Journal of Environmental Management 193 (2017) 79e91

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Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Review

Calcium hydroxyapatite-based photocatalysts for environment

remediation: Characteristics, performances and future perspectives
C. Piccirillo*, P.M. L. Castro

lica Portuguesa, CBQF - Centro de Biotecnologia e Qumica Fina e Laborato
Universidade Cato
rio Associado, Escola Superior Biotecnologia, Porto, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Calcium hydroxyapatite Ca10(PO4)6(OH)2 (HAp) is a material widely used in biomedicine, for bone im-
Received 29 November 2016 plants manufacture, due to its biocompatibility. HAp has also application for environmental remediation,
Accepted 28 January 2017 as it can be employed as metal removal; moreover, it has the capability of effectively adsorbing organic
Available online 10 February 2017
molecules its surface.
In recent years, the photocatalytic properties of HAp have been investigated; indeed several studies
Keywords:
report of HAp used as photocatalyst, either on its own or combined with other photocatalytic materials.
Hydroxyapatite
Although in the majority of cases the activity was induced by UV light, some reports of visible light-
Photocatalysis
Environment remediation
activated materials were reported.
Pollutants' degradation Here we present a critical review of the latest developments for HAp-based photocatalysts; the ma-
terials discussed are undoped single phase HAp, doped HAp and HAp-containing composites.
For undoped single phase HAp, the possible surface treatment and lattice defects which can lead to a
photoactive material are discussed.
Considering doped HAp, the use of Ti4 (the most common dopant) is described, with particular
attention to the effects that this metal have on the characteristics of the material (i.e. crystallinity) and on
its photocatalytic behaviour. The use of other dopants is also discussed.
For the multiphasic materials, the combination of HAp with other photocatalysts is discussed, mainly
but not only with titanium dioxide TiO2.
Overall, HAp is a compound with high potential as photocatalyst; this property, combined with its
capability for heavy metal removal, makes it a multifunctional material for environmental remediation.
As future perspectives, further studies, based on the results obtained until present, should be per-
formed, to improve the performance of the materials and/or shift the band gap into the visible. The use of
other dopants and/or the combination with other photocatalysts, for instance, are features which is
worth exploring.
2017 Elsevier Ltd. All rights reserved.

Contents

1. Heterogeneous photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2. Hydroxyapatite structure and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3. Photocatalytic single phase HAp . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4. Doped photocatalytic HAp . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5. Multiphasic HAp-containing photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5.1. HAp-TiO2 biphasic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
5.2. HAp-TiO2 multiphasic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.3. Other photocatalytic HAp-containing composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
6. Discussion and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

* corresponding author.
E-mail address: cpiccirillo@porto.ucp.pt (C. Piccirillo).

http://dx.doi.org/10.1016/j.jenvman.2017.01.071
0301-4797/ 2017 Elsevier Ltd. All rights reserved.
80 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91

Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

1. Heterogeneous photocatalysis Natarajan, 2015; Lyandres et al., 2012). The photocatlysts should
also be stable in the environment(s) they will be used in; moreover,
Photocatalysis is a general term which refers to a photoreaction considering in particular the use for environment remediation, the
whose rate is increased due to the action of a catalyst (Castellote photocatalyst should also be non-toxic.
and Bengtsson, 2011). Photocatalytic reactions can be homoge- As already mentioned above, TiO2 is the most used photo-
neous or heterogeneous. In homogeneous photocatalysis, both the catalyst to date. TiO2 can exist in three structures e anatase, rutile
reactants and the photocatalyst are in the same phase; in the het- and brookite; although the anatase is the most effective photo-
erogeneous, on the contrary, the phases are different, the photo- catalyst, materials containing a combination of different TiO2
catalyst being generally in solid phase with the reactants being phases, anatase and rutile in particular, showed the highest pho-
liquids or gases. tocatalytic activity (Di Paola et al., 2012; Tobaldi et al., 2013). In
Heterogeneous photocatalysis processes, in particular, gained recent years, however, there has been increasing interest in the
increasing attention in latest years, due to the interesting applica- development of other photocatalysts, using different semi-
tions in several areas, which include environment remediation, conductor materials. One of the reasons for nding alternative
energy production and catalysis of chemical reactions (Lee, 2016; materials is that TiO2 has a band-gap in the ultraviolet region
Matsuoka et al., 2007; Colmenares and Luque, 2014). Generally (about 3.2 and 3.0 eV for anatase and rutile respectively); therefore,
heterogeneous photocatalysts are inorganic semiconductors (SC), it uses only a small fraction (3e5%) of the solar light (Mo and Ching,
titanium dioxide TiO2 being the most common example. To act as 1995). Indeed several visible-light photocatalysts were developed,
photocatalyst, such semiconductor should have a full valence band some examples being zinc and tungsten oxides or silver phosphate
and an empty conduction band. When irradiated with light whose (Di Paola et al., 2012; Martin et al., 2015).
energy is equal or higher to that of the band gap, an electron will be At the same time, however, composite photocatalysts were also
promoted from the valence band to the conduction band; this will considered; several combinations using different materials were
generate a hole-electron pair, according to the reaction: studied, many of which were still based on TiO2. The presence of
more than one compound can increase the efciency in the
SC hn / e h charges' generation and reduce their combination, hence leading to
materials with higher photocatalytic activity; moreover, photo-
Both charged species can then react with other chemical com- catalysts with different band gap values can be obtained (Marschall,
pounds they are in contact with; a reaction with water or molecular 2014).
oxygen, for instance, are reported below (Hashimoto et al., 2005). Hydroxyapatite was one of the materials studied while search-
ing for alternative photocatalysts. The sections below will describe
H2O h / HO H the structure and the most important properties of this compound;
subsequently a review of the hydroxyapatite application as pho-
O2 e / O
2 tocatalyst will be presented.

The radicals and/or ionic species formed can react further, to

2. Hydroxyapatite structure and properties
form more species, which are referred to as Reactive Oxygen Spe-
cies (ROS).
Calcium hydroxyapatite (HAp) is a phosphate with the formula
Ca10(PO4)6(OH)2. HAp can have two possible structures, as it can be
O
2

H / HO2
either monoclinic or hexagonal (space groups P21/b and P63/m
respectively); the most common form is the hexagonal one, shown
h O
2 / 2O

in Fig. 2. It can be seen that calcium has two possible positions, Ca1
and Ca2 (Chiatti et al., 2012).
The full reaction scheme is shown in Fig. 1. Considering the
Hexagonal HAp is the main component of human and animal
application for environment remediation, ROS can then react with
bones (Figueiredo et al., 2010); because of this, synthetic HAp is
other molecules, such as organic contaminants or toxic gaseous
widely used in biomedicine. HAp, in fact, it replicates the compo-
species; such reactions can eventually lead to a partial or full
sition and behaviour of human bones; it is therefore used to
degradation of these molecules.
fabricate bone implants. For this particular application, carbonated
A photocatalyst should have several characteristics to be usable
HAp is used, to mimic more closely the composition of human
in technological applications; a very important parameter is the
bones (Boutinguiza et al., 2012). HAp is very biocompatible and
efciency in photogenerating the (e- h) charges under appro-
osteoconductive, as it favours the formation of new bone through
priate light irradiation. Also, once the charges are generated, it is
osteoblast cells' growth (Nathanael et al., 2016). Other applications
important to avoid their recombination; fast recombination is in
in biomedicine include drug delivery (Cole et al., 2016) and bio-
fact one of the main drawbacks of the heterogeneous photo-
imaging (Xu et al., 2016).
catalysis (Xu et al., 2014). Several parameters, further than the
HAp has very low solubility at neutral pH; in literature, however,
nature of the photocatalyst, can affect both these properties; the
very different acidity constants were reported. According to Ber-
morphology of the material, for instance, can be determinant. In the
tazzo, in fact, pK values in the range between 84 and 120 were
case of nanomaterials, on the other hand, the dimensions and the
measured (2010); these differences can be due to different pa-
shape of the particles are also crucial, while for deposited coatings,
rameters. The stoichiometry of the compound, for instance, can
preferred orientation can play a role (Hu et al., 2016; Jo and
have a signicant effect; the presence of carbonate in the HAp
 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91
Fig. 1. Representation of the photocatalysis reaction scheme for an inorganic semiconductor (SC).
lattice can also play a key role (Bengtsson et al., 2009; Pan and
Darvell, 2007). Moreover, in the case of nanomaterials, the size
and the shape of the particles is also determinant (Bose and Tarafde,
2012). HAp is stable in basic solution and it can be slowly dissolved
in acidic environment; studies of the dissolution rate showed that
HAp does not dissolve according to its stoichiometry but that,
depending on the conditions, a preferential dissolution of either
calcium or phosphorus can take place (Hankermeyer et al., 2002;
Piccirillo et al., 2014).
Due to its crystal structure, HAp can effectively capture metal
ions, particularly bivalent ones such as lead, zinc, cadmium, etc.
According to literature, there are two possible mechanisms for the
ion capture, that is ion exchange between the calcium and the
bivalent ions and dissolution-precipitation (Nzihou, 2010). Both
mechanisms are favoured by HAp exible framework and by the
fact that the calcium ions are placed on the external crystal faces.
Due to this property, HAp is used for environmental remediation, to
remove heavy metals from contaminated wastewaters and/or soils
(Viipsi et al., 2013).
Stoichiometric defect-free HAp is not a good electrical
conductor (Dubey et al., 2013); indeed literature reports of single-
phase HAp sample with band gap value higher than 6 eV, corre-
sponding to an insulator (Tsukada et al., 2011). Because of this, HAp
with these characteristics does not have any photocatalytic activity.
Fig. 2. Crystallographic structure of hexagonal HAp (Nzihou, 2010).
81
The presence of either defects or dopants, however, can change the
electronic levels and lead to a decrease in the band gap value; the
material, therefore, can behave as a photocatalyst. Similarly the
combination with other photocatalytic compounds such as TiO2 can
lead to HAp-based multiphasic photocatalysts.
In the sections below we will report on the various forms of
photocatalytic HAp (see Fig. 3), starting from the single phase un-
doped materials; then doped HAp compounds will be described.
Finally, HAp-based multi-phasic photocatalysts will be considered.
3. Photocatalytic single phase HAp
As mentioned above, stoichiometric defect-free HAp does not
have photocatalytic activity, due to its insulating nature. Some
forms of HAp, however, were reported to show photocatalytic
properties; although the reasons for this behaviour are not
completely clear, the most likely explanation for this is the presence
of defects in the HAp lattice, as well as some specic surface
modications.
Table 1 summarises the most important reports on this topic.
The rst study on photocatalytic single phase HAp was published
almost 15 years ago and described the UV-induced degradation of
methyl mercaptane (Nishikawa and Omamiudab, 2002). Authors
reported that the HAp powder (prepared by chemical precipitation)
effectively degraded the S-containing pollutant after a heat treat-
ment at 200  C; treating the same powder at 1150  C, on the other
hand, did not lead to a photoactive material. The same research
group performed more studies on this, showing that HO and O 2

species were detected by EPR technique for the material treated at
200  C but not for that treated at 1150  C (Nishikawa, 2003a).
Further subsequent analysis of these materials showed that 200  C
heat treatment caused some changes in the phosphate groups on
the surface of the material, leading to a vacancy in the HAp lattice
(Nishikawa, 2007); this vacancy made the trapping of the above
mentioned ROS possible and, consequently, the material showed
photocatalytic behaviour.
The key role of the phosphate groups in the photocatalysis
mechanism was further investigated by Tanaka et al. (2012); au-
thors showed that the rst step in the UV photodegradation of
dimethyl sulphide was its adsorption on the P-O-H groups. Indeed
other studies reported that a decrease in the intensity of the PO4
peak could be observed in the infrared spectra of photocatalytic
HAp powders, after the material was used in photocatalytic ex-
periments (Nishikawa, 2003b; Sharifudin et al., 2013). Such
decrease corroborated the hypothesis that the phosphate groups
were involved in the photocatalaysis and were consumed/dissolved
82 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91
Fig. 3. Scheme of HAp-based photocatalytic materials.
during the process.
Photocatalytic activity for single phase HAp can depend on
many other features, which are not yet completely claried.
Sharifdin et al. (2013), for instance, reported that HAp derived
from waste mussel shells showed higher photocatalytic activity
than a commercial material; their hypothesis was that the powder
derived from mussel shells had higher carbonate content, due to
the incomplete conversion of the calcium carbonate of the shells
into phosphate. The authors of this study, however, acknowledged
that further analyses were necessary to conrm this and further
elucidating the mechanisms.
The pH value at which the photodegradation is performed can
also play a crucial role; in a study performed by Reddy et al. (2007),
for instance, single-phase HAp showed photoactivity comparable to
that of commercial TiO2 P25 Evonik-Degussa for the degradation of
an azo-dye in an acid environment. In basic conditions, on the
contrary, the material was much less effective.
Surface modication(s) can also have an effect on the photo-
catalytic behaviour; Tripathi et al. (2015) described the synthesis of
HAp nanobers with precipitation method using yeast extract as
template agent. Their material acted as a photocatalyst, as it
effectively degraded methylene blue; a possible explanation for this
is that the proteins for the yeast extract acted as active site for the
dye adsorption, hence favouring its degradation.
Some forms of HAp derived from sh bones was also reported to
have photocatalytic activity (Piccirillo et al., 2013). The authors of
this study treated cod sh bones with calcium acetate and suc-
cessively annealed the bones at high temperature (1000  C); the
resulting HAp powder showed photocatalytic behaviour. The au-
thors explained such behaviour proposing the formation of oxygen
vacancy in HAp lattice during the bones calcination; such vacancy
formation would have been favoured by the reducing environment,
due to the presence of organic molecules/fragments derived from
calcium acetate.
This hypothesis was successively conrmed by a modelling
study, performed using the Density Functional Theory (DFT)
(Bystrov et al., 2016). This research showed that an oxygen vacancy
in the phosphate groups would lead to an energy band gap of about
3.45 eV; this value is in agreement with that measured by Piccirillo
et al. (2013). Moreover, DFT calculations also showed that removing
an OH group would lead to a band gap value in the range
1.6e2.4 eV; this would correspond to a visible light activated
photocatalyst. No material with such characteristics, however, has
been reported up to date.
4. Doped photocatalytic HAp
The most common dopant to obtain photocatalytic HAp is tita-
nium. The rst report on Ti-doped HAp was published by
Wakamura et al. (2003); they prepared the powder material by co-
precipitation method, adding a titanium salt (Ti(SO4)2) to the re-
action between calcium and phosphorus. Results showed that
titanium-doped powders could absorb light with wavelength
smaller than 380 nm, i.e. in the UV range. The photocatalytic ac-
tivity of these rst materials was tested both in liquid and gas
phase, monitoring the degradation of albumine and acetaldehyde
under UV light irradiation (see Table 2), with both chemicals being
effectively degraded.
Ti-doped HAp materials behave as semiconductors; literature
reports that such change is due to a hybrid orbital formed
combining the 2p orbital of the oxygen atom and the 3d orbital of
the titanium; this leads to the formation of an additional electronic
level which reduces the value of the band gap energy (see Fig. 4)
(Tsukada et al., 2011). As for every semiconductor, the value of the
energy band gap may be affected by several parameters, including
the microstructure and morphology of the material, its shape/di-
mensions in case of nanocrystals, etc. (Lin et al., 2006). Indeed
different energy were measured for Ti-doped HAp, such as 3.75,
3.65 and 3.13 eV (Tsuruoka et al., 2015; Tsukada et al., 2011; Kandori
et al., 2012); in all cases, such values fall in the UV. Modelling
studies predicted that the ion Ti4 gets substituted into the lattice,
replacing the calcium in position Ca1, in a material with Ca1 de-
ciency and with a columnar structure (Tsukada et al., 2011). Ti4
insertion causes a shrinkage in the HAp lattice volume, due to the
smaller ionic radius of titanium when compared to calcium e 0.68
vs 0.99 A respectively (Ergun, 2008; Ribeiro et al., 2006).
The rst study on Ti-doped HAp showed the potential of these
materials, but also highlighted one possible problem, that is the
decrease of crystallinity in the HAp structure due to the insertion of
the Ti4 ion in its lattice. Indeed literature data conrmed that Ti-
substituted HAp is less crystalline than undoped HAp, and such
 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91 83

Table 1
Single-phase photocatalytic HAp materials.

Preparation method Characteristics of the Testing conditions (irradiation, Degradation efciency/ Reference
material pollutant, catalyst load) photocatalyst performance

Gas phase
Chemical precipitation followed Surface area: 66.5 m2/g l 254 nm, 8.8 mW/cm2 96% in 4 h Nishikawa and
by heating at 200  C Methyl mercaptane Omamiudab (2002)
Hydrothermal synthesis followed Rod-shaped particles l 254 nm, 6 W 30% in 1 h Tanaka et al. (2012)
by heating at 200  C (80  14 nm) Dimethyl sulphide
2
Surface area: 101 m /g
Ca/P 1.64
Liquid phase
Chemical precipitation followed by heating at Surface area: 56 m2/g UV mercury lamp, 250 W 92% in 12 h Reddy et al. (2007)
400  C Calmagite
3.0 g/L
Chemical precipitation from mussel shell, Ca/P 1.66 l 340 nm, 0.81 mW/cm2 62% in 24 h Sharifdin et al. (2013)
followed by heating at 800  C Methylene blue
2.0 g/L
Thermal extraction from cod sh bones Needle-like crystals (1 l 365 nm, 8 W 80% in 8 h Piccirillo et al. (2013)
(treatment in calcium acetate) e2 mm) Methylene blue 75% in 24 h Ma
rquez-Brazo
n et al.
Surface area: 19.29 m2/ l 365 nm, 1.84 mW/cm2 (2016)
g Fluoxetine
Ca/P 1.60 4.0 g/L
Chemical precipitation in presence of yeast Nanobres l 365 nm, 300 W 75% in 5 h Tripathi et al. (2015)
(300  6 nm) Methylene blue
0.1 g/L

effect is more enhanced for higher Ti4 concentration (Anmin et al., that a titanium ion doping concentration of XTi 0.2 corresponded
2007; Ribeiro et al., 2006). Consequently, materials with high ti- to the HAp with the maximum photocatalytic activity; higher Ti4
tanium content may not be more active photocatalysts, due to the ion concentrations (i.e. XTi 0.5), on the other hand, led to a
lower crystallinity level. Anmin et al. (2007), for instance, reported decrease in the photocatalytic performance. The opposite effect

Table 2
Ti-doped photocatalytic HAp materials.

Preparation method Characteristics of the Testing conditions (irradiation, Degradation efciency/ Reference
material pollutant, catalyst load) photocatalyst performance

Gas phase
Hydrothermal XTi  0.8 XTi 0.1 100% after 100 h Wakamura
Nanoparticles with UV, 1 mW/cm2 et al. (2003)
irregular shape (~50 nm) Acetaldehyde
Surface area: 85 m2/g
Co-precipitation followed by thermal treatment (650  C) XTi 0.1 XTi 0.1 CO2 formed from the Tsukada et al.
Particle smaller than Xe lamp (UV Vis), 1.25 mW/cm2 degradation about (2011)
100 nm Acetaldehyde half than that formed with
Surface area: 85 m2/g TiO2
4
Commercial material (Tahiei Chemical Industrial Co), XTi 0.1, Cr3 grafting up 3
XTi 0.1, Cr grafting 10 mol/L Complete degradation Wakamura
subsequent Cr3 impregnation of the powder to 102 mol/L Visible (Xe lamp) after 3 h et al. (2011)
Rod-shaped particles Acetaldehyde
(60  20 nm)
Surface area 46e50 m2/g
Hydrothermal, subsequent Cu2 impregnation XTi  0.1, Cu2 grafting up XTi 0.1, Cu2 0.05 % wt CO2 formed from the Nishikawa
of the powder to 0.1 % wt l 365 nm, 1 mW/cm2 degradation about et al. (2013)
Surface area: 47.8 m2/g Acetaldehyde double for Cu2-
impregnated material than
for unmodied Ti-HAp
Commercial material (Hautoform TA) Surface area: 39 m2/g UV, 1 mW/cm2 CO2 formed from the Tsuruoka et al.
2-propanol (IPA) degradation about a (2015)
quarter than that formed
with TiO2
Liquid phase
Hydrothermal XTi  0.8 XTi 0.1 100% after 12 h Wakamura
Nanoparticles with UV, 1 mW/cm2 (comparable to TiO2) et al. (2003)
irregular shape (~50 nm) Albumine
Surface area: 85 m2/g
Hydrothermal synthesis followed by thermal treatment XTi  0.5 UV (l 365 nm) and Vis UV: 70% after 1 h Anmin et al.
(190  C) Rod-shaped crystals (l > 400 nm) (comparable to TiO2) (2007)
(70  10 nm) Methylene blue Vis: 55% after 1 h (higher
Surface area: 150e177 m2/ 0.4 g/L than TiO2)
g
Co-precipitation followed by thermal treatment (650  C) XTi  0.2 l 365 nm, 1 mW/cm2 Complete selective Kandori et al.
Rod-shaped particles Bovine serum albumin, lysozyme degradation (2013)
Surface area: 34e53 m2/g myoglobin, lysozyme
12.5 g/L

Note: XTi Ti/(Ti Ca) (mol/mol).

84 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91
Fig. 4. Electronic structure in Ti-doped HAp; different band gap values were reported
(see the text), all in the UV range.
Fig. 5. Effect of the titanium concentration as HAp dopant on its structure; these two
features have opposite effect on the photocatalytic activity.
that titanium concentration has on HAp structure is represented in
Fig. 5.
Literature reports that, in specic preparation conditions, Ti-OH
groups were formed on the surface of Ti-doped HAp samples; such
groups could promote ROS generation and hence made the material
a more effective photocatalyst. This hypothesis was corroborated by
the detection of an infrared peak at 3737 cm1, which was detected
only in some more active Ti-doped HAp (Kandori et al., 2012). The
authors of this study suggested that the Ti-OH species was formed
due to a dislocation of an OH group; the mechanisms leading to
such dislocation, however, are not yet clear.
To assess the effectiveness of Ti-doped HAp materials as pho-
tocatalysts on different compounds, a comparison study was per-
formed by Kandori et al. (2013), who tested the photoinduced
degradation of three different high molecular weight proteins e
Table 3
Doped photocatalytic HAp materials using other metals.
Preparation method and dopant Characteristics of the
material
Gas phase
Hydrothermal followed by thermal treatment (400 XV  0.1
e650  C), vanadium (III) Agglomerated particles
(100e200 nm)
Liquid phase
Commercial undoped HAp followed by Fe3 Sphere-like nanoparticles
impregnation (<50 nm)
Surface area: 204 m2/g
bovine serum albumin (BSA), neutral myoglobin (MGB) and basic
lysozyme (LSZ). Results showed that the HAp-based photocatayst
was very effective on LSZ but it did not degrade BSA at all; MGB, on
the other hand, got photodegraded by UV light even in the absence
of photocatalyst. The authors explained the different activity
considering the different structures of the protein, LSZ being more
rigid and with a lower molecular weight. These data indicated that
Ti-doped HAp may be suitable for tailored application such as blood
purication therapies.
As already mentioned in section 1, improved photocatalytic
activity can be achieved by more effective charge separation and by
limited charge recombination. For Ti-doped HAp, an increase in the
photoactivity was obtained by grafting the surface of the material
with Cu2 ions; the grafting consisted in an impregnation process
of a 10% Ti-doped HAp in a 0.05 % wt. solution of Cu2, such process
led to a three-time higher activity. EPR analysis indicated a transfer
of the electrons promoted from the doped HAp valence band to the
copper ions, which reduced the extent of charge recombination
(Nishikawa et al., 2013). This treatment, although benecial for the
photoefciency, did not lead to any photoactivity under visible light
irradiation.
A similar approach was considered by Wakamura et al. (2011),
who treated Ti-doped HAp in a solution containing Cr3 ions;
different chromium concentrations were considered (between
104 and 102 mol/L). Tests of the photocatalytic behaviour showed
that the materials were active under visible light irradiation; this
activity, however, was due to the optical DMSO-d6 transitions of the
Cr3 ions and not to the formation of an additional energy level in
the HAp structure. Detailed FTIR analysis showed the formation of a
layer of Cr-OH group on the surface of the materials, which played a
role in the visible light photocatalysis.
Considering other dopants, only two studies have been pub-
lished up to date, which reported the use of either iron or vanadium
as dopants (see Table 3).
Regarding the use of iron, Fe3 was introduced into the HAp
lattice by treating commercial HAp powder into a FeCl3 solution
and then drying it at 100  C. Despite absorbing in the visible region,
the photocatalytic activity of the Fe-doped HAp was not particularly
high; in fact, when irradiated with visible light, only a 40% degra-
dation of resazurin blue was observed. This may have been due to
the poor crystallinity of the powder. The performance of the ma-
terial, however, improved remarkably when H2O2 was also dis-
solved in the resazurin solution (Liu et al., 2014).
Considering vanadium, Nishikawa et al. (2015) reported on
vanadium-doped HAp prepared by hydrothermal method, suing
VCl3 as vanadium source. Different vanadium concentrations were
considered (up to 10 mol %); the effect of the calcination of the
powder was also investigated. Analysis of the prepared materials
indicated an oxidation to V5 state during the calcination and that
Testing conditions (irradiation, Degradation Reference
pollutant, catalyst load) efciency/
photocatalyst
performance
XTi 1.0 ~7% after 2 h Nishikawa et al.
Visible (LED, l 470 nm), 20 mW/cm2 (2015)
Acetaldehyde
Visible (300 W Xe lamp), in presence of 86% after 4 h Liu et al. (2014)
H2O2 (0.05M)
Rodhamine blue
0.6 g/L
 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91 85

Table 4
Biphasic HAp-TiO2 photocatalytic composites.

Preparation method Characteristics of the material Testing conditions Degradation efciency/ Reference
(irradiation, pollutant, photocatalyst performance
catalyst load)

Gas phase
Commercial HAp and TiO2 powders HAp 50 % wt HAp 50 % wt >99% after 15 min Komazaki et al.
deposited on a diffusion gas scrubber UV, FL8BL 8 W (1999)
NOx
HAp/TiO2 multilayer coating (rf HAp ~ 50 % wt BLB lamp, 1.7 mW/cm2 100% after 4 h (higher than Ozeki et al.
magneton sputtering followed by Formaldehyde simple TiO2 coating) (2007)
heat treatment) 50 mm diameter/1 mm
coating
Plasma spraying coatings of HAp  30 % wt HAp 10 % wt 75% after 3.5 h (about double Ye et al. (2007)
commercial HAp and TiO2 powders Ca/P 2.19 l 360 nm, 1 mW/cm2 than simple TiO2 coating)
Acetaldehyde
HAp precipitation in presence of TiO2 HAp  50% vol HAp 50% vol Photonic efciency double than Mitsionis et al.
From spherical to needle-like particles for l 350 nm, 1 mW/cm2 for TiO2 after 90 min (2011)
increasing HAp concentration (up to 1 mm) NOx
Surface area: 55e100 m2/g Ca/P 1.67
Sol gel N-doped TiO2 in presence of HAp  15% mol Rod-like crystals (100e200 nm) HAp 10% mol Degradation rate 5 time higher Liu et al. (2011)
HAp Surface area: 113e207 m2/g Visible (l > 400 nm) than simple N-doped TiO2
Acetone 0.25 g
Commercial HAp mixed with sol-gel- HAp  80 % wt HAp 50 % wt Photonic efciency about double Giannakopoulou
prepared TiO2 Spherical particles (5e20 mm) l 350 nm, 1 mW/cm2 than for TiO2 after 90 min et al. (2012)
Surface area: 78e123 m2/g NOx
Ca/P 1.67
Liquid phase
Hydrothermal, followed by heat HAp 50e83 % wt Rod-like nanoparticles HAp 83 % wt 75 and 64% with UV and Vis Anmin et al.
treatment at 190  C (10  70 nm) Surface area: 127e205 m2/g Ca/ UV and Vis irradiation (double than for TiO2) (2006)
P 1.66e1.69 Methylene blue
TiO2 coating with HAp lm formed by HAp  1 % wt HAp 0.7% Degradation rate 3 times higher Yang and Zhang
immersion in SBF Elongated crystals (200e300 nm) UV (l 280 nm) than with un-modied TiO2 (2008)
Bilirubin 0.6 mm coatings coating
HAp NPs into TiO2 lm (Chemical HAp < 0.5 % wt HAp < 0.5 % wt 75% after 4 h (higher than with Piccirillo et al.
Vapour Deposition) Needle-like crystals (500 nm) l 365 nm, 1.86 mW/cm2 unmodied TiO2 coating) (2017)
Ca/P 1.67 Methylene blue
1  1 cm2 coating

such ion is effectively substituted into the HAp lattice. UV spectra
showed absorption in the visible, up to 530 nm; this conrmed the
formation of a new electronic level due to the insertion of the V5
ion in the HAp. Indeed these samples showed photocatalytic ac-
tivity under visible light irradiation; depending on the calcination
conditions, however, the materials showed different performances.
For the powders calcined at 400  C, in fact, the maximum 10%
doping level was the more active; for those calcined at 650  C, on
the contrary, the 5% doping was the most effective. This was
because a higher vanadium doping led to the conversion of HAp
into tricalcium phosphate Ca3(PO4)2.
5. Multiphasic HAp-containing photocatalysts
5.1. HAp-TiO2 biphasic composites
The combination of HAp with suitable materials led to the
development of high-performing photocatalysts.
The rst report on HAp-containing photoactive material was
about a biphasic composite made of HAp and TiO2 (Komazaki et al.,
1999); the authors report on the effective gaseous nitrogen oxides
(NOx, x 1,2) degradation by the composite (HAp 50% weight)
under UV illumination. In this work HAp was chosen due to its
absorbent properties (Niimi et al., 2014); the idea was that NOx
could have been more effectively adsorbed on the surface of the
material, for them to be subsequently photodegraded by TiO2. No
proper comparison, however, was performed with the pure TiO2
material.
Some years later a more complete investigation of HAp-TiO2
systems was performed (Anmin et al., 2006); materials with
different HAp:TiO2 relative content were prepared by hydrother-
mal method and their photocatalytic activity was tested by
following the degradation of methylene blue. The results showed
that all three composites were more effective photocalysts than
both single phase HAp or TiO2; this clearly indicated a synergistic
effect due to the combination between the two compounds.
Considering the promising results of these studies, HAp-TiO2
composites were prepared with different methods and their pho-
tocatalytic properties were assessed on different molecules (see
Table 4).
Mitsionis et al. (2011), for instance, prepared HAp by precipi-
tation method in the presence of commercial TiO2 P25 Evonik-
Degussa; depending on the amount of TiO2 added to the precipi-
tation solution, biphasic materials with different HAp:TiO2 pro-
portions were obtained. These composites were tested to
photodegrade NOx; the best degradation, higher than for pure TiO2,
was observed for the samples prepared with equal volumes of HAp
and TiO2. When higher HAp quantities were used, however, the
materials had worse photocatalytic performances. In another study
by the same research group (Giannakopoulou et al., 2012) the
biphasic materials were synthetised using commercial HAp and sol
gel-prepared TiO2; experiments on NOx photodegradation indi-
cated that the materials with 50 and 67 % wt. in HAp were the most
effective, with a better efciency than simple TiO2.
It has been suggested that the combination of TiO2 with HAp
leads to enhanced photocatalytic activity due to the high HAp
absorbent properties; the absorption of the molecules, either liquid
or gaseous, on the surface of the photocatalyst is, in fact, the rst
step for its photocatalytic degradation. A material with higher HAp
proportion can therefore absorb more and, in principle, have
86 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91
enhanced photocatalytic properties. Smaller proportion of the TiO2
photoactive phase, on the other hand, will have a detrimental effect
on the photocatalytic efciency. The overall performance of a TiO2-
HAp composite sample will be, therefore, a compromise between
these two components (see Fig. 6).
The opposite effect of these two elements is well exemplied in
the work of Yang and Zhang (2008). They described the perfor-
mance of TiO2 nanoparticles with small quantity of HAp on their
surface (maximum 1 % wt.); such HAp layer was formed on the
surface of the particles by soaking them in Simulated Body Fluid
(SBF) for different periods of time. In all cases higher protein
(bilirubin) absorption was detected on the surface of the composite
materials; this led to a more effective UV photodegradation of the
protein. The material with the best performance, however, was not
that with the highest surface absorption (1 % wt. HAp) but that with
a lower 0.75 HAp wt % content; this was probably due to the higher
TiO2 proportion (99.25 vs. 99.00 % wt.), which corresponded to
higher photocatalytic efciency.
The examples listed above indicated clearly that, depending on
the materials preparation and characteristics, the ratio between
HAp and TiO2 which corresponds to the material with the best
photocatalytic properties can be very different.
HAp-TiO2 composites have been prepared also in form of thin
lms; magneton sputtering technique, for instance, was used by
Ozeki et al. (2007) to deposit multilayer TiO2-HAp coatings on glass
substrate; subsequent annealing of the samples at 500  C increased
the deposits' crystallinity. Experiment on gaseous formaldehyde
revealed a more rapid photodegradation using the composite
coating than the simple TiO2. Yet spray technology was also used
(Ye et al., 2007); coating containing 0, 10 and 30 % wt. HAp were
fabricated and tested for the degradation of acetaldehyde; the most
photoactive lm was that with 10 % wt. HAp concentration, despite
the 30 % wt. lm being the most adsorbent. These results conrm
what was already reported for composite HAp-TiO2 powders, i.e.
the best photocatalytic activity being a compromise between
different opposite factors.
Literature also report of TiO2 coatings with HAp nanoparticles
embedded in their structure prepared using Aerosol Assisted
Chemical Vapour Deposition (AACVD) (Piccirillo et al., 2017). In this
work, despite the very low concentration of the HAp nanoparticles
(not detectable by XRD technique), their inclusion in the coatings
led to enhanced methylene blue photodegradation. This was due to
signicant changes in the coatings' microstructure due to the in-
clusion of HAp nanoparticles.
Composite materials of HAp and modied TiO2 were also pre-
pared. Liu et al. (2011), in fact, reported on the synthesis of HAp
combined with N-doped TiO2. The aim of this work was to obtain a
visible light photocatalyst; it is well known, in fact, that nitrogen
Fig. 6. Effect of the HAp concentration on the properties of HAp-based photocatalytic
composites (i.e. HAp-TiO2 composites). The higher HAp surface adsorption is benecial
to the photocatalytic degradation, while the lower TiO2 photoactive phase concen-
tration is not.
doping of TiO2 shift the band gap into the visible region (Diesen
et al., 2014). In this work, the authors prepared N-doped TiO2
with sol-gel method; they then added appropriate amounts of HAp
nanoparticles to gel, to subsequently calcine it. The band gap of the
composite materials was 2.76 eV, i.e. in the visible range. Indeed
these composites were able to degrade acetone under visible light
irradiation; the material with 10% mol HAp was the most effective
and had an efciency 11 times higher than commercial Degussa
P25.
5.2. HAp-TiO2 multiphasic composites
In literature few reports are available on (HAp-TiO2)-based
composites, in which additional phase(s) were added to the HAp-
TiO2 system, to shift the band gap in the visible and/or to impart
additional properties to the material (see Table 5).
HAp was, for instance, combined with TiO2 modied with Ag
nanoparticles (Ma et al., 2009); this was done to make the material
antibacterial, due to the known antimicrobial properties of the Ag-
TiO2 systems (Tobaldi et al., 2014). The multiphasic Ag-TiO2/HAp
was prepared on an Al2O3 membrane. In fact a layer of HAp was rst
deposited on the membrane surface using sol gel technique; then
an additional layer of Ag-TiO2 was added (Ag 1% mol). Membranes
prepared like this showed higher inactivation rates of the Gram-
negative strain E. coli under UV irradiation, if compared to the
membranes with just HAp or Ag-TiO2; in fact the decrease in the
bacterial population was about 3 orders of magnitude higher. The
enhanced antibacterial effect was partly due to the antimicrobial
action of silver; moreover, the metal presence also reduced the
charge recombination, leading to higher photocatalytic
performance.
Similarly, palladium (Pd) was also added to HAp-TiO2 systems;
this noble metal was considered as it shifts the TiO2 band gap in the
visible (Abdelaal and Mohamed, 2013). A Pd-TiO2-HAp composite
(Pd: 3 % wt., TiO2: 25 % wt.) was prepared by ultrasonic-assisted
precipitation (Mohamed and Baeissaa, 2013); the material, whose
band gap was 2.66 eV, was effective in the visible-light induced
photodegradation of cyanides, showing higher efciency than Pd-
TiO2 system (the degradation rate was more than twice higher).
Authors explained such better performance considering the higher
surface area, due to the HAp presence, and the lower charge
recombination. HAp addition was also benecial for the photo-
chemical stability of the catalyst, which showed almost no change
in the photocatalytic activity after 6 repeated cycles.
Composites made of HAp, TiO2 and b-Ca3(PO4)2 were also pre-
pared (Piccirillo et al., 2013). The material of this work was obtained
from cod sh bones, which were treated Ti(SO4)2 solution and
successively calcined at 800  C. Analysis of the obtained powder
showed that it contained only about 1e2% of TiO2, the rest being a
mixture of HAp and b-Ca3(PO4)2. The powder was tested in the
photodegradation of blue methylene and showed very high ef-
ciency, despite the very low TiO2 content; this was probably
because TiO2 was placed on the surface of a very porous HAp-based
the material, i.e. a very efcient combination. The presence of the
tricalcium phosphate, however, may have played a role; indeed
composites of TiO2 and b-Ca3(PO4)2 were reported to be effective
photocatalysts (Ryu et al., 2009). This triphasic material of marine
origin was also used successfully for the photodegradation of
diclofenac and uoxetine, two persistent pollutants which pose a
serious threat to the environment (M
arquez-Brazo
n et al., 2016).
5.3. Other photocatalytic HAp-containing composites
Although photocatalytic composites with TiO2 were the most
studied, HAp was also combined with other compounds, which
 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91 87

Table 5
Multi-phasic HAp-TiO2 photocatalytic composites.

Preparation method Characteristics of the Testing conditions (irradiation, Degradation efciency/ Reference
material pollutant, catalyst load) photocatalyst performance

Liquid phase
Ultrasonic assisted precipitation Pd-TiO2-HAp (Pd 3 % wt, HAp 70 % wt >90% degradation (more than Mohamed and
HAp 70 % wt) Visible (l 450 nm), 150 W twice than for Pd-TiO2) Baeissaa (2013)
Rod-like crystals Potassium cyanide
(45  200 nm) 5.3 g/L
Surface area: 150 m2/g
Thermal extraction from cod sh bones HAp-bTCP-TiO2 (54:45:1 l 365 nm, 8 W 100% in 1 h Piccirillo et al.
(treatment in titanium sulphate) % wt) Methylene blue 100% in 24 h (2013)
Needle-like crystals (1 l 365 nm, 1.84 mW/cm2 Ma
rquez-Brazo
n
e2 mm) Fluoxetine et al. (2016)
Surface area: 15.7 m2/g 4.0 g/L
Ca/P 1.60

included either metals or other photocatalysts (see Table 6).
Considering the metals, a biphasic HAp-Pt nanopowder was
prepared by Vukomanovi
c et al. (2012) by sonochemical precipi-
tation, using either H2PtCl6$H2O or C10H14O4Pt as platinum source.
The material showed photocatalytic behaviour with both UV and
visible light; considering in particular visible light, the efciency in
blue methylene degradation was more than double than commer-
cial Degussa Evonik P25. The material prepared with H2PtCl6$H2O
was the most active. The authors explained the photocatalytic
behaviour with a ligand-to-metal-charge transfer mechanism.
Few combinations with other photocatalysts were also re-
ported; several studies were performed, for instance, on multi-
phasic materials comprising iron oxides. Iron can form different
oxides in both its (II) and (III) oxidation states; a-Fe2O3 (hematite) is
a visible light photocatalyts with a band gap of about 2.2 eV (Zeng
et al., 2015) while Fe3O4 (magnetite) is known for its magnetic
behaviour (Zhou et al., 2016).
a-Fe2O3-HAp composites are reported in literature (Bharath and
Ponpandian, 2015); they were prepared by forming HAp nano-
particles on a-Fe2O3 dendritic crystal, using a hydrothermal pro-
cess. The photocatalytic activity of the composite, tested on the
degradation of methyl violet, was higher than for the single phase
a-Fe2O3 crystals. Moreover, the authors of this study also tested the
material for the removal of Pb2 from contaminated solutions; the
composite showed higher removal efciency than a-Fe2O3 alone
and also than pure HAp previously studied in literature and pre-
pared with other techniques. This study is very interesting, as it
conrms that HAp is a suitable material to enhance the perfor-
mance of photoactive compounds other than TiO2; it also shows
that it is possible to obtain multifunctional materials for environ-
ment remediation, i.e. materials which can both degrade organic
compounds and decontaminate from heavy metals.

Table 6
Other HAp-containing photocatalytic composites.

Composite composition and preparation Characteristics of the Testing conditions (irradiation, Degradation efciency/ Reference
method material pollutant, catalyst load) photocatalyst performance

Liquid phase
Pt-HAp <100 nm structure Vis (LED Parathon, 5 W) 60% after 4 h (double than P25 Vukomanovi

c et al.
Sonochemical precipitation Methylene blue TiO2) (2012)
1.8 g/L
a Fe2O3-HAp Dendritic crystal (<1 mm) l 365 nm, 18 W 100% after 75 min Bharath and
Hydrothermal synthesis Surface area 80 m2/g Methyl violet Ponpandian (2015)
Ms 2.8 emu/g 0.1 g/L
Fe3O4-HAp Spherical particles l 254 nm, 30 W 80% after 1 h Yang et al. (2010)
Co-precipitation (<25 nm) Diazinon
Ms 5.2 emu/g 4 g/L
Fe3O4/SiO2/HAp Core-shell spherical l 254 nm, 30 W 85% after 40 min Zhang et al. (2015)
Solvothermal synthesis particles (<100 nm) Simazine
Ms 26.7 emu/g 5 g/L
Ag3PO4-impregnated HAp nanoparticles Ag loading  12.7 % wt Ag loading 12.7 % wt 99 and 98% after 2 h for UVevis Hong et al. (2012)
Nanorod-like crystals UVevis and Vis (300 W Xe lamp) and vis respectively
Surface area: 98e104 m2/ Methylene blue
g 1 g/L
Ag3PO4-impregnated HAp nanowires Ag3PO4 10.5e65 % wt Ag3PO4 50 % wt 100% after 15 min Li et al. (2015)
Wire diameter < 50 nm Visible (300 W Xe lamp, l > 420 nm)
Methylene blue
0.08 g/L
HAp-bTCP-Ag3PO4-Ag Ag3PO4 18e23 % wt Ag3PO4 18 % wt 90 and 60% after 7 h for UV and Vis Piccirillo et al.
Thermal extraction from cod sh bones Surface area 4 m2/g UV (Philips PL-S, 9 W) and Vis respectively (2015)
(treatment in silver phosphate) Nanoparticles (<500 nm) (Philips PL-S 2P, 9 W/840)
Methylene blue
0.25 g/L
Ag3PO4-impregnated Fe3O4-HAp Nanocrystals (<500 nm) Visible 98% after 80 min Valizadeh et al.
nanoparticles Acid blue 25 (2014)
0.2 g/L
HAp-CQDs Nanoparticles (<100 nm) Visible (300 W Xe lamp) 90% after 50 min Chang et al. (2016)
Mixing and autoclaving of the two powders Methylene blue
0.1 mg/L
88 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91
Considering Fe3O4, its use in multicomponent photocatalysts is
quite common; due to its magnetic properties, in fact, it is possible
to have photocatalytic powders with magnetic behaviour, which
can be then easily removed from the pollutants' solution by
applying a magnetic eld. Literature reports, for instance, of many
materials made of Fe3O4 and TiO2 (Chen et al., 2015 and references
therein); only a couple of studies, however, were reported using
HAp and Fe3O4. Yang et al. (2010) prepared Fe3O4/HAp nano-
particles by precipitation method; the powder showed both mag-
netic properties (due to Fe3O4) and photocatalytic behaviour (due
to HAp). The powder was reused several times (7), without
showing signicant decrease in the photocatalytic activity.
A triphasic system comprising HAp, SiO2 and Fe3O4 was also
investigated by Zhang et al. (2015); they prepared core-shell
structured nanoparticles Fe3O4/SiO2/HAp, using Molecular
Imprinted Hydroxyapatite (MIH). The particles showed both mag-
netic properties and photocatalytic activity; their performance,
tested on the degradation of simazine, was higher than for the
particles made of just Fe3O4 and MIH. This higher efciency was
due to the presence of the SiO2 layer, which limited the charge
transfer from the HAp to the Fe3O4, which would have resulted in
lower ROS generation.
Literature also reports of composites of HAp with silver phos-
phate Ag3PO4 which, as stated above, is a visible light photocatalyst
(Martin et al., 2015). Although composites comprising HAp and
Ag3PO4 were already known, their use was limited to the
biomedicine, due to Ag3PO4 antibacterial nature (Buckley et al.,
2010; Suwanprateeb et al., 2012). Recently, however, few reports
were published on their photocatalytic activity. HAp nanoparticles
loaded with Ag3PO4, for instance, were prepared by Hong et al.
(2012) by wet impregnation technique; the powder showed
excellent photocatalytic activity with both UV and visible light (test
on degradation of methylene blue), higher than for the unmodied
Ag3PO4. As already reported for the HAp-TiO2 composites, also for
the HAp-Ag3PO4 systems the material with the best performance
was the compromise of different features, including the concen-
tration of the Ag3PO4 photoactive component, the increased dye
adsorption due to HAp presence, the higher efciency in electron-
hole generation due to the HAp-Ag interactions.
Li et al. (2015), on the other hand, treated HAp nanowires in an
AgNO3 solution, to obtain Ag3PO4-loaded nanowires. The materials,
further than showing visible light photocatalytic behaviour, also
had a higher Pb (II) absorption rate than unmodied HAp; the
authors also showed that this composite could be effectively use to
simultaneously degrade a dye (rodhamine B), adsorb Pb (II) and
inactivate Escherichia coli bacterial strain, truly performing as a
multifunctional material.
Multicomposites based on HAp and Ag3PO4 were also investi-
gated; a multiphasic material of marine origin based on HAp, b-TCP,
Ag3PO4 and metallic Ag was prepared by Piccirillo et al. (2015). The
powder was obtained by treating cod sh bones in a solution
containing an excess of AgNO3, and by subsequently calcining the
bones. The material had photocatalytic behaviour with both visible
and UV light; this was due as the composite showed a band gap in
the visible (2.47 eV) but also in the UV (3.89 eV). The visible ab-
sorption was attributed to Ag3PO4; the UV one, on the other hand,
was explained considering the Ag/Ag3PO4 co-presence, as previous
studies already reported UV light activity for this composite
(Gondal et al., 2013).
A magnetic HAp/Ag3PO4 photocatalyst was prepared by
combining these two compounds with Fe3O4 (Valizadeh et al.,
2014). The protocol followed to prepare the material was similar
to that described above (Li et al., 2015), i.e. treatment of the HAp
particles in an AgNO3 solution; in this case, however, this was done
on a biphasic HAp-Fe3O4 material, hence leading to a HAp-Ag3PO4-
Fe3O4 composite with visible light catalytic activity and magnetic
properties.
HAp was also used together with N-doped carbon quantum dots
(N-CQDs), which were uniformly deposited on HAp nanopowders
(Chang et al., 2016); this was done by mixing HAp and CQD solu-
tions and then autoclaving them. Materials with different pro-
portions of HAp and N-CQDs were prepared, to see which was the
composition leading to the best performance. Results showed that
all composites had better visible light photocatalytic efciency that
simple N-CQDs; as already observed for other composite systems,
the most effective material was not the one with the highest pho-
tocatalyst content, as other features such as absorption properties
and charge recombination also played a role.
6. Discussion and future perspectives
The development of innovative heterogeneous photocatalysts
alternative and/or complementary to TiO2 has been a topic of
growing interest in recent years; the study of HAp-based photo-
catalysts attracted particular attention, due to the unique proper-
ties of this compound.
HAp is in fact a well-known material for its biocompatibility and
its capacity of adsorbing molecules (i.e. proteins) on its surface;
these are both properties which make it suitable for applications in
heterogeneous photocatalysis. In addition to this, HAp can also be
used for heavy metal removal; hence, photocatalytic HAp has the
characteristics to be a multifunctional material for environmental
remediation, which can be used for degradation of organic pollut-
ants and, at the same time, for heavy metal decontamination. All
these characteristics make it a material with unique properties,
which stands out from other photocatalysts. The studies reported
above indeed show the potential but, at the same time, also some
critical issues of HAp as photocatalyst, which need to be addressed.
As it could be seen in the previous sections, various materials
were prepared using many different techniques; consequently,
their characteristics such as surface area, shape and dimensions of
the crystals, etc. were very different. Moreover, the functional tests
to assess the photocatalytic effectiveness of these materials were
performed in different experimental conditions, as often things
such as experimental set up, irradiation power and sources, catalyst
load etc. were different. All this makes very difcult, if not impos-
sible, to compare the various materials and their performances.
Despite this, however, some general considerations can still be
made regarding HAp-based photocatalysts.
Considering single-phase HAp, for instance, it can be seen that
for all cases reported in liquid phase, high degradation rates of the
pollutants were always achieved with high catalyst load and/or
over relatively long periods of time; these data indicate a relatively
low activity compared to other photocatalysts. For the experiments
in gas phase, on the contrary, much better performances were
observed.
One of the reasons for this difference could be the possible HAp
dissolution during the liquid-phase photocatalytic tests; this can
surely have an effect the photoactivity of the material. As
mentioned in section 2, HAp has very low solubility at neutral pH;
some dissolution, however, indeed occurs, especially in case of non-
stoichiometric powders. It has also to be reminded that photo-
catalytic activity in single phase HAp is often due to the presence of
defects in the lattice; such defects, although benecial for the
photocatalytic behaviour, could also favour the dissolution (Smith
et al., 1977). This, in turn, can have a detrimental effect on the
photocatalytic performance. Moreover, as often the dissolution
does not follow HAp stoichiometry (Oliva et al., 2012), the Ca/P ratio
can deviate even more from the 1.67 stoichiometric ratio as the
reaction goes on; this can enhance the dissolution even more.
 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91
These features do not affect the experiments carried out in the gas
phase; indeed the materials showed to be much more effective.
Unfortunately in none of the published studies the authors report
about the reuse of the catalyst for successive reactions; similarly no
characterisation of the materials after their use as photocatalysts
was ever published. This is a point which should explored further,
to see if features such as Ca/P ratio, crystallinity and morphology
are signicantly affected during the reaction (especially in liquid)
and could be possibly responsible for the limited photocatalytic
activity.
Overall a more systematic investigation should be performed on
single-phase photocatalytic HAp, to better understand which fea-
tures can give a higher efciency in the photogeneration of the
charges and/or limit their recombination. This kind of studies was
done for TiO2; in fact various reports were published, for instance,
on the factors affecting the charge recombination, with work were
based on both experimental data and theoretical modelling (Fazio
et al., 2016; Ke et al., 2006; Garcia et al., 2015]. A similar
approach, if applied to HAp, could lead to a proper understanding of
the material and, eventually, to improve its photocatalytic
behaviour.
Theoretical/modelling studies could also help improving the
knowledge and, hence, the performances of HAp-based photo-
catalysts. To the best of our knowledge, the only theoretical/
modelling study on this topic was performed by Bystrov et al.
(2016). This work showed the importance and the potential of
more theoretical calculations to try to predict which features could
lead to a photocatalytic material; the possibility of inducing a defect
which could lead to a visible light band gap, in particular, seems
very interesting and worth studying further. Modelling studies
similar to this should be performed also for other HAp-based sys-
tems, such as doped compounds, to establish which combination(s)
could potentially give best results, in terms for instance of band gap
values.
The photoactivity of Ti-doped HAp showed to be much higher
than for undoped single phase HAp; some of the published studies,
in fact, reported that Ti-doped HAp had efciency comparable or
even higher than for commercial TiO2, both in gas and liquid phase
(Wakamura et al., 2003; Anmin et al., 2007). Based on the published
data, the best performing powders appear to be those prepared by
hydrothermal synthesis. It has to be considered, however, that not
all studies reported a comparison with TiO2 or other commercial
catalysts; it is therefore not possible to assess with certainty which
photocatalysts are the most active.
To improve the efciency of the photocatalytic reactions,
grafting processes should be explored more; indeed the use of Cu2
ions gave interesting results on Ti-doped HAp. Literature reports of
signicant improvement in the photocatalytic efciency achieved
for TiO2 through grafting with appropriate organic molecules such
as silanes (Zhao et al., 2012; Pazokifard, 2012); this method should
indeed be applied also to HAp-based photocatalysts, testing suit-
able molecules/ions.
Combining HAp with other photocatalytic compounds in bi- or
multiphasic materials was the approach which led to the most
effective photocatalysts; when HAp was used together with TiO2,
for instance, all published studies reported an enhanced photo-
catalytic efciency in comparison to just HAp or TiO2. These data
indicate that the combination of the excellent HAp adsorbing
properties and of the high TiO2 photoactive behaviour is indeed
very effective, giving materials with improved performances. As
already mentioned above, depending on the materials and their
preparation methods, the HAp:TiO2 ratio corresponding to the
highest photocatalytic activity will be different; it is interesting to
note, however, that in some studies improved performances were
observed with very low HAp concentrations (<1% wt) (Yang and
89
Zhang, 2008; Piccirillo et al., 2017). This conrms the potential of
this compound, leading to signicant better properties even if
present in very small amount.
HAp combination with other photocatalysts (i.e. Fe2O3, Ag3PO4),
on the other hand, can lead to either visible light photocatalysts or
multifunctional materials, i.e. magnetic photocatalysts.
Considering these promising results, more studies could be
performed exploring the combination of HAp with different pho-
tocatalysts; multiphasic materials comprising ZnO, for instance,
could be considered. ZnO-HAp composites were already prepared
by different methods (Grenho et al., 2014; Cai et al., 2015) but they
were investigated only as biomaterials, especially considering their
antimicrobial properties; exploring the photocatalytic behaviour
could therefore widen the applications of these materials and
potentially lead to photocatalysts with enhanced efciency.
Regarding the applications of HAp-based materials for envi-
ronment remediation, one peculiarity is surely their double func-
tionality photocatalyst/heavy metal remover; this feature, however,
was explored properly only in a couple of more recent studies
(Bharath and Ponpandian, 2015; Li et al., 2015); this is, hence, a
promising eld which should be investigated more.
Further studies should also be performed on the efcacy of
these materials to degrade molecules with different structures, to
assess whether they could be effectively employed as environment
remediation agent. Testing the photodegradation of persistent
pollutants, for instance, would be crucial, considering how impor-
tant it is to eliminate these compounds from the environment
(Dong et al., 2015). To date, only one study has been published on
this topic (Ma
rquez-Brazo
n et al., 2016); results showed the po-
tential of HAp-based materials to degrade such more resistant or-
ganics and indicated that further molecules could be also tested.
7. Conclusions
HAp is a material with great potential applications in photo-
catalysis; indeed undoped single phase HAp, doped HAp and HAp-
based multiphasic materials have been reported to be photoactive.
Studies developed until now showed that the materials with
best performance are obtained when HAp is combined with other
photocatalysts, such as TiO2, Ag3PO4, etc. For bi- or multi-phasic
materials, in fact, the measured photocatalytic efciency was
often higher than that of the different single phases the materials
are made of, for experiment both in liquid and gas phases. Of the
reasons for the improved photocatalytic activity is the well-known
high adsorbing property of HAp, which favours and facilitate the
degradation of the pollutants. Due to these promising results, the
combination of HAp with different photocatlysts (i.e. ZnO) should
also be explored.
As for undoped and doped HAp, Ti-doped materials indeed
showed signicant photocatalytic properties; undoped materials,
on the other hand, tend to exhibit lower activity e more studies
should be performed to better understand the features which could
improve such performance.
Overall HAp-based materials could be used for environment
remediation, due to their biocompatibility/low toxicity; their
multifunctional properties should be exploited, to obtain com-
pound which can degrade organic/gaseous pollutants under light
irradiation and which can also remove heavy metals from
contaminated waters.
Acknowledgments
This work was supported by National Funds from FCT - Fundaa ~o
^ncia e a Tecnologia through the project UID/Multi/50016/
para a Cie
2013. C. Piccirillo thanks FCT for the grants SFRH-BPD-86483-2012.
90 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91

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