Layered Aluminophosphate Research Articles

A Layered Aluminophosphate [C17H21N2]3[Al3(PO4)4]·5H2O with Fluorescent Property Derived from Carbazolyl-Modified Template.

Designing and innovating organic structure-directing agents is the key to synthesizing novel molecular sieve structures. Herein, we design a novel carbazolyl-modified template and further synthesize a two-dimensional layered aluminophosphate with [C17H21N2]3[Al3(PO4)4]·5H2O (denoted as ZHKU-2). ZHKU-2 is composed of AA-stacked [Al3P4O16]3- layers constructed from alternating AlO4 and PO3(=O) tetrahedrons to form a 4.6.8 network featured by capped six-ring secondary building units. Carbazolyl-templated ZHKU-2 exhibits strong purple fluorescence with a high quantum yield of 25.98%. This work expands aluminophosphate materials of the [Al3P4O16]3- family and provides a view for synthesizing new molecular sieves by exploring the organic luminescence structure-directing agents.

The embedding of fluorescent N-methyl-9-acridone into a topological new layered aluminophosphate SYSU-2 by one-pot synthesis.

A layered aluminophosphate |C14H11NO|2[Al4(HPO4)4F4(H2O)2] (denoted as SYSU-2) with a new topology has been hydrothermally synthesized with N-methyl-9-acridone (NMA) as the organic structure-directing agent. Single-crystal X-ray diffraction analysis reveals that SYSU-2 crystallizes in a triclinic space group P1[combining macron], with the inorganic sheets stacked in an AA sequence. Hydrogen bonds are responsible for the neutral inorganic-organic layer connection. The layer structure of SYSU-2 is constructed by alternating AlO4F2 octahedra and PO4 tetrahedra. The topological analysis of SYSU-2 indicates an independent topology. The NMA layers are self-assembled with π-π interaction. SYSU-2 crystals show interesting dual-band emission fluorescence properties compared with NMA crystals. Under 406 nm UV irradiation, SYSU-2 crystals emit yellow light with two emission bands at 477 and 566 nm, while NMA crystals emit blue light with only one band at 473 nm. The differences may be derived from the difference of stacking orders and distance of NMA molecule layers between the two crystals.

Solid-state nuclear magnetic resonance characterization of the second generation of the UEC family of molecular sieves

This work reports the characterization using solid-state NMR of the second generation of the UEC family of molecular sieves, such generation is composed by two tridimensional silicoaluminophosphates synthesized from a layered aluminophosphate (AlPO-CJ70). The 3D structures are analogous to SAPO-5 (UEC-4) and SAPO-15 (UEC-5), both were characterized using multinuclear solid-state NMR, 27Al-MQ-MAS and 29Si{27Al} TRAPDOR.

Corrigendum: An NMR-Driven Crystallography Strategy to Overcome the Computability Limit of Powder Structure Determination: A Layered Aluminophosphate Case.

Following discussions among the authors of the paper (Versailles March 3rd, 2014, updated June 5th 2016), the corrections listed below are to be included: The author list has been updated. The full list, plus address [f] for Dr. Julien Dutour, is given below: Boris Bouchevreau,[a] Dr. Charlotte Martineau,*[a] Dr. Caroline Mellot-Draznieks,[b] Dr. Julien Dutour,[f] Dr. Alain Tuel,[c] Dr. Matthew R. Suchomel,[d] Dr. Julien Trébosc,[e] Prof. Olivier Lafon,[e] Prof. Jean-Paul Amoureux,[e] and Dr. Francis Taulelle*[a] [f] Institut Lavoisier de Versailles, CNRS UMR 8180, Université de Versailles Saint-Quentin en Yvelines, 45 avenue des États-Unis, 78035 Versailles Cedex, France. Reference [6] should be added after the sentence on the second page, 4th paragraph, in the left column, to read: The SPD pattern of AlPO4-(Al5P7)-DAE could nonetheless be indexed easily by a tetragonal unit cell with refined parameters a=15.826(1) and c=22.684(1) Å, and the observed hkl reflection conditions indicated the non-centro-symmetrical space group P42bc.[6] Following the addition of a sentence at the end of the 5th paragraph in the left column on the second page, the text should read as follows: However, after ten days of calculations on a standard desktop computer, no convergence to a reliable solution was achieved with this set of small fragments despite the high quality of the SPD data. In order to introduce additional structural information, high-resolution one (1D) and two (2D) NMR experiments were undertaken. This approach differs with the reduction of parameters undertaken in ref. [6] on the basis of crystallochemical intuition. Modified reference [6]: [6] a) Dutour, J., PhD Dissertation, University of Versailles Saint-Quentin en Yvelines, Versailles (France) 2006, http://www.theses.fr/2006VERS0027; b) Guillou, N.; ESRF, 2005, http://ftp.esrf.eu/pub/UserReports/26614_B.pdf; c) N. Guillou, C. Mellot-Draznieks, J. Dutour, A. Tuel, F. Taulelle, W. van Beek, G. Férey, Book of Abstracts 10th European Powder Diffraction Conference, p. 110, MS4-P37, Geneva, 1–4 September 2006.

Co‐templating Ionothermal Synthesis and Crystal Structure of a New Layered Aluminophosphate from a Protic Deep Eutectic Solvent

AbstractProtic deep eutectic mixtures are usually composed of organic amine hydrochloride salts and hydrogen bond donors in a specific molar ratio. Ionothermal synthesis of aluminophosphate as an example, herein, was reported for the first time from an urea‐based protic eutectic mixture, consisting of diethylammonium chloride (DEACl) and 1,3‐dimethyl urea (DMU). As a result, a new two dimensional aluminophosphate with 4.8‐network, [CH3NH3]2[(C2H5)2NH2]Al3(PO4)4, has been successfully synthesized by co‐templating the DEA and methylamine in situ generated from the decomposition of DMU in the absence of HF. Compared to alkyl quaternary ammonium salts with more alkyl‐group connected with N atom, this kind of organic amine salts are more likely as the structure‐directing agents to synthesize aluminophosphates in urea‐based deep eutectic mixtures. It was also found that HF is crucial to the phase selectivity, a known compound with chain‐like structure was obtained with the single methylamine as a structure‐directing agent in the presence of HF. These materials were characterized by powder XRD, SEM, TG‐DSC, 13C CP‐MAS NMR and CHN analyses.

A New Strategy for Simultaneously Improved Flame Retardancy, Thermal Properties, and Scratch Resistance of Transparent Poly(methyl methacrylate)

A novel poly(methyl methacrylate) (PMMA)-based nanocomposite combined with a reactive flame retardant (tetramethyl (3-(triethoxysilyl) propyl-azanediyl) bis(methylene) diphosphonate (TMSAP)) and organo-modified layered aluminophosphate (OLAP) was synthesized by the sol–gel method. The structure of the nanocomposite achieves maximal integration of both merits of each component, such as silane cross-linking function and dehydration charring effect of TMSAP and physical barrier effect and catalytic-charring effect of OLAP, which promotes cross-linked network formation, improves the quality and quantity of char, and inhibits the heat, oxygen, and mass transfer, leading to significant enhancements of scratch resistance, thermal stability, and flame retardancy. Compared to PMMA, the nanocomposites maintain high transparency and exhibit increased shore hardness by 90%, glass transition temperature by 13 °C, and half degradation temperature by 105.1 °C; in addition, peak heat released rate decreased by 59.1%. This work demonstrates the simultaneous enhancement of flame retardancy, thermal properties, and mechanical performance of polymers.

Synthesis and proton conductivity of a new two-dimensional layered aluminophosphate [C9H14N]8[H2O]4·[Al8P12O48H4

A new two-dimensional layered aluminophosphate [C9H14N]8[H2O]4·[Al8P12O48H4] (denoted as AlPO-CJ70) has been synthesized by using N,N-dimethylbenzylamine as the template under solvothermal conditions at 403K. Single-crystal X-ray diffraction analysis reveals that the structure of AlPO-CJ70 consists of AAAA-stacked Al2P3O123− layers made of alternating AlO4 and PO4 (PO3(O) and PO2(O)(OH)) tetrahedra, forming 1D 8-ring channels along the [100] direction. The inorganic layer exhibits a new type of 4×6×8 sheets with the Al/P ratio of 2/3. Protonated N,N-dimethylbenzylamine cations are located between the layers compensating the negative charge of the anionic framework. The existence of guest water and extensive H-bonds in the structure endows AlPO-CJ70 with proton conduction properties, as elucidated by impedance studies of the powder sample.

A novel layered aluminophosphate with corner-sharing AlO6chains

The synthesis, Raman spectroscopy and crystal structure of a novel layered aluminophosphate is described. The new phase was derived by the sol-gel method starting from a modified low hydrothermal ALPO4-34 zeolite synthesis procedure[1].The structure was solved by direct methods using single-crystal X-ray diffraction. The synthesized layered material, with composition [AlPO3(OH)F(H2O)]-(H9C4ON), crystallizes in the monoclinic space group P21/a with a = 9.2282(5) Å, b = 6.9152(4) Å, c = 14.4615(9) Å, β = 101.57(1)0. Layered aluminophosphates with AlO6polyhedra have been previously described [2], although in these compounds Al octahedral share edges. The novel compound has corner sharing AlO4F(H2O) chains along [010], where fluorine is at the shared apex, four oxygen atoms are shared with PO4tetrahedra and the fifth oxygen is a H2O group. This kind of aluminophosphate chains is found in nature in tancoite [3]. Chains are linked along [100] through corner sharing with a PO4group of the adjacent chain plus hydrogen bonding of the H2O group. Layers are stacked along c* through hydrogen bonding with a double layer of morpholine (H9C4ON) molecules. The chemical stability field of the novel materialis strongly dependent from the fluorine/aluminum ratio of the starting gel. At lower fluorine concentrations only ALPO4-34 and/or AlPO4(berlinite) are stable depending on the morpholine content. Crystals growth morphology depends on the supersaturation conditions of the starting gel: at low concentrations crystals are well developed hexagonal like plate shaped and are very thin. At higher concentrations they show a more elongated morphology. A treatment with H2CO3leads to a complete morpholine removal, as shown by in situ Raman spectroscopy. Powder X-ray diffraction reveals that after morpholine extraction, the material diffract still coherently in two dimensions while a strong broadening is shown for basal planes.

The structure-directing effect of n-propylamine in the crystallization of open-framework aluminophosphates

Using n-propylamine as a template, deioned water and secondary-butanol (butan-2-ol) as solvents, a three-dimensional (3D) open-framework aluminophosphate [C3NH10]·[HAl3P3O13] (1) and a two-dimensional layered aluminophosphate [C3NH10]3·[Al3P4O16] (2) were crystallized from the initial mixtures with compositions of Al2O3: 2.4 P2O5: 5.0 n-propylamine: 100 H2O/butan-2-ol, respectively. They are characterized by X-ray powder diffraction (XRD), thermogravimetric (TG), and elemental (CHN) analyses and structurally determined by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic space group P21/c with a = 0.85831(13) nm, b = 1.7677(3) nm, c = 1.04353(12) nm, β = 123.887(9)°, and V = 1.3143(3) nm3. Compound 2 crystallizes in the monoclinic space group P21/c with a = 1.1313(2) nm, b = 1.4874(3) nm, c = 1.8020(6) nm, β = 125.07(2)°, and V = 2.4817(11) nm3. The results show that the properties of solvent have a significant influence on the structure-directing effect of n-propylamine in the crystallization of the open-framework aluminophosphates.

Ag/lamellar hosts composites: a route to morphology-controllable synthesis of Ag nanoparticles

An easy and novel routine are reported for the preparation of metallic silver nanoparticles (AgNPs) with controlled morphology, using Na+–magadiite swelled with hexadecyltrimethylammonium bromide (CTA+–magadiite) and a layered aluminophosphate with kanemite-type structure modified with n-dodecylammonium and n-butylammonium (but,dod-AlPO-kan) as hosts. For the preparation of the metallic AgNPs (Ag0) in the interlamellar space, the CTA+–magadiite and but,dod-AlPO-kan hosts were dispersed in N,N-dimethylformamide (DMF) solution with different AgNO3 concentrations. DMF acts as reducing agent of Ag+ ions leading to nanoparticles with disk-like morphology of magadiite silicate; these were characterized by TEM and UV–Vis spectroscopy. On the other hand, the AgNPs are intercalated in but,dod-AlPO-kan showing spherical-like morphology. The UV–Vis spectra of the nanocomposites based on Ag0 and magadiite silicate show bands at 565 nm that can be attributed to Ag0 nanodisks. The Ag-but,dod-AlPO-kan-based nanocomposites present a band at 422 nm attributed to the surface plasmon resonance of Ag0 nanospheres. The results of transmission electron microscopy agree very well with XRD and UV–Vis analysis, indicating the formation of AgNPs with different morphologies using the two kinds of lamellar materials. The magadiite host has an important role in the synthesis of Ag nanodisks, because it controls the growth of nanoparticles inside the interlayer region with disk-like morphology due the high interlayer interactions of the silicate, leading to the growth of nanoparticles in only two directions (xy plane). On the other hand, when but,dod-AlPO-kan is used a sphere-like morphology is preferred due the best accommodation of AgNPs between the layers of aluminophosphate host.

An NMR‐Driven Crystallography Strategy to Overcome the Computability Limit of Powder Structure Determination: A Layered Aluminophosphate Case

Just in time: An NMR-driven structure resolution that allows structure determination from the powder diffraction data of a highly complex layered aluminophosphate, and was otherwise not possible despite the high quality of the synchrotron diffraction data, is proposed. This study shows that the strategy is general and allows reduction of the number of free parameters to search for a structure and converge under the limit of the combinatorial explosion of computing time (see figure).

Signal enhancement of J-HMQC experiments in solid-state NMR involving half-integer quadrupolar nuclei

We show that for half-integer quadrupolar nuclei, the manipulation of the satellite transitions can accelerate and enhance coherence transfer to other isotopes. This novel strategy is demonstrated to improve the sensitivity of (31)P-{(27)Al} J-HMQC experiments for a layered aluminophosphate Mu-4.

Molecular engineering of microporous crystals: (VI) Structure-directing effect in the crystallization process of layered aluminophosphates

The products of piperazine-directed synthesis of two-dimensional (2D) aluminophosphates, AP2pip and AlPO-CJ9, that were crystallized under different conditions for different periods of time were freeze-dried and characterized using XRD and NMR techniques. The core units of the layered aluminophosphates including AP2pip, AlPO-CJ9, and L-DAP, which was hydrothermally synthesized in the presence of racemic 1,2-diaminopropane, were obtained by applying a “reverse evolution” process to their structures. The factors affecting the structure-directing ability of piperazine under acidic and basic conditions were analyzed. The cooperative role of water in directing the layered aluminophosphate of AP2pip under acidic conditions is discussed. After a thorough analysis of the core units of AlPO-CJ9 and L-DAP, a new phenomenon of a “topological-structure-directing effect” or a “topological-templating effect” was observed. The observation of the new phenomenon of a topological-structure-directing effect or a topological-templating effect may contribute to a deeper understanding of the nature or origin of the “structure-directing or templating effect”.

Co-templating ionothermal synthesis and structure characterization of two new 2D layered aluminophosphates

For the first time, the co-templating ionothermal methodology was used in the preparation of layered aluminophosphate materials. With the addition of either 1,2-ethylenediamine or 1,6-hexanediamine to the ionic liquid 1-ethyl-3-methyl imidazolium chloride, two new 2D layered aluminophosphates RUB-A1 [Al(3)P(4)O(16)][NH(3)CH(2)CH(2)NH(3)](0.5)[C(6)N(2)H(11)](2) and RUB-A2 [Al(3)P(4)O(16)][NH(3)(CH(2))(6)NH(3)][NH(3)(CH(2))(6)NH(2)](0.5)[C(6)N(2)H(11)](0.5)[H(2)O] have been synthesized ionothermally by co-templating. The structure of RUB-A1 has been determined from single-crystal X-ray diffraction data using direct methods, while the structure of RUB-A2 has been solved ab initio from powder X-ray diffraction data with limited resolution using direct-space methods. Both of these two compounds have a 2D layered structure consisting of macroanionic sheets of composition [Al(3)P(4)O(16)](3-) stacked in an AAAA sequence. The inorganic layers are built up from alternatively vertex-sharing [AlO(4)]- and [PO(3)(=O)]-tetrahedral units forming a 4.6.8 and a 4.6.12 network for RUB-A1 and RUB-A2, respectively. The layer topology of RUB-A1 is closely related to the previously known 4.6.8-layer topology but with a different sequence of phosphoryl group orientation. Combining the results of structure analysis with the NMR, chemical analysis and TG-DTA experiments, we show that both the ionic liquid cation and the protonated diamines are located in the interlayer space and together direct the formation of these two structures.

ChemInform Abstract: Mu-7, a New Layered Aluminophosphate [CH3NH3]3 [Al3P4O16] with a 4 x 8 Network: Characterization, Structure, and Possible Crystallization Mechanism.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Cs2Al2P2O9: An Exception to Loewenstein′s Rule. Synthesis and Characterization of a Novel Layered Aluminophosphate Containing Linear Al-O-Al Linkages.

ChemInform Abstract: Cs2Al2P2O9: An Exception to Loewenstein′s Rule. Synthesis and Characterization of a Novel Layered Aluminophosphate Containing Linear Al-O-Al Linkages.

Preparation of aluminophosphate/polyethylene nanocomposite membranes and their gas permeation properties

Composite membranes were prepared by the incorporation of a porous layered aluminophosphate (ALPO) into polyethylene (PE) matrix, through both in situ polymerization with metallocene catalyst and melt compounding methods. ALPO was previously swollen with protonated octadecylammine (ODA) and cetyltrimethylammonium (CTA), which generated intercalated particles with different morphologies and dimensions. ODA–ALPO particles incorporated by in situ polymerization were found to be completely exfoliated in the composite, although probably with partial damage of their microporous structure. Composites prepared by melt compounding with CTA–ALPO particles, were found to contain particles predominantly in intercalated form, and apparently with good preservation of the aluminophosphate structure. Permeability results demonstrate that the incorporation of swollen-ALPO particles significantly improves the gas permeation properties of the semicrystalline polyolefin membrane. Gas permeability increase is attributed to novel transport pathways provided by the presence of the microporous ALPO layers as well as to the reduction of PE crystal size and the disruption of polymer-chain packing. Permeability of smaller gas molecules tended to be favoured, suggesting a molecular sieve effect through the microporous ALPO structure. ALPO/PE membranes exhibited particular H 2/CO permselectivity. Highest H 2/CO selectivity values were achieved at 5 wt.% loading of swollen-ALPO, particularly for membranes prepared by melt compounding using CTA–ALPO particles (H 2/CO = 9.5–17.0 as compared to H 2/CO = 1.0–2.6 for pure PE). The better performance of CTA–ALPO/PE membranes is attributed to a better preservation of the microporous structure of CTA–ALPO particles as well as to a better dispersion degree achieved through melt mixing technique. The results of this work open the possibility of the use of polyolefin composites prepared with the porous layered ALPO as a novel membrane material. Particular H 2/CO permselectivity exhibited by these membranes makes of it promising for hydrogen purification applications.

One Step Further in Understanding the Role of Hydrogen Bonds in Directing the Synthesis of CHA Analogue Molecular Sieves

In this work, the synthesis of CAL-4, a SAPO-44 structural analogue, is studied. This silicoaluminophosphate molecular sieve was prepared starting from the layered aluminophosphate n-butylammonium-...

Porous layered oxide/Nafion ® nanocomposite membranes for direct methanol fuel cell applications

Nanocomposite membranes were prepared by exfoliating, intercalating and/or dispersing nanoporous layered aluminophosphate or silicate materials in Nafion ®. Specifically, the layered aluminophosphate-triethylamine (APO-TE), aluminophosphate-isopropanolamine (APO-IPA), aluminophosphate-imidazole (APO-ImH), and the swollen layered silicate AMH-3, were used as selectively permeable barriers that can potentially block methanol permeation but maintain proton conductivity in the membrane. The presence of the layered materials in Nafion ® membranes reduced the methanol permeability by up to an order of magnitude while maintaining proton conductivities close to that of neat Nafion ® at room temperature. Small-angle X-ray scattering (SAXS) characterization shows substantial differences in microstructure of the nanocomposite membranes from that of neat Nafion ®. The performance of the nanocomposite membranes was also found to be strongly dependent on the membrane pre-treatment conditions. Detailed comparison of our data to the previous literature indicates that for certain conditions of membrane preparation, the proposed approach yields promising results in controlling methanol and proton transport through membranes for direct methanol fuel cell (DMFC) applications.

Interface Between Alkylammonium Ions and Layered Aluminophosphates Materials: A Combined Theoretical and Experimental Study

n-Butylammonium ions intercalated in a layered aluminophosphate (AlPO-ntu) with kanemite-type structure (hereafter AlPO-kan) have been studied by IR spectroscopy and modeled with density functional theory (DFT) calculations. This joint approach clarified the local structure of the inorganic/organic interface, not yet described. The acidity of the surface hyroxyls was investigated with a finite cluster model, while the structure and the theoretical IR spectra were obtained with 3D and 2D periodic boundary conditions. In the structure here optimized, each organic ion forms three hydrogen bonds with the surface phosphate and aluminate oxygens; the theoretical frequencies, including anharmonic corrections on the main stretching modes, were compared to the experimental IR spectra. The very satisfactory agreement confirms the optimized structure and allowed all the observed peaks to be assigned, providing for the first time a clear-cut interpretation of the broad and complex absorption at 2800−1700 cm−1 in term...