Publish with Nova Science Publishers
We publish over 800 titles annually by leading researchers from around the world. Submit a Book Proposal Now!
Kathlen C. E. S. Yokoo, MD, Felipe Baião Ferreira, MD, Valéria Stephanny Oliveira Amorim, MD, and Gustavo Paim Valença, PhD
Laboratory for the Study of Adsorptive and Catalytic Processes (LEPAC), School of Chemical Engineering, University of Campinas (UNICAMP), Campinas, SP, Brazil
Part of the book: What to Know about Hydroxyapatite
Hydroxyapatite (HAP, Ca10(PO4)6(OH)2) and its applications in catalysis have attracted considerable attention in recent years. Mild acid and basic sites uniformly distributed on the surface of HAP makes it an attractive solid catalyst for condensation reactions with high conversion, selectivity, and stability. Thus, HAP is the subject of increasing interest in producing chemicals from oxygenated molecules such as ethanol. This chapter addresses the various modified hydroxyapatites applications in catalysis. The first part of the review will include HAP as a catalyst totally or partially substituted with different ions. The unique structure of HAP allows it to accept many anionic and cationic substituents. The second part will present HAP as the active phase support. Different metals supported on HAP showed improvement in the many catalytic reactions. More recent findings and the current challenges owing to the development of modified hydroxyapatite are summarized.
Keywords: hydroxyapatite, modified apatites, catalysis
Boechat CB, Eon JG, Rossi AM, Perez CAC, San Gil RAS. Structure of vanadate in
calcium phosphate and vanadate apatite solid solutions. Phys Chem Chem Phys (2000)
Boukha Z, Choya A, Cortés-Reyes M, de Rivas B, Alemany LJ, et al. Influence of the
calcination temperature on the activity of hydroxyapatite-supported palladium catalyst
in the methane oxidation reaction. Appl Catal B (2020) 277:119280.
Chakraborty R, Roy Chowdhury D. Fish bone derived natural hydroxyapatite-supported
copper acid catalyst: Taguchi optimization of semibatch oleic acid esterification.
Chemical Engineering Journal (2013) 215–216:491–499.
Chlala D, Giraudon JM, Labaki M, Lamonier JF. Formaldehyde Total Oxidation on
Manganese-Doped Hydroxyapatite: The Effect of Mn Content. Catalysts (2020)
Chlala D, Giraudon JM, Nuns N, Lancelot C, Vannier RN, et al. Active Mn species well
dispersed on Ca2+ enriched apatite for total oxidation of toluene. Appl Catal B (2016)
El-Aal MA, Ali HM, Ibrahim SM. Cu-Doped 1D Hydroxyapatite as a Highly Active
Catalyst for the Removal of 4-Nitrophenol and Dyes from Water. ACS Omega (2022)
Fihri A, Len C, Varma RS, Solhy A. Hydroxyapatite: A review of syntheses, structure and
applications in heterogeneous catalysis. Coord Chem Rev (2017) 347:48–76.
Goldberg MA, Akopyan AV, Gafurov MR, Makshakova ON, Donskaya NO, et al. Iron Doped Mesoporous
Powders of Hydroxyapatite as Molybdenum-Impregnated
Catalysts for Deep Oxidative Desulfurization of Model Fuel: Synthesis and
Experimental and Theoretical Studies. J Phys Chem C (2021) 125(21):11604–11619.
Gruselle M. Apatites: A new family of catalysts in organic synthesis. J Organomet Chem
Guo J, Yu H, Dong F, Zhu B, Huang W, Zhang S. High efficiency and stability of Au–
Cu/hydroxyapatite catalyst for the oxidation of carbon monoxide. RSC Adv (2017)
Hara T, Kanai S, Mori K, Mizugaki T, Ebitani K, et al. Highly efficient C-C bond-forming
reactions in aqueous media catalyzed by monomeric vanadate species in an apatite
framework. J Org Chem (2006) 71(19):7455–7462.
Ho CR, Zheng S, Shylesh S, Bell AT. The mechanism and kinetics of methyl isobutyl
ketone synthesis from acetone over ion-exchanged hydroxyapatite. J Catal (2018)
Ibrahim M, Labaki M, Giraudon JM, Lamonier JF. Hydroxyapatite, a multifunctional
material for air, water and soil pollution control: A review. J Hazard Mater (2020)
Jamwal N, Gupta M, Paul S. Hydroxyapatite-supported palladium (0) as a highly efficient
catalyst for the Suzuki coupling and aerobic oxidation of benzyl alcohols in water.
Green Chem (2008) 10(9):999-1003.
Jia W, Xu G, Liu X, Zhou F, Ma H, et al. Direct Selective Hydrogenation of Fatty Acids
and Jatropha Oil to Fatty Alcohols over Cobalt-Based Catalysts in Water. Energy
Fuels (2018) 32(8):8438–8446.
Jun J. Nickel–calcium phosphate/hydroxyapatite catalysts for partial oxidation of methane
to syngas: characterization and activation. J Catal (2004) 221(1):178–190.
Kalita J, Das B, Dhar SS. Synergistic effect of iron and copper in hydroxyapatite nanorods
for Fenton-like oxidation of organic dye. Colloids and Surfaces A: Physicochemical
and Engineering Aspects (2022) 643:128750.
Kamieniak J, Kelly PJ, Doyle AM, Banks CE. Influence of the metal/metal oxide redox
cycle on the catalytic activity of methane oxidation over Pd and Ni doped
hydroxyapatite. Catal Commun (2018) 107:82–86.
Khachani M, Kacimi M, Ensuque A, Piquemal JY, Connan C, et al. Iron–calcium–
hydroxyapatite catalysts: Iron speciation and comparative performances in butan-2-ol
conversion and propane oxidative dehydrogenation. Applied Catalysis A: General
Lamonier C, Lamonier JF, Aellach B, Ezzamarty A, Leglise J. Specific tuning of acid/base
sites in apatite materials to enhance their methanol thiolation catalytic performances.
Catal Today (2011) 164(1):124–130.
Lan YT, Yang XY, Liu SX, Miao YX, Zhao Z. Highly dispersed silver nanoparticles
supported on a hydroxyapatite catalyst with different morphologies for CO oxidation.
New J Chem (2022) 46(15):6940–6945.
Li X, Sun L, Zou W, Cao P, Chen Z, et al. Efficient Conversion of Bio-Lactic Acid to 2,3-
Pentanedione on Cesium-Doped Hydroxyapatite Catalysts with Balanced Acid-Base
Sites. Chem Cat Chem (2017) 9(24):4621–4627.
Lovón-Quintana JJ, Rodriguez-Guerrero JK, Valença PG. Carbonate hydroxyapatite as a
catalyst for ethanol conversion to hydrocarbon fuels. Applied Catalysis A: General
Maeda Y, Washitake Y, Nishimura T, Iwai K, Yamauchi T, Uemura S. Calcium phosphate
vanadate apatite (CPVAP)-catalyzed aerobic oxidation of propargylic alcohols with
molecular oxygen. Tetrahedron (2004) 60(41):9031–9036.
Matsumura Y, Sugiyama S, Hayashi H, Shigemota N, Saitoh K, Moffat JB. Strontium
hydroxyapatites: Catalytic properties in the oxidative dehydrogenation of methane to
carbon oxides and hydrogen. Journal of Molecular Catalysis (1994) 92(1):81–94.
Mayer I, Wahnon S, Cohen S. Preparation of hydroxyapatites via the MSO4 sulphates
(M = Ca, Sr, Pb and Eu). Mater Res Bull (1979) 14(11):1479–1483.
Mekrattanachai P, Cao C, Li Z, Li H, Song W. Cobalt immobilized on hydroxyapatite as a
low-cost and highly effective heterogeneous catalyst for alkenes epoxidation under
mild conditions. RSC Adv (2018) 8(65):37303–37306.
Miao D, Goldbach A, Xu H. Platinum/Apatite Water-Gas Shift Catalysts.
ACS Catal (2016) 6(2):775–783.
Mondelli C, Ferri D, Baiker A. 2008. Ruthenium at work in Ru-hydroxyapatite during the
aerobic oxidation of benzyl alcohol: An in situ ATR-IR spectroscopy study. J Catal
More RK, Lavande NR, More PM. Copper supported on Co substituted hydroxyapatite for
complete oxidation of diesel engine exhaust and VOC. Molecular Catalysis (2019)
Mori K, Oshiba M, Hara T, Mizugaki T, Ebitani K, Kaneda K. Michael reaction of 1,3-
dicarbonyls with enones catalyzed by a hydroxyapatite-bound La complex.
Tetrahedron Lett (2005) 46(25):4283–4286.
Mori K, Tano M, Mizugaki T, Ebitani K, Kaneda K. Efficient heterogeneous oxidation of
organosilanes to silanols catalysed by a hydroxyapatite-bound Ru complex in the
presence of water and molecular oxygen. New J Chem (2002) 26(11):1536–1538.
Moussa S ben, Mehri A, Badraoui B. Magnesium modified calcium hydroxyapatite: An
efficient and recyclable catalyst for the one-pot Biginelli condensation. J Mol Struct
Munirathinam R, Pham Minh D, Nzihou A. Hydroxyapatite as a new support material for
cobalt-based catalysts in Fischer-Tropsch synthesis. Int J Hydrogen Energy (2020)
Nakayama A, Sodenaga R, Gangarajula Y, Taketoshi A, Murayama T, et al. Enhancement
effect of strong metal-support interaction (SMSI) on the catalytic activity of
substituted-hydroxyapatite supported Au clusters. J Catal (2022) 410:194–205.
Ogo S, Onda A, Iwasa Y, Hara K, Fukuoka A, Yanagisawa K. 1-Butanol synthesis from
ethanol over strontium phosphate hydroxyapatite catalysts with various Sr/P ratios. J
Catal (2012) 296:24–30.
Ogo S, Onda A, Kajiyoshi K, Yanagisawa K. Hydrothermal synthesis and particle size
control of hydroxyapatite solid solutions with vanadate. Phosphorus Research Bulletin
Ogo S, Onda A, Yanagisawa K. Hydrothermal synthesis of vanadate-substituted
hydroxyapatites, and catalytic properties for conversion of 2-propanol. Applied
Catalysis A: General (2008) 348(1):129–134.
Ogo S, Onda A, Yanagisawa K. Selective synthesis of 1-butanol from ethanol over
strontium phosphate hydroxyapatite catalysts. Applied Catalysis A: General (2011)
Onda A, Ogo S, Kajiyoshi K, Yanagisawa K. Hydrothermal synthesis of vanadate/
phosphate hydroxyapatite solid solutions. Mater Lett (2008) 62(8–9):1406–1409.
Othmani M, Bachoua H, Ghandour Y, Aissa A, Debbabi M. Synthesis, characterization and
catalytic properties of copper-substituted hydroxyapatite nanocrystals. Mater Res Bull
Pang Y, Kong L, Chen D, Yuvaraja G, Mehmood S. Facilely synthesized cobalt doped
hydroxyapatite as hydroxyl promoted peroxymonosulfate activator for degradation of
Rhodamine B. J Hazard Mater (2020) 384:121447.
Park JH, Lee DW, Im SW, Lee YH, Suh DJ, et al. Oxidative coupling of methane using
non-stoichiometric lead hydroxyapatite catalyst mixtures. Fuel (2012) 94:433–439.
Qu Z, Sun Y, Chen D, Wang Y. Possible sites of copper located on hydroxyapatite structure
and the identification of active sites for formaldehyde oxidation. J Mol Catal A: Chem
Rego de Vasconcelos B, Pham Minh D, Martins E, Germeau A, Sharrock P, Nzihou A.
Highly-efficient hydroxyapatite-supported nickel catalysts for dry reforming of
methane. Int J Hydrogen Energy (2020) 45(36):18502–18518.
Saha D, Chatterjee T, Mukherjee M, Ranu BC. Copper(I) hydroxyapatite catalyzed
Sonogashira reaction of alkynes with styrenyl bromides. Reaction of cis-styrenyl
bromides forming unsymmetric diynes. J Org Chem (2012) 77(20):9379–9383.
Said AE-AA, El-Wahab MMMA, Alian AM. Selective oxidation of methanol to
formaldehyde over active molybdenum oxide supported on hydroxyapatite catalysts.
Catal Lett (2016) 146(1):82–90.
Sudhakar M, Kumar VV, Naresh G, Kantam ML, Bhargava SK, Venugopal A. Vapor phase
hydrogenation of aqueous levulinic acid over hydroxyapatite supported metal (M =
Pd, Pt, Ru, Cu, Ni) catalysts. Appl Catal B (2016) 180:113–120.
Sugiyama S, Osaka T, Hashimoto T, Sotowa KI. Oxidative Dehydrogenation of Propane
on Calcium Hydroxyapatites Partially Substituted with Vanadate. Catal Lett (2005)
Sugiyama S, Osaka T, Hirata Y, Sotowa K. Enhancement of the activity for oxidative
dehydrogenation of propane on calcium hydroxyapatite substituted with vanadate.
Applied Catalysis A: General (2006) 312:52–58.
Sugiyama S, Shono T, Nitta E, Hayashi H. Effects of gas- and solid-phase additives on
oxidative dehydrogenation of propane on strontium and barium hydroxyapatites.
Applied Catalysis A: General (2001) 211(1):123–130.
Tahir R, Banert K, Solhy A, Sebti S. Zinc bromide supported on hydroxyapatite as a new
and efficient solid catalyst for Michael addition of indoles to electron-deficient olefins.
J Mol Catal A: Chem (2006) 246(1–2):39–42.
Tõnsuaadu K, Gruselle M, Villain F, Thouvenot R, Peld M, et al. A new glance at
ruthenium sorption mechanism on hydroxy, carbonate, and fluor apatites: Analytical
and structural studies. J Colloid Interface Sci (2006) 304(2):283–291.
Wang QN, Weng XF, Zhou BC, Lv SP, Miao S, et al. Direct, Selective Production of
Aromatic Alcohols from Ethanol Using a Tailored Bifunctional Cobalt–
Hydroxyapatite Catalyst. ACS Catal (2019) 9(8):7204–7216.
Wang Y, Chen B, Crocker M, Zhang Y, Zhu X, Shi C. Understanding on the origins of
hydroxyapatite stabilized gold nanoparticles as high-efficiency catalysts for
formaldehyde and benzene oxidation. Catal Commun (2015) 59:195–200.
Xu J, Xu XC, Yang XJ, Han YF. Silver/hydroxyapatite foam as a highly selective catalyst
for acetaldehyde production via ethanol oxidation. Catal Today (2016) 276:19–27.
Xu Z, Huang G, Yan Z, Wang N, Yue L, Liu Q. Hydroxyapatite-Supported Low-Content
Pt Catalysts for Efficient Removal of Formaldehyde at Room Temperature. ACS
Omega (2019) 4(26):21998–22007.
Yamaguchi K, Mori K, Mizugaki T, Ebitani K, Kaneda K. Creation of a monomeric ru
species on the surface of hydroxyapatite as an efficient heterogeneous catalyst for
aerobic alcohol oxidation. J Am Chem Soc (2000) 122(29):7144–7145.
Yazdani ME, Monjezi BH, Mokfi M, Bozorgzadeh H, Gil A, Ghiaci M. Synthesis and
characterization of new hydrodesulphurization Co–Mo catalysts supported on
calcined and pyrolyzed bone. RSC Adv (2015) 5(51):40647–40656.
Zhang P, Wu T, Jiang T, Wang W, Liu H, et al. Ru–Zn supported on hydroxyapatite as an
effective catalyst for partial hydrogenation of benzene. Green Chem (2013)