Rev. Adv. Mater. Sci.

2020; 59:538–552

Review Article

Xiaoxing Zhang*, Li Zhang, Hui Liu, Binxia Cao, Libo Liu, and Weimin Gong

Structure, morphology, size and application of

iron phosphate
https://doi.org/10.1515/rams-2020-0039 ture. At atmospheric pressure, it exists as an α-quartz
Received Apr 08, 2020; accepted Jul 17, 2020 structure. And it becomes tetragonal under high pressure.
The temperature change leads to an a-β phase transition
Abstract: Iron phosphates have rich chemical structures
from a P622 to a P32 phase [1].
with various morphologies and sizes. Since they are en-
Early studies focused on microporous iron phos-
vironment friendly with good biocompatibility, they have
phate materials with open framework structure, and
good performances in the fields of catalysis and battery
then mesoporous iron phosphate nanomaterials also at-
electrode material rising in recent years, as well as in
tracted great attention of researchers due to their excel-
the traditional fields like agriculture and steel. They also
lent performance in application. Now there have been re-
have important applications in adsorption, separation and
ports on the synthesis of one-dimensional tube/rod/wire,
concentration due to their unique structural characteris-
two-dimensional disc/plate, three-dimensional nanopar-
tics. In this paper, iron phosphates are classified based
ticles, hollow spheres and other iron phosphate ma-
on their common characteristics such as structure, mor-
terials. This paper mainly introduces FePO4 with var-
phology and size, and their application in the past two
ious crystal forms, sizes and morphologies. Since the
decades is reviewed, with emphasis on their application
iron phosphates are a wide group of compounds of
in adsorption, separation and concentration of different
different structural and chemical composition, some
species. Further, their application in adsorption, separa-
other compounds (e.g., Fe5 (PO4 )4 (OH)2 ·2H2 O, Fe4 (P2 O7 )3 ,
tion and concentration of heavy metals is prospected.
Fe3 (PO4 )2 ·(H2 O)8 ) and related composites (e.g., FePO4 /C,
Keywords: iron phosphate, classification, application, ad- GO-FePO4 , Fe3 O4 @FePO4 ) are also mentioned.
sorption Iron phosphates were firstly applied in areas of agri-
culture, ceramic glass, steel, and surface passivation, etc.
Later, especially in the past two decades, they have had
good performances in the fields of catalytic and battery
1 Introduction
electrode materials since their unique catalytic and elec-
tric properties were found, which has greatly broadened
Iron phosphates belong to a rather new group of mate-
the scope of their application. In addition, they have had
rials whose interest is growing. They have rich chemi-
important applications in fields of adsorption, separation
cal structures and their preparation methods are differ-
and concentration due to their unique local structures,
ent with various characteristics. The synthesis methods
and have good application prospects.
of iron phosphates commonly used include hydrothermal
In recent years, the author has paid great attention to
method, solvothermal method, precipitation, coprecipita-
the application of iron phosphates in the field of adsorp-
tion, etc. Many structures of iron phosphates have been
tion, separation and concentration of heavy metals, and
synthesized presently, including, α-quartz, amorphous,
has done some research work. In the process of consulting
monoclinic, orthorhombic, triclinic, and so on. The tem-
related literatures, it is found that the existing review ar-
perature and pressure have a great influence on the struc-
ticles generally focus on some aspects of work, and lack
an overall introduction of this kind of material. In this pa-
per, for the first time, iron phosphates are classified based
*Corresponding Author: Xiaoxing Zhang: College of Environ- on their common characteristics such as structure, mor-
mental Sciences and Engineering, Dalian Maritime University, phology and size, and their application in various fields
Dalian 116026, China; Email: [email protected]; Tel.:
in the past two decades is reviewed, with emphasis on
+86 411 84729205; Fax: +86 411 84727670
Li Zhang, Hui Liu, Binxia Cao, Libo Liu, Weimin Gong: College of their application in adsorption, separation and concentra-
Environmental Sciences and Engineering, Dalian Maritime Univer- tion of different species. Further, their application in ad-
sity, Dalian 116026, China

Open Access. © 2020 X. Zhang et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0
License
 Structure, morphology, size and application of iron phosphate | 539

sorption, separation and concentration of heavy metals

is prospected. Such a review may be valuable for a broad
scientific community, from scientists focusing on different
synthesis methods, up to those targeting on applications.
Thus, it should be interesting for chemists, materials sci-
entists, physicist, etc.

2 Classification of iron phosphate

Iron phosphates, with various crystal forms, sizes and mor-
phologies, can be synthesized using different synthesis
methods. And their controllable preparation can be real-
ized by adjusting the initial concentration of precursors
or adding different reactants and templates. Separately, in
terms of crystal form, there are amorphous, monoclinic, or-
thorhombic structures, etc.; in terms of morphology, there
are solid spheres, hollow spheres, rods, tubes, flakes, flow-
ers, branches, etc.; in terms of size, there are nanometer,
micrometer, or larger scales; in terms of pore size, there are Figure 1: Projection of three-dimensional open structure of iron
microporous, mesoporous, macroporous structures, etc. It phosphate [3].
is difficult to classify the synthesized products into a cer-
tain category accurately. Therefore, the products of iron 2.2 Mesoporous iron phosphate
phosphate are roughly classified according to their com-
mon and obvious characteristics in this section. It was reported for the first time by Guo et al. [6] of Nan-
jing University in 2000 that meso-structured lamellar iron
phosphates with varied d-spacings were synthesized from
2.1 Microporous iron phosphate ferric acetylacetonate and n-alkylammonium dihydrogen-
phosphates as both template and reactant. Then Guo [7]
Huang et al. [2] synthesized a microporous iron phos- synthesized a novel mesoporous layered iron phosphate
phate with an open framework structure by hydrothermal with a surface area of 254 m2 g−1 and average pore size
method, and its pore volume is 2957.5 Å3 . Hydrothermal of 2.6 nm by using hydrofluoric acid as mineralizer. The
organically templated magnetic iron phosphates with a introduction of hydrofluoric acid can connect iron phos-
three-dimensional open framework were synthesized by phate and anionic surfactant sodium dodecyl sulfate, and
Riou-Cavellec et al. [3], the projection of which is shown make iron phosphate aggregate on the surface of surfac-
in Figure 1 [3]. The hydrothermal method promoted the for- tant which is conducive to the synthesis of mesoporous
mation of open-framework iron phosphate. If fluoride ions structure. However, the mesoporous structure obtained by
were introduced into the hydrothermal process as a miner- this method is disordered. Subsequently, Yu et al. [8] in
alizer, part of fluoride ions may participate in the compo- Guo’s research group synthesized well-ordered hexagonal
sition of the framework structure, which is conductive to mesoporous iron phosphate with a narrow pore diameter
the synthesis of new phases and metal phosphates with of 2.4 nm and the lattice period length of 4.5 nm and a
supermicropores. The role of fluoride mineralizer is par- surface area of 423 m2 g−1 by using the similar method
ticularly obvious in the synthesis of open-framework iron as above [7]. Santos-Pena et al. [9] also synthesized amor-
phosphate [4]. A three-dimensional open framework iron phous FePO4 ·2H2 O composed of nanoparticles with size of
phosphate which contains organic ethylenediammonium 40-80 nm by using a similar method [7]. The mesophase
dication in the framework voids was synthesized under obtained by using CTAB as a template, is more ordered
solvothermal conditions [5]. The most important feather compared with the literature [7]. Using cationic surfac-
of the compound is that it contains four coordinated iron tant CTMACl as the template, Zhu et al. [10] synthesized
atoms which is very rare in iron phosphates. a highly-ordered hexagonally mesostructured iron phos-
540 | X. Zhang et al.

phate with a d spacing of 4.18 nm and a lattice constant with carbon were obtained [15]. Iron hydroxyl phosphate
of 4.82 nm. Fe3 (PO4 )2 (OH)2 microspheres with diameters of several
Bastakoti et al. [11] synthesized large-sized meso- micrometers were prepared by a facile one-step glycerin-
porous iron phosphate with 30 nm pore diameter and 15 assisted solvothermal method. The microspheres have
nm wall thickness by a soft-template method based on good biocompatibility and can transform into FePO4
polymeric micelles assembly. Pramanik et al. [12] reported through thermal treatment at 800∘ C in the air [16].
the shape controlled synthesis of crystalline mesoporous Monodispersed Fe5 (PO4 )4 (OH)3 ·2H2 O microspheres were
iron phosphate with 2D-plates and 1D-rods, the dimen- prepared by a one-step hydrothermal method without
sionality of which can be switched by changing the po- templates [17]. The microspheres, with diameters of 1.0-
larity of the synthetic medium. Shi et al. [13] prepared 3.0 µm, are constructed by the polyhedral nanoparticles
mesoporous FePO4 by a modified template method using with an average diameter of 100 nm. The correspond-
P123 surfactant as a template with further calcination be- ing FePO4 microspheres assembled by mesoporous poly-
low 500∘ C. El Haskouri et al. [14] synthesized relatively hedral nanocrystals can be obtained after calcination.
high surface area mesoporous iron phosphate through a Sphere FePO4 with a diameter of 15 µm, controllably syn-
generalized one-pot procedure by using a cationic surfac- thesized by a hydrothermal route with the molar ratio
tant as co-assembling template. A soft chemical extraction FeCl3 /KH2 PO4 of 3:3, was consisted of small nanoparticles
procedure allows opening the pore system of the parent (<50 nm) [18].
as-prepared materials by exchanging the surfactant with-
out mesostructure collapse. The final solids pose a well-
established oxo-phosphate-based mesostructure, without 2.4 Hollow spheres
segregation of metal oxide domains.
Li’s team obtained hollow colloidal spheres of iron phos-
phate by low-temperature solution-phase reactions [19].
2.3 Microspheres The size of the colloidal spheres can be easily controlled
by adjusting the concentration of the precursor. No visi-
Fe5 (PO4 )4 (OH)2 ·2H2 O spheres with a diameter of ca. 5 ble change in particle size and morphology after anneal-
µm were formed through hydrothermal reaction. After ing at 500∘ C. The colloidal spheres are stable, negatively
carbonization at 500∘ C, Fe3 (PO4 )2 (OH)2 spheres coated charged, and well-dispersed in solution. Cao et al. [20]

Figure 2: TEM images of FePO4 nanospheres synthesized at the molar ratio of Fe2+ /PO3− 4 of 1:1 (a, b), 1:2 (c, d), 1:3 (e, f), and 1:4 (g, h),
respectively. (a) and (b) are solid nanospheres, (c)-(h) are hollow nanospheres with the shell thickness of approximately 40 (c, d), 22 (e, f),
and 10 nm (g, h), respectively [22].
 Structure, morphology, size and application of iron phosphate | 541

prepared monodispersed iron phosphate hollow micro- nanoparticles on hydroxyl-terminated SiO2 /Si substrates
spheres with a high degree of crystallization through a with a narrow size distribution (average diameter = 2.2
facile in-situ deposition method using rape pollen grains nm) by a simple room temperature spontaneous reaction
as a biotemplate. Cao et al. [21] synthesized iron hy- of ferric chloride and phosphoric acid. Yin et al. [31] syn-
droxyl phosphate microspheres with the core in the hollow thesized amorphous iron(III) phosphate by solid-state re-
shell, and double-shelled hollow microspheres by a sim- action at room temperature. The particle size is in the
ple one-step microwave-solvothermal ionic liquid method. range of 100-200 nm. Yin et al. [32] synthesized iron phos-
Yin et al. [22] synthesized amorphous FePO4 hollow phate nanostructures by a fast, simple microwave heat-
nanospheres with tunable shell thickness by a one-step hy- ing method. The morphology and size of the nanomate-
drothermal approach, as shown in Figure 2 [22]. A similar rials are significantly influenced by the concentration of
method [22] was used to grow amorphous FePO4 hollow the precursors and the kinds of surfactants. Qian et al. [33]
nanospheres directly on the surface of graphene [23]. The synthesized unique amorphous FePO4 with particle size of
outer diameter of the nanospheres is ca. 30-60 nm, hollow- 20-80 nm by a new cost-effective electrochemical method.
structured with a wall thickness of 4-6 nm. This FePO4 possesses a mesoporous structure with spe-
cific surface area of 65.2 m2 g−1 and dominant pore diam-
eter of 23.6 nm. Liu et al. [34] reported a novel strategy us-
2.5 Nanometer iron phosphate ing a confined area impinging jet reactor to continuously
produce amorphous FePO4 nanoparticles within 10-30 nm.
Nanoparticle The particles transform into trigonal iron phosphate and
the size turns to 40-60 nm after calcination at 600∘ C. Yang
The precipitation method is commonly used in prepar- et al. [35] synthesized FePO4 with well-defined ellipsoid
ing iron phosphate nanoparticles. Guo et al. [24] prepared morphology and uniform particle size distribution via a
iron phosphate nanoparticles by quick homogeneous pre- green spray drying method with formic acid as additive.
cipitation with an amorphous structure. Compared with The material consisting of ellipsoid particles (ca. 100 nm)
that obtained by the general precipitation method, the has a higher specific surface (13.45 m2 g−1 ). The added
size and morphology of the particles have a better disper- formic acid plays a crucial role in the formation of the well-
sion, and the particle size uniformity (15-25 nm) is signif- distributed FePO4 particles.
icantly better than the latter (5-80 nm). Wang et al. [25]
synthesized amorphous FePO4 ·2H2 O nanoparticles with
average particle size of 80 nm by a facile coprecipitation
method at ambient temperature. Lu et al. [26] prepared
nanosized iron phosphate, with high purity, well disper-
sion and narrow size distribution around 59 nm, by cou-
pling fast precipitation in membrane dispersion micro-
contactor and hydrothermal treatment. Zhang et al. [27]
conducted the size adjustment of FePO4 nanoparticles in
the range of 9-50 nm by using mixed acids on a general
platform of coupling fast precipitation and thermal treat-
ment process. The as-prepared nanoparticles were high-
purity amorphous FePO4 ·2H2 O with good dispersity and
narrow size distribution. Fang et al. [28] synthesized FePO4
nanospheres successfully through a simple chemically in-
duced precipitation method with a diameter of ca. 100 nm.
The nanospheres present a mesoporous amorphous struc-
ture with pore size of ca. 10 nm and surface area of 19.33
m2 g−1 .
Compared with conventional precipitation method, Figure 3: TEM images of nanotubular iron phosphate with meso-
porous structure [36].
FePO4 ·2H2 O prepared by microreaction technology shows
a uniformly distributed granular morphology with a
smaller mean size of ca. 200 nm [29]. Additionally, Yang
et al. [30] achieved the direct formation of iron phosphate
542 | X. Zhang et al.

Nanotube The diffraction lines were indexed to the hexagonal struc-

ture [38, 39]. The diameter of these nanorods is about in
On the basis of the concepts developed in the previous syn- the range of 20-30 nm and the length 50-100 nm.
thesis of mesoporous iron phosphate [7], iron phosphate Amorphous α-FePO4 ·H2 O nanowires with diameters
nanotubes with mesoporous walls are solvothermally syn- of 10-20 nm were synthesized using genetically engineered
thesized, with diameters of 50-400 nm, lengths of sev- M13 virus [40], as shown in Figure 4 [40].
eral microns, and wall thickness of 20-40 nm [36]. The
novel nanotubular iron phosphate with composite meso-
macroporous structure possesses a specific surface area of Nanosheet/nanoplate/nanoflake
232 m2 g−1 and bimodal distribution of pore sizes with two
maxima at ~3 nm and ~50 nm, respectively, as shown in Ultra-thin iron phosphate nanosheets, with some meso-
Figure 3 [36]. Cai et al. [37] reported an oil-phase synthesis
porous morphologies, were designed as a new 2D material
of uniform double-wall amorphous FePO4 (α-FePO4 ) nan- with high surface area of 27.77 m2 g−1 [41].
otubes with each wall thickness of only ~20 nm. Amorphous FePO4 ·2H2 O nanoplates were prepared
via liquid exfoliation method [42]. The nanoplates were
exfoliated from the diethylamine-modified FePO4 ·2H2 O
Nanorod/nanowire that were sourced from recycled steelmaking slag. The ob-
tained nanoplates feature in an average lateral size of 46.76
Iron phosphate nanorods (FePO4 particles with the nm and transversal size of 31.62 nm with an average thick-
nanorod shape) were synthesized via a novel facile route. ness of 30.4 nm.

Figure 4: TEM images of α-FePO4 ·H2 O nanowires [40].

Figure 5: SEM images of branch-like (A-D), flower-like (E-H) FePO4 [18].

 Structure, morphology, size and application of iron phosphate | 543

Iron phosphate nanopowders were synthesized by

precipitation method with yeast cells as a biologic tem-
3 Application of iron phosphate
plate [43]. The product calcined shows flake shapes with
This section introduces the application of iron phosphates
length of 500-600 nm and width of 200-300 nm. Ultrathin
in other fields except that in adsorption, separation and
2D nanoflakes of FePO4 were synthesized with highly or-
concentration, which will be focused on in the next sec-
dered mesoporous structures [44]. The thicknesses of the
tion.
as-obtained nanoflakes are about 3.7 nm.

3.1 Immobilization of chemical wastes

2.6 Others
Vitrification is the most effective method for the immo-
The FePO4 ·2H2 O submicrometer-discs with a diameter of bilization of hazardous waste by incorporating toxic ele-
1-1.5 µm and thickness of 300-500 nm were prepared by ments into a glass structure for safe storage and burying.
a facile heat reflux method [45]. Without using any tem- Iron phosphate glasses have been studied for their poten-
plates and additive, the prepared material is single-phase tial waste immobilization applications since the mid-1990s
monoclinic FePO4 ·2H2 O without any impurities phase. Ul- [51]. They have been proposed as matrices for the storage
trafine disc-shaped FePO4 ·2H2 O with a diameter of 1-5 µm of radioactive waste, even those that cannot be vitrified us-
and thickness of 0.5-1 µm was prepared by the hydrogen ing conventional borosilicate waste glass. The effect of dif-
peroxide-assisted oxidation with reduced iron powder and ferent proportions of additives on their performance was
phosphoric acid as precursors [46]. No obvious agglomer- studied in literatures [52, 53]. A model based on the crystal
ation was observed. structure of FePO4 was optimized using the DFT method
Two new iron(III) phosphates were synthesized from and corresponding theoretical spectroscopic studies [54].
the dehydration of hydrothermally prepared monoclinic The maximal predicted load of waste constituents into the
and orthorhombic hydrated phosphates [47]. Both of the glass without rebuilding of the structure is 30 mol%. The
phases are thermally unstable relative to the trigonal amorphous and crystalline structures of iron phosphate
quartz-like FePO4 . Lin et al. [48] designed novel routes via were investigated as candidate materials for encapsulation
phosphation of beta-FeOOH nanorods for the controlled of nuclear waste [55]. An iron phosphate ceramic waste
synthesis of iron phosphate dihydrates of varying crystal- form was developed to immobilize radioactive waste solu-
lographic phases (monoclinic and orthorhombic) and mor- tion using converter slag which is a by-product of the steel
phologies. industry [56].
FePO4 with branch-like and flower-like morpholo-
gies (Figure 5 [18]) were achieved with the molar ratio
FeCl3 /KH2 PO4 of 1:3 and 2:3, respectively [18]. The branch- 3.2 Anti-corrosion
like FePO4 consisted of four main branches, of which the
length and the width were 10 µm and 2 µm, respectively. As a pollution-free auxiliary agent in the anticorrosive
The flower-like FePO4 with the particle diameter of around paint, FePO4 ·2H2 O can replace the toxic agents such as
10 µm was regularly formed from a small branch struc- red lead, lead chrome yellow and zinc chrome yellow etc.
ture of 200 nm. Iron hydroxyl phosphate with various It can form a passivation film on the surface of steel to
morphologies such as star-like and flower-like structures prevent air and water erosion [57, 58]. Electrocrystalliza-
were also obtained by controlling the experimental param- tion mechanism of iron phosphate coatings onto mild steel
eters [21]. electrode surfaces was studied [59]. The formation of a thin
The investigation on the crystallization of iron phos- and continuous iron phosphate layer showed an improve-
phate glasses shows that the structure of phosphate glass ment in anti-corrosion behavior in the research of electro-
changes from metaphosphate chain structures to the py- chemical corrosion behaviour of sintered composites [60].
rophosphate and eventually, to orthophosphate structures
with increasing Fe2 O3 content [49]. The doping of Al2 O3 ,
SiO2 or B2 O3 might improve the thermal stability of iron 3.3 Plant nutrition and fertilization
phosphate glasses [50].
FePO4 can be applied in the field of plant nutrition and fer-
tilization. The research indicates that FePO4 NPs prepared
by continuous industrially scalable method improved the
544 | X. Zhang et al.

availability of P and Fe for two hydroponically grown Compared with the crystalline sample, the mesoporous
crop species compared with bulk FePO4 [61]. Modified iron iron phosphate revealed better catalytic performance in
phosphate/polyvinyl alcohol composite film was designed the hydroxylation reaction of phenol in glacial acetic acid
as a new concept of controlled-release P fertilizer via incor- by hydrogen peroxide [8]. Catalytic behaviour of meso-
poration of FePO4 as a P source in polyvinyl alcohol films, porous iron phosphate in the gas-phase glycerol transfor-
which offers a new opportunity for the application of insol- mation exhibited a higher yield to acrolein than the other
uble phosphate as a phosphorous fertilizer [62]. simple phosphates, which possess a high crystalline char-
acter [68]. Nanotubular iron phosphate with composite
meso-macroporous structure, in favor of the diffusion of
3.4 Food additive reactive molecules, showed better catalytic performance
compared with the conventional particulate mesoporous
Iron phosphate can be used as an additive for food and iron phosphate in the direct hydroxylation of benzene with
feed, as a quality improver and iron fortifier. Food for- hydrogen peroxide [36]. Compared with flower-like, spher-
tification with iron phosphate is a promising new ap- ical and amorphous FePO4 , branch-like FePO4 presented
proach to reducing iron deficiency and FePO4 nanopar- a better catalytic performance in the cellulose conversion
ticles combine high bioavailability with superior sensory into 5-HMF [18]. In addition, novel 1,4-DHPs are prepared
performance in difficult-to-fortify foods. It can be as safe efficiently using aldehydes, benzylacetoacetate and cat-
for ingestion as FeSO4 , a commonly used food fortifica- alytic amount of iron(III) phosphate under solvent-free
tion [63, 64]. conditions in good yields [69].
SILAR deposited iron phosphate as a bifunctional elec-
trocatalyst for efficient water splitting was studied, which
3.5 Sensing may provide a facile and scalable approach to design a
high-efficiency, earth abundant electrocatalyst for water
Iron phosphate nanoparticles can be used as materials for splitting [70]. With the introduction of graphene oxide, en-
thin film optical waveguide due to its high transparency, hanced photo-Fenton degradation of rhodamine B was ob-
high refractive index and good film-forming property. The served using GO-FePO4 composites as effective and stable
bromothymol blue film-iron phosphate nano film/K+ ex- heterogeneous catalyst [71]. GO-FePO4 also displayed im-
changed glass composite optical waveguide sensing unit proved photocatalytic activities compared to pure FePO4
was developed to detect ammonia vapor with a detection in the degradation of methylene blue under simulated sun-
limit of 0.35 mg m−3 . It has features of fast response (10 s), light irradiation [72].
short recovery time (90 s), good reversibility and reusabil-
ity [65]. Iron phosphate nanoparticles were also employed
as an electrode substrate to immobilize myoglobin (Mb) 3.7 Battery electrode material
[32]. The Mb-FePO4 /GC electrode displays good features
in the electrocatalytic reduction of H2 O2 and can be used Iron phosphate has attracted extensive interest as a poten-
as a biosensor for detecting substrates with a low detec- tial cathode material for Li-ion batteries. As a precursor,
tion limit of 5 ± 1 µM. This study provides a simple and the synthesis methods, morphology, size, doping of FePO4
effective biosensing platform for the integration of pro- may affect the performance of batteries [73]. Goodenough
teins/enzymes and electrodes. et al. [74] firstly reported in 1997 that the olivine LiFePO4
could realize reversible extraction and insertion of lithium
with a theoretical specific capacity of 170 mA h g−1 . It is
3.6 Catalyst considered to be an ideal candidate for the cathode of a
low-power, rechargeable lithium battery that is inexpen-
Iron phosphate can be used as a catalyst for selective oxi- sive, nontoxic, and environmentally benign. LiFePO4 was
dation. The selective oxidation of methane was catalyzed synthesized in the presence of high-surface area carbon-
by iron phosphate with O2 , H2 O2 or N2 O as oxidant [66]. black as the cathode material of lithium battery [75]. Its
Fe-P-O based catalysts in the gas-phase direct oxidation discharge capacity can reach 170 mA h g−1 with good cycle
of benzene to phenol with N2 O as an oxidant are simi- stability. The cell was cycled for over 230 cycles with an av-
lar to the non-zeolite iron containing catalysts with high erage specific capacity of about 95 mA h g−1 . The discharge
selectivity like FeZSM-5 [67]. The tetrahedral coordinated capacity of amorphous nanoparticles FePO4 ·2H2 O as cath-
FeO4 would play an important role during the reaction. ode materials is about twice that of crystalline iron phos-
 Structure, morphology, size and application of iron phosphate | 545

phate [25]. A mesoporous structure imported into FePO4 directly used as the cathode material for rechargeable Mg-
could improve lithium intercalation/deintercalation kinet- ion batteries, and reversible capacity is achieved for the
ics of electrode materials for rechargeable lithium batter- first time [78]. Huang et al. [79] synthesized hollow FePO4
ies. Mesoporous FePO4 could deliver 120 mAh g−1 , which spheres wrapped by reduced graphene oxide as an effi-
was higher than that of reported amorphous and crys- cient sulfur host material. The material showed impressive
talline FePO4 [13]. With the preparation of mesoporous cycle stability with a low capacity decay rate of 0.037% per
iron phosphate, one promising lithium ion electrode was cycle at 0.5 C upon 1000 cycles, suggesting its enormous
obtained providing a stable capacity close to 100 mA h g−1 potential for high-performance of Li-S battery.
[9]. Amorphous iron phosphate nanowires were used for
lithium ion battery cathodes. The first discharge capac-
ity at a discharge rate of C/10 and 1C was 165 mAh g−1
(93% of the theoretical value) and 110 mAh g−1 , respec-
4 Application of iron phosphate in
tively [40]. The double-wall α-FePO4 nanotubes show in- adsorp-
teresting properties as a cathode material for Li ion bat-
tery, delivering a specific capacity of 125 mAh g−1 at a cur-
tion/separation/concentration
rent density of 35.6 mA g−1 [37]. Amorphous FePO4 hol-
Iron phosphates have good biocompatibility and impor-
low nanospheres directly grown on graphene were used
tant applications in biology. And, the unique local struc-
as a cathode material in lithium ion batteries [23]. This
tures of iron phosphates have the potential for the adsorp-
hybrid exhibits high rate capability and good cycle stabil-
tion of various species of environmental significance, espe-
ity because of efficient Li+ ion diffusion through the thin
cially metal ions. Some of their important applications in
wall of the hollow nanospheres and fast electron transport
adsorption, separation and concentration in recent years
through the graphene. The discharge capacity saturates
are as follows. Table 1 summarizes some typical applica-
to 174 mAh g−1 after 5 cycles, with high reversibility, and
tions on metals.
maintains a reversible capacity after 50 cycles of approxi-
mately 173 mAh g−1 . Compared with the traditional precip-
itation method, the cycling stability and rate performance
4.1 H2 O
of the LiFePO4 /C material synthesized by micro reaction
technology significantly improved [29]. The discharge ca- The study investigated the controlling on size and ad-
pacity reaches 162.7, 153.6, 142.7, 130.6 and 117.6 mAh g−1 sorptive properties of spherical ferric phosphate parti-
at the rate of 0.1, 1, 2, 3 and 5 C, respectively. A facile strat- cles [80]. The amorphous spherical ferric phosphate par-
egy to construct composites of amorphous FePO4 nanopar- ticles showed high selective adsorption of H O by penetra-
2
ticles and carbon additives with high dispersion and tap tion of H O molecules into ultramicropores. The more par-
2
density was developed as cathodes of lithium-ion batteries ticles grew, the more adsorption selectivity of H O became
2
[76]. Hybrid carbon additives were uniformly introduced remarkable.
into the α-FePO4 cathode to form a hierarchical 3D conduc-
tive network. the reversible discharge capacity could reach
175.6 mAh g−1 at 0.1 C and 139.1 mAh g−1 at 5 C. 4.2 Biomolecules
Recently, there have also been some reports about its
application as electrode materials for other batteries such Iron phosphate was reported for the selective adsorption
as Na-ion battery, Mg-ion battery, Li-S battery, etc. The of specific protein species from human whole blood by
findings indicated that amorphous FePO4 could be trans- Wang’s team in 2011 [81]. The favorable selectivity to-
formed into active NaFePO4 , which may have great poten- ward cytochrome c in the presence of acidic and neutral
tial as an electrode material for Na-ion batteries. The amor- proteins could be obtained under controlled experimen-
phous FePO4 shows better electrochemical performance in tal conditions, with a theoretical adsorption capacity of
terms of cyclic stability and discharge capacity, compared 37.59 µg mg−1 . No conformational change for cytochrome
with trigonal FePO4 [77]. FePO4 /C nanospheres demon- c after the adsorption and desorption processes, demon-
strate a high initial discharging capacity of 151 mAh g−1 strating the favorable biocompatibility of the as-prepared
at 20 mA g−1 , stable cyclability (94% capacity retention iron phosphate. In 2015, the team found a spherical
ratio over 160 cycles), as well as high rate capability (44 polyethyleneimine-iron phosphate nanocomposite with a
mAh g−1 at 1000 mA g−1 ) for Na-ion storage [28]. FePO4 /C size of ca. 100 nm showing favorable selective adsorption
prepared via electrochemical delithiation of LiFePO4 /C is to DNA against proteins [82]. The adsorption behavior fits
546 | X. Zhang et al.

Table 1: Applications of iron phosphate in adsorption, separation and concentration of metals in recent years.

Adsorbent Metals ACa Mechanism Ref.

(mg g−1 )
Fe7 (PO4 )6 nanosheets U(VI) 704.23 Monolayer Surface Complexation and Stacking mode [41]
Nano hierarchical Fe4 (P2 O7 )3 U(VI) 14 Inner-sphere surface complexation [83]
FePO4 Li+ , Na+ , K+ , Ion exchange [84–88]
Ca2+ , Mg2+ ,
Zn2+ , Cu2+ ,
Ni2+ , Co2+
PFP Cd2+ Co-precipitation [90]
Amorphous FePO4 Hg(II) 1.831b [31]
Ag(I) 1.354b
Amorphous FePO4 As(III)/As(V) 21/10 As (III) oxidized to As(V), replacing phosphate group, producing [91]
crystalline FePO4 16/9 Fe3 (AsO4 )2 ·8H2 O and FeAsO4 ·2H2 O precipitation
FePO4 As(V) Anion exchange [92]
FePO4 (SCS) Cr(VI) 21 [94]
FePO4 (SS) 13.2
FePO4 (SM) 12.1
FePO4 Cr(III) 8.12 Electrostatic interaction and coordination [95]
FePO4 Cr(III) 0.182 ± [27]
different sizes 0.005c
FePO4 (microsheet) Cr(III) 14.17 Consistent with 92 [96]
FePO4 (microsphere) 9.90
FePO4 (nanoparticle) 5.30
Vivianite Fe3 (PO4 )2 ·(H2 O)8 Cr(VI) Reduced to Cr(III) via adsorption and inner-sphere complexation [97]
FePO4 -MWNTs Cd(II) 32.68 [98]
Fe3 O4 @FePO4 nanoparticles Cd(II) 13.51 Electrostatic interaction, ion insertion and coordination [99]
pollen@FePO4 Cd(II) 4.20 Electrostatic and complexation
microspheresd Pb(II) 61.35 Mainly complexation
FePO4 ·2H2 O Cd(II) 51.7 Ion-exchange [100]
Pb(II) 151.2 Chemical adsorption [101]
Hybrid bio-nanocomposites As(III) 162.00 Cd(II), Pb(ll): transformation of hydroxyl groups and precipitation [102]
Cd(II) 205.83 with phosphate
Pb(II) 730.79
Cellulose-stabilized Pb(II) Cu(II): formation of Cu3 (PO4 )2 and Cu5 (PO4 )3 OH [103,
nanoparticlese Cu(II) 104]
ACa : Adsorption capacity; b : mmol g−1 ; c : mg m−2 ; d : unpublished work; e : for soil remediation

Langmuir model, corresponding to an adsorption capac- plexation, which was a spontaneous and endothermic pro-
ity of 61.88 mg g−1 . The adsorbed DNA could be readily re- cess. The ultra-thin iron phosphate nanosheets with fine-
covered by using a 0.04 mol L−1 BR buffer at pH 10. The controlled morphology were used as a new 2D material for
nanocomposites were further used for the isolation of DNA uranium adsorption [41]. It shows an extreme-high U(VI)
from a series of real sample matrices. adsorption capacity of 704.23 mg g−1 , about 27 times of
conventional 3D material (24.51 mg g−1 ) and higher than
most 2D absorbent materials. The sorption is spontaneous
4.3 Radioactive element and endothermic, and can be conformed to single molecu-
lar layer adsorption. The possible adsorption mechanism
Iron phosphate has shown great value in the treatment can be described as a Monolayer Surface Complexation
of radioactive wastewater. The nano-size hierarchical and Stacking mode.
Fe4 (P2 O7 )3 with high stability in solution, synthesized by
using high temperature solid state reaction method, was
applied to adsorb U(VI) ions from aqueous solutions [83].
The maximum sorption capacity of Fe4 (P2 O7 )3 towards
U(VI) at pH 5.5 was calculated to be 14 mg g−1 . The sorption
of U(VI) is mainly dominated by inner-sphere surface com-
 Structure, morphology, size and application of iron phosphate | 547

4.4 Alkali metals, alkaline earth metals and precipitator [90]. Over 95% of Cd was adsorbed. The deter-
some divalent metal cations mination of Cd in river water samples was achieved by us-
ing spectrophotometry.
Mustafa and Naeem et al. studied the adsorption perfor- Lenoble et al. [91] considered that both amorphous
+ + + and crystalline iron(III) phosphate were efficient at arsenic
mance of iron phosphate on alkali metals (Li , Na , K ),
2+ 2+ removal. Results showed that the maximum adsorption ca-
alkaline earth metals (Ca , Mg ) and divalent metal
2+ 2+ 2+ 2+ −1
cations (Zn , Cu , Ni , Co ) [84–88]. They consider pacities were higher towards As(III), i.e., 21 mg g and 16
−1 −1
that the adsorption mechanism is related to the ion ex- mg g , and, the capacities to As(V) were 10 mg g and
−1
change between protons on the surface of iron phosphate 9 mg g , respectively. The mechanism might involve: As
and metal cations in the solution. (III) is oxidized to As(V) by Fe (III), and then As(V) replaces
Potentiometric titrations of iron(III) phosphate have the phosphate group in iron phosphate, resulting in the
shown an apparently weak monobasic acid behavior to- precipitation of Fe3 (AsO4 )2 ·8H2 O and FeAsO4 ·2H2 O. This
wards alkali, alkaline earth and divalent transition metal sorbent could be a potential candidate for industrial waste
ions [85]. The selectivity sequence and dissociation of the treatment, although the high release of phosphate and
exchanger was found to increase in the order Cu2+ > Zn2+ iron will exclude its application in drinking water plants.
> Ni2+ > Ca2+ > K+ . The sorption process of iron(III) phos- Hamayun et al. [92] studied the equilibrium and kinetics
−
phate toward Zn2+ was found to be endothermic in nature of H2 AsO4 adsorption by FePO4 . Adsorption of arsenic on
and the dissociation process was also observed to be en- FePO4 was favorable in lower pH range at higher tempera-
dothermic [86]. Naeem et al. [88] further studied adsorp- ture. Anion exchange process might be responsible for the
−
tion of Cu2+ and Co2+ ions from the aqueous electrolyte uptake of H2 AsO4 onto FePO4 . He et al. [93] discussed the
solution onto the FePO4 . The isosteric heat (∆H) of metal effects of pH, arsenic concentration, temperature and mix-
ions sorption showed that the adsorption reaction is en- ing speed on adsorption performances of iron phosphate
dothermic and the surface of FePO4 is energetically het- for arsenic. The adsorption efficiency of arsenic adsorp-
erogeneous. The desorption mechanism might be cation tion reached 99. 6% under the optimum conditions: initial
−1
exchange, between the metal ions released from metal arsenic concentration of 0.0001 mol L , pH of 7, stirring
−1 ∘
loaded surface of FePO4 and H+ adsorbed from the aque- speed of 600 r min , temperature of 80 C, reaction time
ous solution into the solid phase. The mechanism for ad- of 1 h. It was considered meaningful to solve the arsenic
sorption and desorption of metal ions can be proposed ac- pollution problem in drinking water or soil.
cording to the reactions 1 and 2, respectively. Baykan et al. [94] prepared iron orthophosphate by
different methods. The equilibrium data for the adsorp-
P-OH + M+ ⇔ P-OM + H+ (1) tion of chromium on the prepared materials were ana-
lyzed in Langmuir and Freundlich isotherm models. The
+
P-OM + H ⇔ P-OH + M +
(2) adsorption process could be described by pseudo-second-
order kinetic model. The maximum adsorption capacity of
+
Where P stands for the solid surface and M represents di- Cr(VI) on the iron orthophosphate synthesized by solution
valent metal ion in its hydrolyzed form (MOH+ ). combustion (SCS), solid state (SSS), and solution method
(SM) are 21, 13.2, and 12.1 mg g−1 , respectively, at 100 ppm
chromium concentration with 1 g L−1 adsorbent dose for
4.5 Heavy metals 2 h. The solution combustion synthesized material is the
most efficient adsorbent because of its high surface area.
Yin et al. [31] studied the adsorption properties of amor- The research shows that iron orthophosphate is cheap and
phous iron(III) phosphate for heavy metal ions and found easy to operate for adsorption of Cr(VI) from wastewater.
that its excellent absorption capacity for Hg(II) and Ag(I) The author has been studying the adsorption behav-
could reach to 1.831 mmol g−1 and 1.354 mmol g−1 , respec- ior and mechanism of iron phosphate for heavy metals in
tively, at pH = 5.98. The adsorption properties for Hg(II) recent years. One of the studies showed that Cr(III) was ad-
were stronger than those for Ag(I). sorbed on the prepared iron phosphate with an ca. 62/1 se-
Xia et al. [89] prepared a complex polymeric ferrum lectivity over Cr(VI) [95]. The adsorption of Cr(III) fits Lang-
oxydatum phosphate and studied its flocculation in 2000. muir model, corresponding to a maximum adsorption ca-
The results predict that it will be a flocculating agent pacity of 8.12 mg g−1 . The retained Cr(III) could be readily
with good stability. It can also be used to concentrate mi- recovered and quantified with detection by electrothermal
cro amounts of cadmium in water as a new inorganic co- atomic absorption spectrometry (ETAAS), with an enrich-
548 | X. Zhang et al.

ment factor of 8.7 and a detection limit (LOD) of 0.02 µg L−1 . author’s recent work not published, the maximum adsorp-
Total chromium was determined after reduction of Cr(VI) tion capacities of iron phosphate modified pollen micro-
to Cr(III). The content of Cr(VI) was achieved by difference. spheres (pollen@FePO4 ) for Cd(II) and Pb(II) are 4.20 and
Thus, chromium speciation of different kinds of environ- 61.35 mg g1 , respectively. The preliminary study showed
mental samples was achieved. The adsorption mechanism that the adsorption mechanism of Cd(II) is related to elec-
was related to electrostatic and coordination. Zhang et al. trostatic and complexation, and that for Pb (II) is mainly
[27] studied the adsorption of Cr(III) on FePO4 nanoparti- complexation.
cles with different sizes. The adsorption of capacity was Phosphated residue generated from iron and steel
in proportion to the specific surface area. The same Cr(III) plants, mainly composed of FePO4 ·2H2 O, can be directly
adsorption capacity was obtained as 0.182 ± 0.005 mg m−2 reused for removing Pb2+ and Cd2+ from wastewater by
when expressing the results as per m2 adsorbent. They fur- adsorption [100, 101]. The sorption behavior of Cd2+ and
ther realized morphology control of iron phosphate from Pb2+ could be described better by pseudo-second order
amorphous nanoparticle to monoclinic microsheet or mi- kinetic model and Langmuir isotherm model. The maxi-
crosphere simply by only changing the addition of H3 PO4 mum adsorption capacities for Cd2+ and Pb2+ derived from
in the reaction system [96]. The maximum adsorption ca- Langmuir model were 51.7, 151.2 mg g−1 , respectively. The
pacities of Cr(III) for different morphologies of nanoparti- possible adsorption mechanism of Cd2+ was mainly the
cle, microsheet, and microsphere are 5.30, 14.17, and 9.90 ion-exchange between the metal cation Cd2+ and Fe of
mg g1 , respectively. The result is not proportional to the the phosphated residue. The mechanism of Pb2+ sorption
surface area and pore volume. The adsorption behavior might be chemical adsorption predominantly by dissolu-
is consistent with the explanation of adsorption mecha- tion of FePO4 ·2H2 O and formation of precipitation, i.e.,
nism in literature [95]. Bae et al. [97] conducted experi- Pb3 (PO4 )2 and Pb5 (PO4 )3 OH. Simultaneous adsorption of
mental and theoretical studies to identify the molecular- As(III), Cd(II) and Pb(II) by hybrid bio-nanocomposites of
scale reaction mechanism for Cr(VI) removal by a ferrous nano hydroxy ferric phosphate and hydroxy ferric sulfate
phosphate mineral, vivianite, Fe3 (PO4 )2 ·(H2 O)8 . Cr(VI) is particles coating on Aspergillus niger was studied [102].
readily reduced to Cr(III) by vivianite via adsorption and The adsorption capacities for As(III), Cd(II), and Pb(II)
inner-sphere complexation, suggesting that in anoxic iron- were 162.00, 205.83 and 730.79 mg g−1 , respectively. The
phosphate-enriched environments, vivianite may signifi- adsorption of Cd(II) and Pb(ll) was associated with trans-
cantly influence the fate and transport of Cr(VI). formation of hydroxyl groups and precipitation with phos-
The author modified multi-walled carbon nanotubes phate.
with iron phosphate to obtain a composite material FePO4 - The sorption of heavy metals on iron phosphate ma-
MWNTs for the purpose of improving its selectivity and terials also plays a role in the remediation of polluted
sorption capacity to cadmium [98]. The FePO4 -MWNTs of- soils. Liu et al. [103, 104] prepared and tested sodium car-
fer a much-improved sorption capacity of 32.68 mg g1 for boxymethyl cellulose-stabilized iron phosphate nanopar-
cadmium over 6.72 mg g1 by bare carbon nanotubes af- ticles for in-situ immobilization of heavy metals in soils.
ter oxidation at pH 6. The composites were packed into a The particle size was 8.4 ± 2.9 nm. The nanoparticles can
mini-column for on-line selective preconcentration of cad- effectively reduce the leachability and bioaccessibility of
mium with detection by ETAAS, with an enhancement fac- Pb and Cu in three representative soils (calcareous, neu-
tor of 31.2 and LOD of 1.3 ng L−1 . In the author’s another tral, and acidic). The results showed that the leachability
work [99], superparamagnetic Fe3 O4 @FePO4 nanoparti- of Pb and Cu was reduced by 85-95% and 63-87%, and
cles with core shell structure were prepared by coating iron the bioaccessibility was lowered by 31-47% and 54-69%
phosphate on the surface of Fe3 O4 nanoparticles by liquid after the soils were treated for 56 days. The formation of
phase deposition method. Its unique magnetic properties copper phosphate minerals through precipitation and ad-
are favorable for rapid separation and preconcentration of sorption was probably responsible for the decrease of Cu
trace cadmium from aqueous solutions. The adsorption of availability in soils [104]. Further tests revealed the forma-
Cd(II) fits Langmuir model, deriving a maximum adsorp- tion of Cu3 (PO4 )2 and Cu5 (PO4 )3 OH resulting in the de-
tion capacity of 13.51 mg g1 . The retained Cd(II) could be creased solubility of the Cu(II) in the acidic pH range. Yuan
readily recovered with detection by ETAAS, along with an et al. [105] prepared a polymeric hydroxyl ferric phosphate
enrichment factor of 10.3 and LOD of 0.021 µg L−1 . In ad- (PHFP) from industrial byproducts for in-situ immobiliza-
dition, the adsorption mechanism of Cd(II) onto the sur- tion of Cd(II) and Pb(II) in soils. PHFP amendment can
face of Fe3 O4 @FePO4 nanoparticles might involve electro- enhance the formation of stable Cd and Pb fractions and
static interaction, ion insertion and coordination. In the decrease Cd and Pb bioavailability. The removal rates of
 Structure, morphology, size and application of iron phosphate | 549

DTPA-extractable Cd and Pb in soils reached up to 33% and

45%, and the water-soluble Cd and Pb decreased by 56%
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