One-pot synthesis of magnetic iron phosphide nanoparticles

Article abstract of DOI:10.1080/24701556.2020.1728551

A novel one-pot synthetic method to produce crystalline tri-octylphosphine (TOP) capped iron phosphide nanoparticles is reported here. Standard method of synthesizing FeP includes preparation of a precursor, sodium phosphide, which is finally reacted with ferric chloride (FeCl₃).The methods for synthesizing iron phosphide (FeP), reported so far, rely on the use of toxic red or yellow phosphorus to generate the precursor, Sodium phosphide (Na₃P). In present investigation, instead of red or yellow phosphorus, a relatively less toxic substance TOP and sodium metal (Na) have been used to yield Na₃P. The synthesized nanoparticles were fully characterized by X-ray diffraction pattern (XRD), Infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM) and superconducting quantum interference device (SQUID) analyses. The results showed that the synthesized FeP nanoparticles have the characteristic orthorhombic crystal structures, with the size ～10 nm and the coercivity 70 Oe at RT.

Full text of DOI:10.1080/24701556.2020.1728551

Inorganic and Nano-Metal Chemistry
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One-pot synthesis of magnetic iron phosphide
nanoparticles
Deepali Ahluwalia, Atul Varshney, Sachin Kumar, Anil Kumar, Sudhir
Gopalrao Warkar, Narendra Singh & Prashant Dubey
To cite this article: Deepali Ahluwalia, Atul Varshney, Sachin Kumar, Anil Kumar, Sudhir Gopalrao
Warkar, Narendra Singh & Prashant Dubey (2020): One-pot synthesis of magnetic iron phosphide
nanoparticles, Inorganic and Nano-Metal Chemistry, DOI: 10.1080/24701556.2020.1728551
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INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2020.1728551
One-pot synthesis of magnetic iron phosphide nanoparticles
a
a
a
a
a
a
Deepali Ahluwalia , Atul Varshney , Sachin Kumar , Anil Kumar , Sudhir Gopalrao Warkar , Narendra Singh , and
Prashant Dubey
b
a
b
Department of Applied Chemistry, Delhi Technological University, Delhi, India; Center for Material Science, University of Allahabad,
Allahabad, India
ABSTRACT
ARTICLE HISTORY
A novel one-pot synthetic method to produce crystalline tri-octylphosphine (TOP) capped iron
phosphide nanoparticles is reported here. Standard method of synthesizing FeP includes prepar-
Received 12 August 2019
Accepted 2 February 2020
ation of a precursor, sodium phosphide, which is finally reacted with ferric chloride (FeCl
methods for synthesizing iron phosphide (FeP), reported so far, rely on the use of toxic red or yel-
low phosphorus to generate the precursor, Sodium phosphide (Na P). In present investigation,
3
).The
KEYWORDS
Synthesis; nanoparticles;
sodium phosphide; iron
phosphide; toxic
3
instead of red or yellow phosphorus, a relatively less toxic substance TOP and sodium metal (Na)
have been used to yield Na P. The synthesized nanoparticles were fully characterized by X-ray dif-
3
fraction pattern (XRD), Infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS),
Transmission electron microscopy (TEM) and superconducting quantum interference device
(
SQUID) analyses. The results showed that the synthesized FeP nanoparticles have the characteris-
tic orthorhombic crystal structures, with the size ꢀ10 nm and the coercivity 70 Oe at RT.
[
19,20]
Introduction
precursors,
and injection of metal nanoparticles-trioctyl
phosphine complex into hot solution of trioctyl phosphine
TOP) and trioctyl phosphine oxide (TOPO) utilizing it as a
surfactant for achieving nano-sized dimensions of the prod-
The transition metals phosphides specifically of Group VIII
are well known in the literature like Group III-V phosphides
such as Gallium phosphide (GaP) and indium phosphide
(
[21–29]
uct.
TOP has been extensively used as a source of
(InP). The Group III-V phosphides are synthesized by the
phosphorus as well as co-solvent for the synthesis of metal
phosphides. TOP can produce phosphorus by the catalytic
cleavage of P-C bond in the presence of metal nanoparticles
reaction of metals of Group III and phosphorus of Group
V. Transition metal carbides and nitrides have shown sig-
nificant applications in catalyzing various chemical reac-
(Fe, Ni or In), either generated during the reaction or
[
1,2]
tions.
Very few methodologies could be developed for
injected in the hot solution of TOP already prepared in
another flask. Subsequently, free phosphorus, generated dur-
ing the reaction, may form metal phosphides. This hypoth-
the synthesis of metal phosphides due to implication of
highly sensitive phosphorus sources. Although, transition
metal phosphides, for instance, molybedum phosphide,
nickel phosphide, cobalt phosphide, iron phosphide and
tungsten phosphide have shown good catalytic properties in
esis of catalytic cleavage of P-C bond was proposed by Chen
[30]
et al.for TOP-capped FeP nanoparticles.
Similar hypothe-
[
31]
ses have also been proposed for the synthesis of InP
and
[
3–6]
[
32]
hydrotreating reactions.
Multiple synthetic routes have
nickel phosphide (Ni P) nanoparticles.
In addition, phos-
2
[
33]
been developed for Ni P and MoP as reported by Phillips
2
phorus pentachloride (PCl5)
was also used as a source of
[
7–9]
and Sawhill.
Recently, magnetic metal phosphides nano-
phosphorus for the synthesis of highly reactive sodium
structures have gained popularity due to their potential
phosphide (Na P) by the reaction of the transition metal
3
[
6,10–15]
applications in magnetic and electronic devices.
These magnetic metal phosphides were synthesized by vari-
precursor to yield transition metal phosphide. Schaak and
Henkes also synthesized iron phosphides nanoparticles by
and using iron nanoparticles and TOP under argon at high tem-
[
16]
[17]
ous techniques including thermal,
solvothermal methods.
sonochemical
[
18]
Nanostructures of iron phosphide perature and transferred this into n-hexadecylamine at high
[
33]
(
FeP) orthorhombic, FeP3 (tetragonal), Fe P (hexagonal/ temperature.
There are some reports that also utilized
2
[
18,31]
orthorhombic), FeP (orthorhombic), FeP2 (orthorhombic), red or yellow phosphorus to synthesize Na P.
Such
3
and FeP (orthorhombic) are found to exhibit different mag- methodologies require formidable challenges because of tox-
4
netic properties. The methodologies, reported to synthesize icity and difficulty in handling of the red or yellow phos-
iron phosphides nanostructures, includes thermal decompos- phorus. Therefore, a route utilizing less toxic phosphorus
ition of single source (iron & phosphorus) organometallic precursor is required, Na P.
3
CONTACT Anil Kumar
anil_kumar@dce.ac.in
Department of Applied Chemistry, Delhi Technological University, Delhi, India.
ß 2020 Taylor & Francis Group, LLC

2
D. AHLUWALIA ET AL.
Sodium phosphide (Na P) synthesis was first reported by
3
th
Alexandre Baudrimont in mid-19 century using phos-
[
33]
phorus pentachloride (PCl ) as the phosphorus source.
5
Subsequently, various methods were reported based on the
use of sodium metal and red or yellow phosphorus as the
[
15]
phosphorus source to yield Na3P
to generate FeP. The
very tedious method for the synthesis of Na P was reported
3
by DiSalvo and coworkers by using sodium azide (NaN3),
titanium nitride (TiN), and Phosphorus with potassium iod-
ide, halide flux under argon atmosphere at very high tem-
perature in niobium (Nb) sealed tube and found single
[
33]
crystals of Na P as red-block.
Toxicity of the chemicals
3
used rendered these approaches difficult and challenging.
The synthesis of Na P is also very challenging due to tox-
3
icity of TOP that may arise by the formation of phosphine
gas as a by-product during the reaction in solution.
Scheme 1. Schematic presentation of the synthesis of TOP capped FeP
A simple method to synthesize Na P by reacting TOP
3
and sodium metal, without the use of red or yellow phos-
phorus, has been proposed in this study. In this method,
free phosphorus was generated by the reaction of Na and
TOP via catalytic mechanism. The synthesized sodium phos-
phide was further reacted with FeCl3 in the presence of
TOP to yield FeP/TOP-NPs. This method avoids direct use
of the red or yellow phosphorus and proposes a novel one-
pot synthetic route for the production of FeP/TOP-NPs.
turned black with green reflection color indicated the forma-
tion of Na P. During stirring, anhydrous FeCl3 (0.5 g,
3
0
.0031moles) dissolved in 4 mL TOP was slowly added to
ꢂ
Na P mixture. The temperature was raised to 320 C fol-
3
lowed by constant stirring for 3-4 h under inert atmosphere.
The mixture turned from greenish-black to black indicating
completion of the reaction. After cooling of the reaction
mixture to RT, methanol (75 mL) was slowly added to
decompose the un reacted sodium metal; and then the mix-
ture was centrifuged at 8000 rpm for 5 min. After the centri-
fuge, the obtained black pellet was re-dispersed in toluene
(25 mL); and was re-precipitated by the addition of metha-
nol (50 mL). The precipitate was separated by the centrifuga-
tion; subsequently pellet was washed with water (25 mL x 2)
and finally with methanol and dried under vacuum.
Experimental
General
Tri-octylphosphine (TOP), anhydrous ferric (III) chloride
(
FeCl ), sodium metal (Na), were purchased from Sigma-
3
Aldrich (San Louise, USA). Toluene and methanol were pur-
chased from J.T. Baker (Phillipsburg, NJ). The magnetic
properties of iron phosphide were measured using a super- Results and discussion
conducting quantum interference device (SQUID) magnet-
In this work, FeP nanoparticles were synthesized using TOP
ometer with a maximum field of 20000 Oe. X-ray diffraction
XRD) measurements were performed using a Philips
as a phosphorus source and a capping reagent to control the
size of particles (Scheme 1). The availability of free phos-
phorus, generated during the reaction by the catalytic cleav-
age of P-C bond in the presence of Na metal, led to the
(
X’Pert-Pro diffractometer with Cu-K radiation with a wave-
a
length of k ¼ 1.5406 Å. X-ray photoelectron spectra (XPS)
were recorded with a PHI 5000 Versa Probe (Chigaski,
Japan) XPS system. Transmission electron microscopy
ꢂ
formation of Na P at 280 C under argon atmosphere. Na P,
3
3
a highly reactive source of phosphorus, produced a black
(TEM), Electron dispersion X-ray (EDX) and Selected area
[33]
colored product upon reaction with FeCl3.
electron diffraction (SAED) of samples were performed ona
JEOL JEM-2100F (Tokyo, Japan) that was operated at
The powder was examined by XRD to characterize the
crystal structure of the synthesized FeP/TOP-NPs. The XRD
pattern of the synthesized FeP/TOP-NPs is shown in Figure
2
00 keV. Dynamic light scattering (DLS) was performed at
room temperature by using 35mW diode laser on a
Brookhaven 90Plus (Holtsville NY) particle size analyzer. IR
1
. The pattern showed all major peaks at 2h values of 30.80
002), 32.75 (011), 34.60 (200), 35.76 (102), 37.14 (111),
7.60 (201), 46.27(112), 46.92 (202), 48.36 (211), 50.34
103), 55.98 (301) and 59.66 (020) degrees, which are char-
acteristic features of crystalline planes of orthorhombic
(
3
(
spectra were recorded on
a
Perkin-Elmer Spectrum
series between 400
(
Massachusetts,
USA)
100
ꢁ
1
and 4000 cm
.
[
18,26]
structure of FeP.
A weak peak at an angle of 40.30 in
XRD pattern (Figure 1) indicated the presence of trace Fe P.
The orthorhombic XRD pattern matched well with the
2
Synthesis of iron phosphide
In-situ Na P was prepared by mixing TOP (2.24 mL, JCPDS (78-1443) data of FeP; the broadening of the Bragg’s
3
0
.0072moles
þ
1.76 mL excess TOP) and sodium peaks indicating poor crystallinity of TOP capped nano
ꢂ
(0.5 gm,0.022moles) metal at 250 C under argon atmos- sized FeP particles was also observed. The average thickness
ꢂ
phere; the mixture was left for stirring at 280 C for 2-3 it of grain is calculated by the Scherrer’s equation (D ¼ 0.9k/b

INORGANIC AND NANO-METAL CHEMISTRY
3
cos h, where D ¼ average thickness of grain in perpendicular
TEM images of FeP nanoparticles revealed a particle size
to specific facet, k ¼ frequency of X-ray and b ¼ FWHM at below 10 nm (Figure 2a and b). The aggregates appearing in
a selected 2h) was found to be ꢀ11.4 nm (Table 1).
the images are due to the drying process of the powder on
TEM grid. The majority of nanoparticles showed a spherical
morphology while only few of them showed an elliptical
shape. The diffused rings in the electron diffraction pattern
indicated nano-crystalline nature of the product, which is
consistent with the XRD data. Furthermore, elemental ana-
lysis by EDX confirmed the presence of Fe & P with the
stoichiometric ratio of Fe: P (21.60: 21.10). The observed
percentage of Fe was slightly more due to the presence of
impurity of Fe P or Fe nanoparticles in the product. The
2
particle size and size distribution of the synthesized FeP/
TOP-NPs measured by DLS showed average size 13.5 nm
(Figure 3).
The XPS spectra of TOP capped FeP nanoparticles are
shown in Figure 4. The high-resolution spectrum of FeP
showed splitting in 2p3/2 & 2p1/2 of the binding energies
Figure 1. XRD pattern of FeP/TOP-NPs prepared from Na
depicted by ‘ ’.
3
P. Fe
2
P phase is
[18,25]
ꢃ
711 eV and 720 eV respectively.
Similarly, the spectrum
of P 2p3 showed two peaks one of lower energy at 129.5 eV
that can be assigned to FeP and other one of higher energy
Table 1. Average grain thickness and lattice spacing of FeP/TOP-NPs calcu-
lated using Scherrer’s formula.
[
18,25]
at 133.5 eV
corresponding to the oxidized phosphor-
Lattice
Average
ous due to oxidation of the surface of nanoparticles in pres-
ence of oxygen absorb form surrounding
Infrared spectroscopy was employed to examine the pres-
ence of TOP capping around FeP nanoparticles where TOP
was employed as a phosphorus source as well as a stabilizer
to control the particle size. The IR spectra of TOP and the
ꢂ
ꢂ
hkl planes 2 h ( )
h ( )
FWHM
spacing (Å) grain thickness (nm)
.[9,19,34]
011
111
211
301
020
32.75
37.14
48.36
55.98
59.66
16.38
18.57
24.18
27.99
29.83
0.75
0.57
0.81
0.98
1.04
2.750
2.406
1.880
1.638
1.542
11.54
15.37
11.24
9.60
9.21
Figure 2. TEM (a) HRTEM (b) SAED (c), and EDX (d) of FeP/TOP-NPs.

4
D. AHLUWALIA ET AL.
Figure 3. The particle size distribution of FeP/TOP-NPs as observed in DLS
measurements.
Figure 5. Infrared spectra of TOP and FeP/TOP-NPs.
3
Figure 4. XPS of FeP/TOP-NPs as prepared from Na P showed the binding ener-
gies of (a) Iron & (b) Phosphorus.
synthesized FeP/TOP nanoparticles are shown Figure 5. The
characteristic IR absorption bands of TOP at 2852 and
ꢁ
1
2
1
921 cm
(corresponding to -CH stretching); and at
ꢁ
1
468and1376 cm (corresponding toCH deformation) were
2
observed in the spectrum. The other IR absorption bands,
ꢁ
1
Figure 6. The magnetic properties of Iron phosphides measured by SQUID (a)
Magnetization as a function of field at RT and the inset displays the field
dependence of magnetization with coercivity 70 Oe for FeP/TOP-NPs. (b) The
ZFC & FC curves measured with an applied magnetic field of 100 Oe.
appearing at 1199, 1100 and 1036 cm , were attributed to
[
25,35]
C-P stretching of TOP.
Thus, it is evident from the IR
data that all absorption bands attributed to TOP were
observed in the analysis of the product confirming the
proper capping of FeP nanoparticles by trioctylphosphine.
The temperature dependent magnetic properties of the
(200 K) and irreversibility temperature (300 K) were
observed for FeP that may be attributed to high aspect ratio
FeP/TOP-NPs samples were measured by SQUID magnet- (length/width) and greater thermal energy required to align
ometer. The results obtained in this study indicating super disordered spin. The small hysteresis loop was observed at
paramagnetic behavior and is typical for magnetic nanopar- room temperature with a coercivity 70 Oe. Thus, the present
[
25,30]
ticles (Figure 6a).
The higher blocking temperature results affirm that it is possible to obtain magnetism at

INORGANIC AND NANO-METAL CHEMISTRY
5
room temperature for a material showing antiferromagnetic
nature at low temperature. However, the bulk iron phos-
phide does exhibit antiferromagnetic property, with a Neel
5. Song, L.; Zhang, S.; Wei, Q. An Approach to Preparing Porous
and Hollow Metal Phosphides with Higher Hydrodesulfurization
Activity. J. Sol. Stat. Chem. 2011, 184, 1556–1560. DOI: 10.1016/
j.jssc.2011.03.057.
[
19,34]
temperature at 115 K,
but contrary to that a ferromag-
6.
Brock, S. L.; Perera, S. C.; Stamm, K. L. Chemical Routes for
Production of Transition Metal Phosphides on the Nanoscale:
implications for Advanced Magnetic and Catalytic Materials.
Chem. Eur. J. 2004, 10, 3364–3371. DOI: 10.1002/chem.
netic like behavior of FeP was also reported by Chen
[
30]
et al.
The magnetization profile from the present results
showed a small hysteresis loop indicating the presence of
ferromagnetic traces in the product, which may be due to
200305775.
7.
Wang, A.; Ruan, L.; Teng, Y.; Li, X.; Lu, M.; Ren, J.; Wang, Y.;
Hu, Y. Hydrodesulfurization of Dibenzothiophene over Siliceous
MCM-41-Supported Nickel Phosphide Catalyst. J. Catal. 2005,
presence of a ferromagnetic material- Fe P. The presence of
2
Fe P traces in the product was also supported by XRD
2
(Figure 1) and EDX (Figure 3d). Furthermore, in order to
2
29, 314–321. DOI: 10.1016/j.jcat.2004.09.022.
estimate the blocking temperature of FeP/TOP-NPs, the
zero-field cooling (ZFC) and field-cooling (FC) magnetiza-
tion curves were measured at an applied field of 100 Oe in
the temperature range of 0 to 350 K (Figure 6b). ZFC curve
showed a maximum at T > 200 K, associated to the blocking
temperature of the nanoparticles system and gradually
8. Clark, P. A.; Oyama, S. T. Alumina-Supported Molybdenum
Phosphide Hydroprocessing Catalysts. J. Catal. 2003, 218, 78–87.
DOI: 10.1016/S0021-9517(03)00086-1.
9.
Yao, Z.; Hai, H.; Lai, Z.; Zhang, X.; Peng, F.; Yan, C. A Novel
Carbothermal Synthesis Route for Carbon Nanotube Supported
Fe
2
P Nanoparticles. Top. Catal. 2012, 55, 1040–1045. DOI: 10.
1007/s11244-012-9885-0.
dropped to zero at 350 K. However, ZFC and FC curves 10. DeLong, L. E.; Meisner, G. P. The Pressure Dependence of the
Superconducting Transition Temperature of LaT4P12 (T ¼ Fe,
showed irreversible temperature at T > 300 K indicating the
presence of a size distribution or nanoparticles aggregation.
The blocking temperature depends on many factors such as
the material total anisotropy (K) and the volume of the
nanoparticles. Similar results have been reported where esti-
mated blocking temperature was 140 K with an irreversible
Ru, Os). Solid State Comm. 1985, 53, 119–1239. DOI: 10.1016/
0038-1098(85)90108-5.
1
1. Bichat, M.-P.; Pascal, J.-L.; Gillot, F.; Favier, F. Electrochemical
Lithium Insertion in Zn3P2 Zinc Phosphide. Chem. Mater. 2005,
17, 6761–6771.
2. Chikazumi, S. Physics of Ferromagnetism; Clarendon Press:
Oxford, 1997.
3. Pei, Y.; Cheng, Y.; Chen, J.; Smith, W.; Dong, P.; Ajayan, P. M.;
Ye, M.; Shen, J. Recent Developments of Transition Metal
Phosphides as Catalysts in the Energy Conversion Field. J.
1
1
[
30,36–40]
temperature at 233 K.
Conclusion
Mater. Chem.
A
2018, 6, 23220–23243. DOI: 10.1039/
C8TA09454C.
In conclusion, this study provides a simpler alternative route
1
4. Maria Iqbal, J.; Ludwig, R.; Ayub, K. Phosphides or Nitrides for
Better NLO Properties? a Detailed Comparative Study of Alkali
Metal Doped Nano-Cages. Mater. Res. Bull. 2017, 92, 113–122.
DOI: 10.1016/j.materresbull.2017.03.065.
for the synthesis of Na P without the use of toxic red or yel-
3
low phosphorus, where reaction of TOP with Na metal led
to the formation of Na P. Subsequently, Na P further
3
3
reacted with iron chloride to form FeP/TOP-NPs along with 15. Munsifa, S.; Mariaa Khana, S.; Ali, A.; Gilani, M. A.; Iqbal, J.;
Fe P traces. The phosphorus source was generated from
Ludwig, R.; Ayub, K. Remarkable Nonlinear Optical Response of
Alkali Metal Doped Aluminium Phosphide and Boron
Phosphide Nanoclusters. J. Mol. Liq. 2018, 271, 80–95.
2
TOP through the catalytic cleavage of P-C bond in the pres-
ence of Na-metal. Moreover, these FeP/TOP-NPs exhibited
significant superparamagnetic properties, compared to their
bulk counterparts.
1
6. Lukehart, C. M.; Milne, S. B.; Stock, S. R. Formation of
Crystalline Nanoclusters of Fe
2 2 2 2 5 2
P, RuP, Co P, Rh P, Ni P, Pd P ,
or PtP in a Silica Xerogel Matrix from Single-Source Molecular
2
Precursors. Chem. Mater. 1998, 10, 903–908. DOI: 10.1021/
cm970673p.
Acknowledgement
17. Sweet, J. D.; Casandonte, D. J. Sonochemical Synthesis of Iron
Phosphide. Ultrason. Sonochem. 2001, 8, 97–101. DOI: 10.1016/
S1350-4177(00)00065-1.
Authors thank Delhi Technological University Delhi for providing
infrastructural facilities.
1
8. Yunle, G.; Fan, G.; Yitai, Q.; Huagui, Z.; Ziping, Y. A
Solvothermal Synthesis of Ultra-Fine Iron Phosphide. Mater. Res.
Bull. 2002, 37, 1101–1105.
9. Perera, S. C.; Fodor, P. S.; Tsoi, G. M.; Wenger, L. E.; Brock,
S. L. Application of De-Silylation Strategies to the Preparation of
Transition Metal Pnictide Nanocrystals: The Case of FeP. Chem.
Mater. 2003, 15, 4034–4038. DOI: 10.1021/cm034443o.
References
1
1
.
Chen, G. J. Carbide and Nitride Overlayers on Early Transition
Metal Surfaces: Preparation, Characterization, and Reactivities.
Chem. Rev. 1996, 96, 1477–1498. DOI: 10.1021/cr950232u.
Hargreaves, J. S. J.; Mckay, D. A Comparison of the Reactivity of
Lattice Nitrogen in Co3Mo3N and Ni2Mo3N Catalysts. J. Mol.
Catal. A: Chem. 2009, 305, 125–129. DOI: 10.1016/j.molcata.
2
0. Junli, W.; Qing, Y.; Zude, Z. Selective Synthesis of Magnetic
2.
2
Fe P/C and FeP/C Core/Shell Nanocables. J.Phys. Chem. Lett.
2
010, 1, 102–106.
2
1. Brock, S. L.; Senevirathne, K. Recent Developments in Synthetic
Approaches to Transition Metal Phosphide Nanoparticles for
Magnetic and Catalytic Applications. J. Solid State Chem. 2008,
181, 1552–1559. DOI: 10.1016/j.jssc.2008.03.012.
22. Park, J.; Koo, B.; Yoon, K. Y.; Hwang, Y.; Kang, M.; Park, J.-G.;
Hyeon, T. Generalized Synthesis of Metal Phosphide Nanorods
via Thermal Decomposition of Continuously Delivered
Metal ꢁ Phosphine Complexes Using a Syringe Pump. J. Am.
Chem. Soc. 2005, 127, 8433–8440. 2005) DOI: 10.1021/ja0427496.
2
008.08.006.
3
.
.
Yao, Z. W. Exploration on Synthesis of Activated Carbon
Suppoted Molybdenum Carbide, Nitride and Phosphide Viab
Carbothermal Reduction Route. J. Alloys Compd. 2009, 475,
L38–L41. DOI: 10.1016/j.jallcom.2008.07.130.
Zhao, H. Y.; Li, D.; Bui, P.; Oyama, S. T. Hydrodeoxygenation of
Guaiacol as Model Compound for Pyrolysis Oil on Transition
Metal Phosphide Hydroprocessing Catalysts. Appl. Catal. A
4
2
011, 391, 305–310. DOI: 10.1016/j.apcata.2010.07.039.

6
D. AHLUWALIA ET AL.
2
3. Park, J.; Koo, B.; Hwang, Y.; Bae, C.; An, K.; Park, J. G.; Park,
M. H.; Hyeon, T. Novel Synthesis of Magnetic Fe2P Nanorods
from Thermal Decomposition of Continuously Delivered
Cleavage of Phosphorus Carbon Bond in n-Trioctylphosphine by
Indium. Mater. Chem. Phys. 2005, 92, 54–58. DOI: 10.1016/j.
matchemphys.2004.12.029.
Precursors Using a Syringe Pump. Angew. Chem. Int. Ed. 2004, 32. Chiang, R.-K.; Chiang, R.-T. Formation of Hollow Ni2P
4
3, 2282–2285. DOI: 10.1002/anie.200353562.
Nanoparticles Based on the Nanoscale Kirkendall Effect. Inorg.
Chem. 2007, 46, 369–371. DOI: 10.1021/ic061846s.
3. Baudrimont, E. M. Research on chlorides and phosphorus bro-
mides. Ann. Chim. Phys. 1864, 13, 5-513. http://catalogue.bnf.fr/
ark:/12148/cb300676181.
2
4. Lo, C.-T.; Kuo, P.-Y. Synthesis and Magnetic Properties of Iron
Phosphide Nanorods. J. Phys. Chem. C 2010, 114, 4808–4815.
DOI: 10.1021/jp9103239.
5. Singh, N.; Khanna, P. K.; Joy, P. A. Solid State Synthesis and
Room Temperature Magnetic Properties of Iron Phosphide
Nanoparticles. J. Nanopart. Res. 2009, 11, 491–497. DOI: 10.
3
3
3
2
4. Lee, S. P.; Chen, Y. W. Selective Hydrogenation of Furfural of
Ni-P, Ni-B and Ni-P-B Ultrafine Materials. Ind. Eng. Chem. Res.
1
007/s11051-008-9458-0.
1
999, 38, 2548–2556. DOI: 10.1021/ie990071a.
2
2
2
6. Muthuswamy, E.; Kharel, P. R.; Lawes, G.; Brock, S. L. Control
5. Chen, S.; Zhang, X.; Zhang, Q.; Tan, W. Trioctylphosphine as
Both Solvent and Stabilizer to Synthesize CdS Nanorods.
Nanoscale Res Lett. 2009, 4, 1159–1165. DOI: 10.1007/s11671-
of Phase in Phosphide Nanoparticles Produced by Metal
Nanoparticle Transformation: Fe
2
2
P and FeP. ACS Nano 2009, 3,
383–2393. DOI: 10.1021/nn900574r.
0
09-9375-x.
6. Felcher, G. P.; Smith, F. A.; Bellavance, D.; Wold, A. Magnetic
Structure of Iron Monophosphide. Phys. Rev. 1971, 3,
046–3052. DOI: 10.1103/PhysRevB.3.3046.
7. Henkes, A. E.; Vasquez, Y.; Schaak, R. E. Converting Metals into
Phosphides: A General Strategy for the Synthesis of Metal
Phosphide Nanocrystals. J. Am. Chem. Soc. 2007, 129,
3
3
B
3
1
896–1897.
7. Panda, R. N.; Dalavi, S. B.; Theerthagiri, J. Synthesis of High
Surface Area W2N and Co–W–N Nitrides by Chemical Routes.
Adsorp. Sci. Technol. 2012, 30, 345–354. DOI: 10.1260/0263-
8. Zhang, H.; Ha, D. H.; Hovden, R.; Kourkoutis, L. F.; Robinson,
R. D. Controlled Synthesis of Uniform Cobalt Phosphide
Hyperbranched Nanocrystals Using Tri-n-Octylphosphine Oxide
as a Phosphorus Source. Nano Lett. 2011, 11, 188–197. DOI: 10.
6174.30.4.345.
3
3
8. Panda, R. N.; Dalavi, S. B.; Theerthagiri, J.; Raja, M. M.,
Characterization and Magnetic Properties of Nanocrystalline
FexNi80- xCo20 Ternary Alloys. J. Magn. Magn. Mater. 2013,
1
021/nl103400a.
2
3
3
9. Khanna, P. K.; Singh, N.; More, P. Synthesis and Band-Gap
Photoluminescence from Cadmium Phosphide Nano-Particles.
Curr. App. Phys. 2010, 10, 84–88. DOI: 10.1016/j.cap.2009.05.
3
44, 30–34.
9. Theerthagiri, J.; Dalavi, S. B.; Raja, M. M.; Panda, R. N.
Magnetic Properties of Nanocrystalline E-Fe N and Co N Phases
0
02.
0. Chen, J.-H.; Tai, M.-F.; Chi, K.-M. Catalytic Synthesis,
Characterization and Magnetic Properties of Iron Phosphide
Nanowires. J. Mater. Chem. 2004, 14, 296–298. DOI: 10.1039/
B311943B.
1. Khanna, P. K.; Jun, K.-W.; Hong, K. B.; Baeg, J.-O.; Mehrotra,
G. K. Synthesis of Indium Phosphide Nanoparticles via Catalytic
3
4
Synthesized by Newer Precursor Route. Mater. Res. Bull. 2013,
48, 4444–4448. DOI: 10.1016/j.materresbull.2013.07.043.
40. Mishra, P. P.; Theerthagiri, J.; Panda, R. N. Mesoporous
Vanadium Nitride Synthesized by Chemical Routes. Adsorp. Sci.
Technol. 2014, 32, 465–474. DOI: 10.1260/0263-6174.32.6.465.