effects with the small curvature tunneling method (SCT). We found that the NPN system possesses a considerable multireference character, and the DFT approach cannot properly describe the available destruction mechanisms. Our best estimate for the rate coefficients, at the MRCI+Q/AVTZ+d level, can be described by the modified Arrhenius equation 1.09×10−11(T/300)−1.02exp (− 7919/T). We show for the first time that this reaction may be considerably fast in shock regions and in high temperature environments of solar-type star forming regions, and of significant importance to model the abundance of PN in such environments.

Front Cover: Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′‐P3N5, δ‐P3N5 and PN2 (Chem. Eur. J. 62/2022)

For the last 30 years, the lack of a binary phosphorus nitride containing PN6 octahedra formed a scientific chasm between carbon-group and oxygen-group nitrides, both featuring a variety of solids with XN6 units (X being a non-metal element). Now, the discovery of the δ-P3N5 and PN2 phosphorus nitrides—formed under high pressure and both composed of the elusive PN6 octahedron—builds a long-sought-after bridge between these two groups of nitrides. More information can be found in the Research Article by D. Laniel, F. Trybel, and co-workers (DOI: 10.1002/chem.202201998).

A theoretical study on the electronically excited-state spectroscopic properties of phosphorus nitride

ABSTRACT The potential energy curves of 103 Ω states generated from the 39 Λ–S states of PN have been calculated using the internally contracted multireference configuration interaction method with the Davidson modification. Core-valence correlation and scalar relativistic corrections, as well as the basis-set extrapolation to the complete basis set limit are considered. The spin–orbit coupling is computed using the state interaction approach with the Breit-Pauli Hamiltonian. The spectroscopic parameters and molecular constants of bound and quasibound Λ–S and Ω states are evaluated. Our calculated spectroscopic results agree quite well with the available experimental data. The interactions among different electronic states in curve crossing regions have been discussed with the help of computed spin–orbit coupling matrix elements. The perturbations and predissociation phenomena of the A1 , b3 , D1Δ, E1Σ+, and 21 states and so on have been revealed.