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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.
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 The presence of either defects or dopants, however, can change the
Darvell, 2007). Moreover, in the case of nanomaterials, the size electronic levels and lead to a decrease in the band gap value; the
and the shape of the particles is also determinant (Bose and Tarafde, material, therefore, can behave as a photocatalyst. Similarly the
2012). HAp is stable in basic solution and it can be slowly dissolved combination with other photocatalytic compounds such as TiO2 can
in acidic environment; studies of the dissolution rate showed that lead to HAp-based multiphasic photocatalysts.
HAp does not dissolve according to its stoichiometry but that, In the sections below we will report on the various forms of
depending on the conditions, a preferential dissolution of either photocatalytic HAp (see Fig. 3), starting from the single phase un-
calcium or phosphorus can take place (Hankermeyer et al., 2002; doped materials; then doped HAp compounds will be described.
Piccirillo et al., 2014). Finally, HAp-based multi-phasic photocatalysts will be considered.
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 3. Photocatalytic single phase HAp
ion capture, that is ion exchange between the calcium and the
bivalent ions and dissolution-precipitation (Nzihou, 2010). Both As mentioned above, stoichiometric defect-free HAp does not
mechanisms are favoured by HAp exible framework and by the have photocatalytic activity, due to its insulating nature. Some
fact that the calcium ions are placed on the external crystal faces. forms of HAp, however, were reported to show photocatalytic
Due to this property, HAp is used for environmental remediation, to properties; although the reasons for this behaviour are not
remove heavy metals from contaminated wastewaters and/or soils completely clear, the most likely explanation for this is the presence
(Viipsi et al., 2013). of defects in the HAp lattice, as well as some specic surface
Stoichiometric defect-free HAp is not a good electrical modications.
conductor (Dubey et al., 2013); indeed literature reports of single- Table 1 summarises the most important reports on this topic.
phase HAp sample with band gap value higher than 6 eV, corre- The rst study on photocatalytic single phase HAp was published
sponding to an insulator (Tsukada et al., 2011). Because of this, HAp almost 15 years ago and described the UV-induced degradation of
with these characteristics does not have any photocatalytic activity. 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
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 Marquez-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
Table 3
Doped photocatalytic HAp materials using other metals.
Preparation method and dopant Characteristics of the Testing conditions (irradiation, Degradation Reference
material pollutant, catalyst load) efciency/
photocatalyst
performance
Gas phase
Hydrothermal followed by thermal treatment (400 XV 0.1 XTi 1.0 ~7% after 2 h Nishikawa et al.
e650 C), vanadium (III) Agglomerated particles Visible (LED, l 470 nm), 20 mW/cm2 (2015)
(100e200 nm) Acetaldehyde
Liquid phase
Commercial undoped HAp followed by Fe3 Sphere-like nanoparticles Visible (300 W Xe lamp), in presence of 86% after 4 h Liu et al. (2014)
impregnation (<50 nm) H2O2 (0.05M)
Surface area: 204 m2/g 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 different HAp:TiO2 relative content were prepared by hydrother-
showed absorption in the visible, up to 530 nm; this conrmed the mal method and their photocatalytic activity was tested by
formation of a new electronic level due to the insertion of the V5 following the degradation of methylene blue. The results showed
ion in the HAp. Indeed these samples showed photocatalytic ac- that all three composites were more effective photocalysts than
tivity under visible light irradiation; depending on the calcination both single phase HAp or TiO2; this clearly indicated a synergistic
conditions, however, the materials showed different performances. effect due to the combination between the two compounds.
For the powders calcined at 400 C, in fact, the maximum 10% Considering the promising results of these studies, HAp-TiO2
doping level was the more active; for those calcined at 650 C, on composites were prepared with different methods and their pho-
the contrary, the 5% doping was the most effective. This was tocatalytic properties were assessed on different molecules (see
because a higher vanadium doping led to the conversion of HAp Table 4).
into tricalcium phosphate Ca3(PO4)2. 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-
5. Multiphasic HAp-containing photocatalysts tation solution, biphasic materials with different HAp:TiO2 pro-
portions were obtained. These composites were tested to
5.1. HAp-TiO2 biphasic composites photodegrade NOx; the best degradation, higher than for pure TiO2,
was observed for the samples prepared with equal volumes of HAp
The combination of HAp with suitable materials led to the and TiO2. When higher HAp quantities were used, however, the
development of high-performing photocatalysts. materials had worse photocatalytic performances. In another study
The rst report on HAp-containing photoactive material was by the same research group (Giannakopoulou et al., 2012) the
about a biphasic composite made of HAp and TiO2 (Komazaki et al., biphasic materials were synthetised using commercial HAp and sol
1999); the authors report on the effective gaseous nitrogen oxides gel-prepared TiO2; experiments on NOx photodegradation indi-
(NOx, x 1,2) degradation by the composite (HAp 50% weight) cated that the materials with 50 and 67 % wt. in HAp were the most
under UV illumination. In this work HAp was chosen due to its effective, with a better efciency than simple TiO2.
absorbent properties (Niimi et al., 2014); the idea was that NOx It has been suggested that the combination of TiO2 with HAp
could have been more effectively adsorbed on the surface of the leads to enhanced photocatalytic activity due to the high HAp
material, for them to be subsequently photodegraded by TiO2. No absorbent properties; the absorption of the molecules, either liquid
proper comparison, however, was performed with the pure TiO2 or gaseous, on the surface of the photocatalyst is, in fact, the rst
material. step for its photocatalytic degradation. A material with higher HAp
Some years later a more complete investigation of HAp-TiO2 proportion can therefore absorb more and, in principle, have
systems was performed (Anmin et al., 2006); materials with
86 C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91
enhanced photocatalytic properties. Smaller proportion of the TiO2 doping of TiO2 shift the band gap into the visible region (Diesen
photoactive phase, on the other hand, will have a detrimental effect et al., 2014). In this work, the authors prepared N-doped TiO2
on the photocatalytic efciency. The overall performance of a TiO2- with sol-gel method; they then added appropriate amounts of HAp
HAp composite sample will be, therefore, a compromise between nanoparticles to gel, to subsequently calcine it. The band gap of the
these two components (see Fig. 6). composite materials was 2.76 eV, i.e. in the visible range. Indeed
The opposite effect of these two elements is well exemplied in these composites were able to degrade acetone under visible light
the work of Yang and Zhang (2008). They described the perfor- irradiation; the material with 10% mol HAp was the most effective
mance of TiO2 nanoparticles with small quantity of HAp on their and had an efciency 11 times higher than commercial Degussa
surface (maximum 1 % wt.); such HAp layer was formed on the P25.
surface of the particles by soaking them in Simulated Body Fluid
(SBF) for different periods of time. In all cases higher protein 5.2. HAp-TiO2 multiphasic composites
(bilirubin) absorption was detected on the surface of the composite
materials; this led to a more effective UV photodegradation of the In literature few reports are available on (HAp-TiO2)-based
protein. The material with the best performance, however, was not composites, in which additional phase(s) were added to the HAp-
that with the highest surface absorption (1 % wt. HAp) but that with TiO2 system, to shift the band gap in the visible and/or to impart
a lower 0.75 HAp wt % content; this was probably due to the higher additional properties to the material (see Table 5).
TiO2 proportion (99.25 vs. 99.00 % wt.), which corresponded to HAp was, for instance, combined with TiO2 modied with Ag
higher photocatalytic efciency. nanoparticles (Ma et al., 2009); this was done to make the material
The examples listed above indicated clearly that, depending on antibacterial, due to the known antimicrobial properties of the Ag-
the materials preparation and characteristics, the ratio between TiO2 systems (Tobaldi et al., 2014). The multiphasic Ag-TiO2/HAp
HAp and TiO2 which corresponds to the material with the best was prepared on an Al2O3 membrane. In fact a layer of HAp was rst
photocatalytic properties can be very different. deposited on the membrane surface using sol gel technique; then
HAp-TiO2 composites have been prepared also in form of thin an additional layer of Ag-TiO2 was added (Ag 1% mol). Membranes
lms; magneton sputtering technique, for instance, was used by prepared like this showed higher inactivation rates of the Gram-
Ozeki et al. (2007) to deposit multilayer TiO2-HAp coatings on glass negative strain E. coli under UV irradiation, if compared to the
substrate; subsequent annealing of the samples at 500 C increased membranes with just HAp or Ag-TiO2; in fact the decrease in the
the deposits' crystallinity. Experiment on gaseous formaldehyde bacterial population was about 3 orders of magnitude higher. The
revealed a more rapid photodegradation using the composite enhanced antibacterial effect was partly due to the antimicrobial
coating than the simple TiO2. Yet spray technology was also used action of silver; moreover, the metal presence also reduced the
(Ye et al., 2007); coating containing 0, 10 and 30 % wt. HAp were charge recombination, leading to higher photocatalytic
fabricated and tested for the degradation of acetaldehyde; the most performance.
photoactive lm was that with 10 % wt. HAp concentration, despite Similarly, palladium (Pd) was also added to HAp-TiO2 systems;
the 30 % wt. lm being the most adsorbent. These results conrm this noble metal was considered as it shifts the TiO2 band gap in the
what was already reported for composite HAp-TiO2 powders, i.e. visible (Abdelaal and Mohamed, 2013). A Pd-TiO2-HAp composite
the best photocatalytic activity being a compromise between (Pd: 3 % wt., TiO2: 25 % wt.) was prepared by ultrasonic-assisted
different opposite factors. precipitation (Mohamed and Baeissaa, 2013); the material, whose
Literature also report of TiO2 coatings with HAp nanoparticles band gap was 2.66 eV, was effective in the visible-light induced
embedded in their structure prepared using Aerosol Assisted photodegradation of cyanides, showing higher efciency than Pd-
Chemical Vapour Deposition (AACVD) (Piccirillo et al., 2017). In this TiO2 system (the degradation rate was more than twice higher).
work, despite the very low concentration of the HAp nanoparticles Authors explained such better performance considering the higher
(not detectable by XRD technique), their inclusion in the coatings surface area, due to the HAp presence, and the lower charge
led to enhanced methylene blue photodegradation. This was due to recombination. HAp addition was also benecial for the photo-
signicant changes in the coatings' microstructure due to the in- chemical stability of the catalyst, which showed almost no change
clusion of HAp nanoparticles. in the photocatalytic activity after 6 repeated cycles.
Composite materials of HAp and modied TiO2 were also pre- Composites made of HAp, TiO2 and b-Ca3(PO4)2 were also pre-
pared. Liu et al. (2011), in fact, reported on the synthesis of HAp pared (Piccirillo et al., 2013). The material of this work was obtained
combined with N-doped TiO2. The aim of this work was to obtain a from cod sh bones, which were treated Ti(SO4)2 solution and
visible light photocatalyst; it is well known, in fact, that nitrogen 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).
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 Marquez-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). behaviour (Zhou et al., 2016).
Considering the metals, a biphasic HAp-Pt nanopowder was a-Fe2O3-HAp composites are reported in literature (Bharath and
prepared by Vukomanovi c et al. (2012) by sonochemical precipi- Ponpandian, 2015); they were prepared by forming HAp nano-
tation, using either H2PtCl6$H2O or C10H14O4Pt as platinum source. particles on a-Fe2O3 dendritic crystal, using a hydrothermal pro-
The material showed photocatalytic behaviour with both UV and cess. The photocatalytic activity of the composite, tested on the
visible light; considering in particular visible light, the efciency in degradation of methyl violet, was higher than for the single phase
blue methylene degradation was more than double than commer- a-Fe2O3 crystals. Moreover, the authors of this study also tested the
cial Degussa Evonik P25. The material prepared with H2PtCl6$H2O material for the removal of Pb2 from contaminated solutions; the
was the most active. The authors explained the photocatalytic composite showed higher removal efciency than a-Fe2O3 alone
behaviour with a ligand-to-metal-charge transfer mechanism. and also than pure HAp previously studied in literature and pre-
Few combinations with other photocatalysts were also re- pared with other techniques. This study is very interesting, as it
ported; several studies were performed, for instance, on multi- conrms that HAp is a suitable material to enhance the perfor-
phasic materials comprising iron oxides. Iron can form different mance of photoactive compounds other than TiO2; it also shows
oxides in both its (II) and (III) oxidation states; a-Fe2O3 (hematite) is that it is possible to obtain multifunctional materials for environ-
a visible light photocatalyts with a band gap of about 2.2 eV (Zeng ment remediation, i.e. materials which can both degrade organic
et al., 2015) while Fe3O4 (magnetite) is known for its magnetic 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 Fe3O4 composite with visible light catalytic activity and magnetic
quite common; due to its magnetic properties, in fact, it is possible properties.
to have photocatalytic powders with magnetic behaviour, which HAp was also used together with N-doped carbon quantum dots
can be then easily removed from the pollutants' solution by (N-CQDs), which were uniformly deposited on HAp nanopowders
applying a magnetic eld. Literature reports, for instance, of many (Chang et al., 2016); this was done by mixing HAp and CQD solu-
materials made of Fe3O4 and TiO2 (Chen et al., 2015 and references tions and then autoclaving them. Materials with different pro-
therein); only a couple of studies, however, were reported using portions of HAp and N-CQDs were prepared, to see which was the
HAp and Fe3O4. Yang et al. (2010) prepared Fe3O4/HAp nano- composition leading to the best performance. Results showed that
particles by precipitation method; the powder showed both mag- all composites had better visible light photocatalytic efciency that
netic properties (due to Fe3O4) and photocatalytic behaviour (due simple N-CQDs; as already observed for other composite systems,
to HAp). The powder was reused several times (7), without the most effective material was not the one with the highest pho-
showing signicant decrease in the photocatalytic activity. tocatalyst content, as other features such as absorption properties
A triphasic system comprising HAp, SiO2 and Fe3O4 was also and charge recombination also played a role.
investigated by Zhang et al. (2015); they prepared core-shell
structured nanoparticles Fe3O4/SiO2/HAp, using Molecular 6. Discussion and future perspectives
Imprinted Hydroxyapatite (MIH). The particles showed both mag-
netic properties and photocatalytic activity; their performance, The development of innovative heterogeneous photocatalysts
tested on the degradation of simazine, was higher than for the alternative and/or complementary to TiO2 has been a topic of
particles made of just Fe3O4 and MIH. This higher efciency was growing interest in recent years; the study of HAp-based photo-
due to the presence of the SiO2 layer, which limited the charge catalysts attracted particular attention, due to the unique proper-
transfer from the HAp to the Fe3O4, which would have resulted in ties of this compound.
lower ROS generation. HAp is in fact a well-known material for its biocompatibility and
Literature also reports of composites of HAp with silver phos- its capacity of adsorbing molecules (i.e. proteins) on its surface;
phate Ag3PO4 which, as stated above, is a visible light photocatalyst these are both properties which make it suitable for applications in
(Martin et al., 2015). Although composites comprising HAp and heterogeneous photocatalysis. In addition to this, HAp can also be
Ag3PO4 were already known, their use was limited to the used for heavy metal removal; hence, photocatalytic HAp has the
biomedicine, due to Ag3PO4 antibacterial nature (Buckley et al., characteristics to be a multifunctional material for environmental
2010; Suwanprateeb et al., 2012). Recently, however, few reports remediation, which can be used for degradation of organic pollut-
were published on their photocatalytic activity. HAp nanoparticles ants and, at the same time, for heavy metal decontamination. All
loaded with Ag3PO4, for instance, were prepared by Hong et al. these characteristics make it a material with unique properties,
(2012) by wet impregnation technique; the powder showed which stands out from other photocatalysts. The studies reported
excellent photocatalytic activity with both UV and visible light (test above indeed show the potential but, at the same time, also some
on degradation of methylene blue), higher than for the unmodied critical issues of HAp as photocatalyst, which need to be addressed.
Ag3PO4. As already reported for the HAp-TiO2 composites, also for As it could be seen in the previous sections, various materials
the HAp-Ag3PO4 systems the material with the best performance were prepared using many different techniques; consequently,
was the compromise of different features, including the concen- their characteristics such as surface area, shape and dimensions of
tration of the Ag3PO4 photoactive component, the increased dye the crystals, etc. were very different. Moreover, the functional tests
adsorption due to HAp presence, the higher efciency in electron- to assess the photocatalytic effectiveness of these materials were
hole generation due to the HAp-Ag interactions. performed in different experimental conditions, as often things
Li et al. (2015), on the other hand, treated HAp nanowires in an such as experimental set up, irradiation power and sources, catalyst
AgNO3 solution, to obtain Ag3PO4-loaded nanowires. The materials, load etc. were different. All this makes very difcult, if not impos-
further than showing visible light photocatalytic behaviour, also sible, to compare the various materials and their performances.
had a higher Pb (II) absorption rate than unmodied HAp; the Despite this, however, some general considerations can still be
authors also showed that this composite could be effectively use to made regarding HAp-based photocatalysts.
simultaneously degrade a dye (rodhamine B), adsorb Pb (II) and Considering single-phase HAp, for instance, it can be seen that
inactivate Escherichia coli bacterial strain, truly performing as a for all cases reported in liquid phase, high degradation rates of the
multifunctional material. pollutants were always achieved with high catalyst load and/or
Multicomposites based on HAp and Ag3PO4 were also investi- over relatively long periods of time; these data indicate a relatively
gated; a multiphasic material of marine origin based on HAp, b-TCP, low activity compared to other photocatalysts. For the experiments
Ag3PO4 and metallic Ag was prepared by Piccirillo et al. (2015). The in gas phase, on the contrary, much better performances were
powder was obtained by treating cod sh bones in a solution observed.
containing an excess of AgNO3, and by subsequently calcining the One of the reasons for this difference could be the possible HAp
bones. The material had photocatalytic behaviour with both visible dissolution during the liquid-phase photocatalytic tests; this can
and UV light; this was due as the composite showed a band gap in surely have an effect the photoactivity of the material. As
the visible (2.47 eV) but also in the UV (3.89 eV). The visible ab- mentioned in section 2, HAp has very low solubility at neutral pH;
sorption was attributed to Ag3PO4; the UV one, on the other hand, some dissolution, however, indeed occurs, especially in case of non-
was explained considering the Ag/Ag3PO4 co-presence, as previous stoichiometric powders. It has also to be reminded that photo-
studies already reported UV light activity for this composite catalytic activity in single phase HAp is often due to the presence of
(Gondal et al., 2013). defects in the lattice; such defects, although benecial for the
A magnetic HAp/Ag3PO4 photocatalyst was prepared by photocatalytic behaviour, could also favour the dissolution (Smith
combining these two compounds with Fe3O4 (Valizadeh et al., et al., 1977). This, in turn, can have a detrimental effect on the
2014). The protocol followed to prepare the material was similar photocatalytic performance. Moreover, as often the dissolution
to that described above (Li et al., 2015), i.e. treatment of the HAp does not follow HAp stoichiometry (Oliva et al., 2012), the Ca/P ratio
particles in an AgNO3 solution; in this case, however, this was done can deviate even more from the 1.67 stoichiometric ratio as the
on a biphasic HAp-Fe3O4 material, hence leading to a HAp-Ag3PO4- reaction goes on; this can enhance the dissolution even more.
C. Piccirillo, P.M. L. Castro / Journal of Environmental Management 193 (2017) 79e91 89
These features do not affect the experiments carried out in the gas Zhang, 2008; Piccirillo et al., 2017). This conrms the potential of
phase; indeed the materials showed to be much more effective. this compound, leading to signicant better properties even if
Unfortunately in none of the published studies the authors report present in very small amount.
about the reuse of the catalyst for successive reactions; similarly no HAp combination with other photocatalysts (i.e. Fe2O3, Ag3PO4),
characterisation of the materials after their use as photocatalysts on the other hand, can lead to either visible light photocatalysts or
was ever published. This is a point which should explored further, multifunctional materials, i.e. magnetic photocatalysts.
to see if features such as Ca/P ratio, crystallinity and morphology Considering these promising results, more studies could be
are signicantly affected during the reaction (especially in liquid) performed exploring the combination of HAp with different pho-
and could be possibly responsible for the limited photocatalytic tocatalysts; multiphasic materials comprising ZnO, for instance,
activity. could be considered. ZnO-HAp composites were already prepared
Overall a more systematic investigation should be performed on by different methods (Grenho et al., 2014; Cai et al., 2015) but they
single-phase photocatalytic HAp, to better understand which fea- were investigated only as biomaterials, especially considering their
tures can give a higher efciency in the photogeneration of the antimicrobial properties; exploring the photocatalytic behaviour
charges and/or limit their recombination. This kind of studies was could therefore widen the applications of these materials and
done for TiO2; in fact various reports were published, for instance, potentially lead to photocatalysts with enhanced efciency.
on the factors affecting the charge recombination, with work were Regarding the applications of HAp-based materials for envi-
based on both experimental data and theoretical modelling (Fazio ronment remediation, one peculiarity is surely their double func-
et al., 2016; Ke et al., 2006; Garcia et al., 2015]. A similar tionality photocatalyst/heavy metal remover; this feature, however,
approach, if applied to HAp, could lead to a proper understanding of was explored properly only in a couple of more recent studies
the material and, eventually, to improve its photocatalytic (Bharath and Ponpandian, 2015; Li et al., 2015); this is, hence, a
behaviour. promising eld which should be investigated more.
Theoretical/modelling studies could also help improving the Further studies should also be performed on the efcacy of
knowledge and, hence, the performances of HAp-based photo- these materials to degrade molecules with different structures, to
catalysts. To the best of our knowledge, the only theoretical/ assess whether they could be effectively employed as environment
modelling study on this topic was performed by Bystrov et al. remediation agent. Testing the photodegradation of persistent
(2016). This work showed the importance and the potential of pollutants, for instance, would be crucial, considering how impor-
more theoretical calculations to try to predict which features could tant it is to eliminate these compounds from the environment
lead to a photocatalytic material; the possibility of inducing a defect (Dong et al., 2015). To date, only one study has been published on
which could lead to a visible light band gap, in particular, seems this topic (Marquez-Brazo n et al., 2016); results showed the po-
very interesting and worth studying further. Modelling studies tential of HAp-based materials to degrade such more resistant or-
similar to this should be performed also for other HAp-based sys- ganics and indicated that further molecules could be also tested.
tems, such as doped compounds, to establish which combination(s)
could potentially give best results, in terms for instance of band gap 7. Conclusions
values.
The photoactivity of Ti-doped HAp showed to be much higher HAp is a material with great potential applications in photo-
than for undoped single phase HAp; some of the published studies, catalysis; indeed undoped single phase HAp, doped HAp and HAp-
in fact, reported that Ti-doped HAp had efciency comparable or based multiphasic materials have been reported to be photoactive.
even higher than for commercial TiO2, both in gas and liquid phase Studies developed until now showed that the materials with
(Wakamura et al., 2003; Anmin et al., 2007). Based on the published best performance are obtained when HAp is combined with other
data, the best performing powders appear to be those prepared by photocatalysts, such as TiO2, Ag3PO4, etc. For bi- or multi-phasic
hydrothermal synthesis. It has to be considered, however, that not materials, in fact, the measured photocatalytic efciency was
all studies reported a comparison with TiO2 or other commercial often higher than that of the different single phases the materials
catalysts; it is therefore not possible to assess with certainty which are made of, for experiment both in liquid and gas phases. Of the
photocatalysts are the most active. reasons for the improved photocatalytic activity is the well-known
To improve the efciency of the photocatalytic reactions, high adsorbing property of HAp, which favours and facilitate the
grafting processes should be explored more; indeed the use of Cu2 degradation of the pollutants. Due to these promising results, the
ions gave interesting results on Ti-doped HAp. Literature reports of combination of HAp with different photocatlysts (i.e. ZnO) should
signicant improvement in the photocatalytic efciency achieved also be explored.
for TiO2 through grafting with appropriate organic molecules such As for undoped and doped HAp, Ti-doped materials indeed
as silanes (Zhao et al., 2012; Pazokifard, 2012); this method should showed signicant photocatalytic properties; undoped materials,
indeed be applied also to HAp-based photocatalysts, testing suit- on the other hand, tend to exhibit lower activity e more studies
able molecules/ions. should be performed to better understand the features which could
Combining HAp with other photocatalytic compounds in bi- or improve such performance.
multiphasic materials was the approach which led to the most Overall HAp-based materials could be used for environment
effective photocatalysts; when HAp was used together with TiO2, remediation, due to their biocompatibility/low toxicity; their
for instance, all published studies reported an enhanced photo- multifunctional properties should be exploited, to obtain com-
catalytic efciency in comparison to just HAp or TiO2. These data pound which can degrade organic/gaseous pollutants under light
indicate that the combination of the excellent HAp adsorbing irradiation and which can also remove heavy metals from
properties and of the high TiO2 photoactive behaviour is indeed contaminated waters.
very effective, giving materials with improved performances. As
already mentioned above, depending on the materials and their Acknowledgments
preparation methods, the HAp:TiO2 ratio corresponding to the
highest photocatalytic activity will be different; it is interesting to This work was supported by National Funds from FCT - Fundaa ~o
note, however, that in some studies improved performances were ^ncia e a Tecnologia through the project UID/Multi/50016/
para a Cie
observed with very low HAp concentrations (<1% wt) (Yang and 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