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Zirconium Phosphate Catalysts
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Zirconium Phosphate Catalysts

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (28 February 2017) | Viewed by 43127

Special Issue Editor

Dr. Monica Pica

E-Mail Website
Guest Editor
Department of Pharmaceutical Sciences, University of Perugia, Via del Liceo 1, 06123 Perugia, Italy
Interests: zirconium phosphate based materials; treatment of wastewater
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

It is a pleasure to announce this Special Issue on "Zirconium Phosphate Catalysts".

Layered tetravalent metal phosphates, especially Zr(IV) phosphates, have been widely studied over the last forty years and continue to draw attention thanks to their robustness, the possibility to modulate their properties by controlling the synthetic conditions, or by surface functionalization. Zirconium phosphates with 1D, 2D, 3D dimensional connectivity are known and, among them, 2D layered zirconium phosphates are highly versatile compounds, due to their numerous properties, such as ion exchange properties, surface acidity or basicity, intercalation, and exfoliation.

In light of this versatility, zirconium phosphates have been employed in several application fields, such as electrochemical devices, polymer nanocomposites, drug delivery systems, and catalysis.

The present Special Issue aims to focus attention on a high impact topic, heterogeneous catalysis. More specifically, researchers all over the world are called to share their experiences on the use of zirconium phosphates in heterogeneous catalysis, trying to bring out and rationalize the manifold aspects of this topic. Some suggestions are below reported:
- catalytic properties of zirconium phosphates;
- zirconium phosphates as inorganic supports of catalytic active species;
- new heterogeneous catalysts by surface modification of zirconium phosphates.

I look forward to receiving original contributions or review papers.

Dr. Monica Pica
Guest Editor

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Published Papers (6 papers)

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Research

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8 pages, 2193 KiB  
Article
Solid Acid Catalyst Based on Single-Layer α-Zirconium Phosphate Nanosheets for Biodiesel Production via Esterification
by Yingjie Zhou, Iman Noshadi, Hao Ding, Jingjing Liu, Richard S. Parnas, Abraham Clearfield, Min Xiao, Yuezhong Meng and Luyi Sun
Catalysts 2018, 8(1), 17; https://doi.org/10.3390/catal8010017 - 10 Jan 2018
Cited by 50 | Viewed by 6616
Abstract
In this study, a solid acid was prepared by the sulfonation of surface modified α-zirconium phosphate (ZrP) single-layer nanosheets (SO3H@ZrP), and the prepared solid acid was investigated for the esterification of oleic acid with methanol to produce biodiesel. For comparison, liquid [...] Read more.
In this study, a solid acid was prepared by the sulfonation of surface modified α-zirconium phosphate (ZrP) single-layer nanosheets (SO3H@ZrP), and the prepared solid acid was investigated for the esterification of oleic acid with methanol to produce biodiesel. For comparison, liquid H2SO4 and commercial Amberlyst® 15 catalyst were also evaluated for the same reaction under the same conditions. The experimental results showed that the SO3H@ZrP solid acid catalyst has a superior catalytic efficiency for the esterification reaction, as well as excellent recyclability. The SO3H@ZrP single-layer solid acid catalyst can be uniformly dispersed in the reaction media, but remains heterogeneous and thus can be easily separated and recycled. Full article
(This article belongs to the Special Issue Zirconium Phosphate Catalysts)
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12773 KiB  
Article
Immobilized Palladium Nanoparticles on Zirconium Carboxy-Aminophosphonates Nanosheets as an Efficient Recoverable Heterogeneous Catalyst for Suzuki–Miyaura and Heck Coupling
by Vadym Kozell, Tommaso Giannoni, Morena Nocchetti, Riccardo Vivani, Oriana Piermatti and Luigi Vaccaro
Catalysts 2017, 7(6), 186; https://doi.org/10.3390/catal7060186 - 9 Jun 2017
Cited by 34 | Viewed by 5798
Abstract
Zirconium phosphate glycine diphosphonate nanosheets (ZPGly) have been used as support for the preparation of solid palladium nanoparticles, namely Pd@ZPGly. Thanks to the presence of carboxy-aminophosponate groups on the layer surface, ZPGly-based materials were able to stabilize a high amount of palladium (up [...] Read more.
Zirconium phosphate glycine diphosphonate nanosheets (ZPGly) have been used as support for the preparation of solid palladium nanoparticles, namely Pd@ZPGly. Thanks to the presence of carboxy-aminophosponate groups on the layer surface, ZPGly-based materials were able to stabilize a high amount of palladium (up to 22 wt %) also minimizing the amount of metal leached in the final products of representative important cross-coupling processes selected for proving the catalysts’ efficiency. The catalytic systems have been fully characterized and used in low amounts (0.1 mol %) in the Suzuki–Miyaura and Heck cross-couplings. Moreover, the protocols were optimized for the use of recoverable azeotropic mixtures (aq. EtOH 96% or aq. CH3CN 84%, respectively) and in the flow procedure allowing one to isolate the final pure products, without any purification step, with very low residual palladium content and with a very low waste production. Full article
(This article belongs to the Special Issue Zirconium Phosphate Catalysts)
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3949 KiB  
Article
Zirconium Phosphate Heterostructures as Catalyst Support in Hydrodeoxygenation Reactions
by Daniel Ballesteros-Plata, Antonia Infantes-Molina, Elena Rodríguez-Aguado, Pilar Braos-García, José Jiménez-Jiménez and Enrique Rodríguez-Castellón
Catalysts 2017, 7(6), 176; https://doi.org/10.3390/catal7060176 - 2 Jun 2017
Cited by 8 | Viewed by 4749
Abstract
A porous phosphate heterostructure (PPHs) formed by a layered zirconium(IV) phosphate expanded with silica galleries was prepared presenting a P/Zr molar ratio equal to 2 and a (Si + Zr)/P ratio equal to 3. This pillared zirconium phosphate heterostructure was used as a [...] Read more.
A porous phosphate heterostructure (PPHs) formed by a layered zirconium(IV) phosphate expanded with silica galleries was prepared presenting a P/Zr molar ratio equal to 2 and a (Si + Zr)/P ratio equal to 3. This pillared zirconium phosphate heterostructure was used as a catalyst support for bi-functional catalysts based on noble metals (Pt or Pd) and molybdenum oxide containing a total metallic loading of 2 wt % and Pt(Pd)/Mo molar ratio equal to 1. The catalysts prepared were characterized by different experimental techniques and evaluated in the hydrodeoxygenation (HDO) reaction of dibenzofuran (DBF) as a model compound present in biomass derived bio-oil, at different reaction pressures. The catalyst characterization evidenced that a high dispersion of the active phase can be achieved by using these materials, as observed from transmission electron microscopy (TEM) characterization, where the presence of small particles in the nanometric scale is noticeable. Moreover, the textural and acidic properties of the phosphate heterostructure are barely affected by the incorporation of metals into its structure. Characterization results evidenced that the presented material is a good candidate to be used as a material support. In both cases, high conversions and high selectivities to deoxygenated compounds were achieved and the active phase played an important role. Thus, Pt/Mo presented a better hydrogenolysis capability, being more selective to O-free products; whereas, Pd/Mo showed a greater hydrogenation ability being more affected by changes in pressure conditions. Full article
(This article belongs to the Special Issue Zirconium Phosphate Catalysts)
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2456 KiB  
Article
Imidazoles-Intercalated α-Zirconium Phosphate as Latent Thermal Initiators in the Reaction of Glycidyl Phenyl Ether (GPE) and Hexahydro-4-Methylphthalic Anhydride (MHHPA)
by Osamu Shimomura, Kensuke Tokizane, Takatoshi Nishisako, Shunro Yamaguchi, Junko Ichihara, Manabu Kirino, Atsushi Ohtaka and Ryôki Nomura
Catalysts 2017, 7(6), 172; https://doi.org/10.3390/catal7060172 - 1 Jun 2017
Cited by 13 | Viewed by 4951
Abstract
The capabilities of imidazoles-intercalated α-zirconium phosphate (α-ZrP·imidazole): imidazol (α-ZrP·Im), 2-methylimidazole (α-ZrP·2MIm), and 2-ethyl-4-methylimidazole (α-ZrP·2E4MIm) as latent thermal initiators were examined by the copolymerization of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA) with the imidazoles-intercalated α-zirconium phosphate at varying temperatures for one-hour periods. [...] Read more.
The capabilities of imidazoles-intercalated α-zirconium phosphate (α-ZrP·imidazole): imidazol (α-ZrP·Im), 2-methylimidazole (α-ZrP·2MIm), and 2-ethyl-4-methylimidazole (α-ZrP·2E4MIm) as latent thermal initiators were examined by the copolymerization of glycidyl phenyl ether (GPE) and hexahydro-4-methylphthalic anhydride (MHHPA) with the imidazoles-intercalated α-zirconium phosphate at varying temperatures for one-hour periods. Polymerization was not observed until the reactants were heated to 100 °C or above. Increasing the temperature, polymerization in the presence of α-ZrP·Im, α-ZrP·2MIm, or α-ZrP·2E4MIm proceeded at 140 °C for 1 h with over 90% conversion. The thermal stabilities of α-ZrP·Im, α-ZrP·2MIm, and α-ZrP·2E4MIm in the reaction at 40 °C for 264 h were tested. With α-ZrP·2MIm, the conversion was less than 15% up to 96 h. In the cases of α-ZrP·Im and α-ZrP·2E4MIm, the conversion reached less than 15% at 264 h. The thermal stabilities of α-ZrP·Im, α-ZrP·2MIm, and α-ZrP·2E4MIm at 40 °C were superior to those of the commercially available thermal latent initiators: HX-3088 and HX-3722. Full article
(This article belongs to the Special Issue Zirconium Phosphate Catalysts)
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2086 KiB  
Article
Transition Metal-Modified Zirconium Phosphate Electrocatalysts for the Oxygen Evolution Reaction
by Joel Sanchez, Mario V. Ramos-Garcés, Ieva Narkeviciute, Jorge L. Colón and Thomas F. Jaramillo
Catalysts 2017, 7(5), 132; https://doi.org/10.3390/catal7050132 - 1 May 2017
Cited by 28 | Viewed by 11260
Abstract
Zirconium phosphate (ZrP), an inorganic layered nanomaterial, is currently being investigated as a catalyst support for transition metal-based electrocatalysts for the oxygen evolution reaction (OER). Two metal-modified ZrP catalyst systems were synthesized: metal-intercalated ZrP and metal-adsorbed ZrP, each involving Fe(II), Fe(III), Co(II), and [...] Read more.
Zirconium phosphate (ZrP), an inorganic layered nanomaterial, is currently being investigated as a catalyst support for transition metal-based electrocatalysts for the oxygen evolution reaction (OER). Two metal-modified ZrP catalyst systems were synthesized: metal-intercalated ZrP and metal-adsorbed ZrP, each involving Fe(II), Fe(III), Co(II), and Ni(II) cations. Fourier transform infrared spectroscopy, X-ray powder diffraction, thermogravimetric analysis, and X-ray photoelectron spectroscopy were used to characterize the composite materials and confirm the incorporation of the metal cations either between the layers or on the surface of ZrP. Both types of metal-modified systems were examined for their catalytic activity for the OER in 0.1 M KOH solution. All metal-modified ZrP systems were active for the OER. Trends in activity are discussed as a function of the molar ratio in relation to the two types of catalyst systems, resulting in overpotentials for metal-adsorbed ZrP catalysts that were less than, or equal to, their metal-intercalated counterparts. Full article
(This article belongs to the Special Issue Zirconium Phosphate Catalysts)
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Review

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456 KiB  
Review
Zirconium Phosphate Catalysts in the XXI Century: State of the Art from 2010 to Date
by Monica Pica
Catalysts 2017, 7(6), 190; https://doi.org/10.3390/catal7060190 - 19 Jun 2017
Cited by 55 | Viewed by 8384
Abstract
An overview on the developments of zirconium phosphate (ZrP) and its organic derivatives in heterogeneous catalysis in recent years is reported in the present review. Two basic aspects have been emphasized: first, the catalytic properties of zirconium phosphates were discussed, with particular attention [...] Read more.
An overview on the developments of zirconium phosphate (ZrP) and its organic derivatives in heterogeneous catalysis in recent years is reported in the present review. Two basic aspects have been emphasized: first, the catalytic properties of zirconium phosphates were discussed, with particular attention to the effect of surface acidity and hydrophobic/hydrophilic character, textural properties, and particle morphology on the catalytic performances. Then, the use of zirconium phosphates as support for catalytic active species was reported, including organometallic complexes, metal ions, noble metal, and metal oxide nanoparticles. Zirconium phosphate plays, in those cases, a dual role, since it promotes the dispersion and stabilization of the catalysts, thanks to their interaction with the active sites on the surface of ZrP, and facilitates the recovery and reuse of the catalytic species due to their immobilization on the solid support. Full article
(This article belongs to the Special Issue Zirconium Phosphate Catalysts)
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