Structure of Metal Aluminophosphates:Al_(9-x)M_xP_(12)O_(48)(TREN)_4·yNH_4·zH_2O [TREN=N(CH_2CH_2NH_3)H_m,M=Mn,Co]

Two large-pore metal-doped aluminophosphates, Mn4Al5（PO4 ）12[N（ C2H4NH3）3]3 [ N（C2H4NH3）2·（C2H4NH2）]（NH4）2·14H=O（Mn4-NJU） and Co4Al5（PO4）12[N（C2H,NH3）3][N（C2H4NH3）2（C2H4NH2）]3· （ NH4 ）4· 13H2O （ Co4-NJU） , which have the same open framework structures, were hydrothermally synthesized. The structures of these compounds consist of TO4 tetrahedra, which are linked together by corner-sharing to form an open framework with unique intersecting twelve-membered ring channels in three dimensions. The compounds crystallize in cubic space group I（-4）3m with α= 1. 6795（2） nm and V=4. 7374（9） nm^3 for Mn4-NJU, and a=1. 67372（19） nm and V = 4. 6887 （9） nm^3 for Co4-NJU, respectively. Single crystal structure analyses show that the protruding O atoms of the frameworks of the compounds are linked to protonated 4-（ 2-aminoethyl ）diethylenetriamine （TREN, C6H18N4 ） ions in the windows by means of hydrogen-bonding under the hydrothermal condition. It is also found that the components inside the super cages of the compounds are changeable, and the metal ions M^2＋ （M = Mn, Co） and Al^3＋ disorderedly occupy the same crystallographic positions.

SYNTHESIS AND CHARACTERIZATION OF NOVEL MICROPOROUS ALUMINOPHOSPHATES.

A series of novel aluminophosphates,named AlPO_4-CJ_n(n=2-5),has been synthesized hydrothermally from R-Al_2O_3-P_2O_5-H_2O systems(R= organic amine molecules),and characterized by means of X-ray powder diffraction,infrared,SEM,XPS,composition and thermal analyses.

Advances in Synthesis of Mesostructured Aluminophosphates

More and more attention has been paid to the synthesis of mesostructuredaluminophosphates for many years. A lot of valuable research results, including various syntheticapproaches and structural materials, have been obtained. This paper reviews the progress in thesynthesis of mesostructured aluminophosphates over the past few years, with the hope of revealingopportunities for future work.

Structure-directing Effect on Synthesis of Layered Aluminophosphates with Same Topology

Three layered aluminophosphates（UiO-15, APDAP12-150 and APDAP-150） with same topology were crystallized from an initial mixture with a molar Composition of A1203：1.SP2Os：5.5R：227HzO, where R is ethylene- diamine, 1,2-diaminopropane or 1,3-diaminopropane, respectively. The crystallization processes of UiO-15, APDAPI2-150 and APDAP-150 were investigated using solid-state NMR in combination with XRD and other cha- racterization techniques. The evolution of the coordination states of Al and P in the solid products was monitored, and the possible starting points of crystallization（core units） of UiO-15, APDAP12-150 and APDAP-150 were obtained and analyzed. The formation ofa trimer as well as a hexamer of aluminophosphate, a monomer of PO4 and a nonamer containing two three-membered rings is critical for the start of crystallization of UiO-15. The formation of a hexamer and a pentamer is critical for the start of crystallization of APDAP12-150. The formation of an A106 monomer and a pentamer containing a three-membered ring is critical for the start of crystallization ofAPDAP-150. The crystal water played a co-structure-directing role in the formation ofAPDAP-150.

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,=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,=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.

Removal of Low-concentration Ammonia from Ambient Air by Aluminophosphates

A series of aluminumphosphate materials was prepared and used as adsorbents for the removal of ammonia at low concentrations. The influence of various preparation parameters, including the pH value of sol, calcination temperature and molar ratio of P/A1, on the structure and surface properties as well as adsorption capacity was investigated. The results showed that large amount of P-OH present on the surface of aluminophosphates was suitable for the removal of ammonia. They were the major source of weak Br6nsted acid sites and acted as the main active centers for capturing ammonia.

Synthesis of Mesoporous Chromium Aluminophosphate (CrAlPO) via Solid State Reaction at Low Temperature

Mesoporous chromium aluminophosphate （CrAIPO） was successfully synthesized via solid state reaction （SSR） route at low temperature in the presence of a cationic surfactant cetyltrimethyl ammonium bromide （CTAB） and inorganic sources such as A1C13 · 6H20, CrCI3 · 6H20 and NaH2PO4 · 2H20. Characterizations by means of powder X-ray diffraction （XRD）, N2 adsorption- desorption, high resolution transmission electron microscopy （HR-TEM）, scanning electron micrography （SEM）, energy dispersion spectroscopy （EDS）, thermo-gravimetry （TG）, Fourier transform infrared spectroscopy （FT-IR）, and ultraviolet visible light spectroscopy （UV-Vis） were carried out to understand both the pore characteristics and electron transition route of these obtained materials. The experimental results show that the meso-CrA1PO materials with various Cr/A1 molar ratios possess a mesostructure and a specific surface area of 193 to 310 m2/g corresponding to an average pore size of 5.5 to 2.2 rim, respectively. The maxium content of Cr in meso-CrA1PO materials synthesized via SSR route can achieve 16.7wt%, being significantly higher than that of the meso-CrA1PO prepared via a conventional sol-gel route. Meanwhile, the formation mechanism of the meso-CrA1PO was also proposed.

非晶态介孔FeAlP催化剂用于合成1,5-苯二氮类化合物(英文)

A simple and versatile method for the synthesis of 1,5-benzodiazepines from o-phenylenediamine and ketones in the presence of solvents and under solvent-free conditions that used an amorphous mesoporous iron aluminophosphate as catalyst was developed.High yields with excellent selectivity were obtained with a wide variety of ketones under mild reaction conditions.The catalyst had the advantages of ease of preparation,ease of handling,simple recovery,reusability,non toxicity,and being inexpensive.

非晶态金属-磷酸铝催化正庚醛和苯甲醛羟醛缩合制茉莉醛(英文)

Amorphous aluminophosphate(AlP) and metal-aluminophosphates(MAlPs, where M = 2.5 mol%Cu, Zn, Cr, Fe, Ce, or Zr) were prepared by coprecipitation method. Their surface properties and catalytic activity for the synthesis of jasminaldehyde through the aldol condensation of nheptanal and benzaldehyde were investigated. The nitrogen adsorption-desorption isotherms showed that the microporosity exhibited by the aluminophosphate was changed to a mesoporous and macroporous structure which depended on the metal incorporated, with a concomitant change in the surface area. Temperature-programmed desorption of NHand COrevealed that the materials possessed both acidic and basic sites. The acidic strength of the material was either increased or decreased depending on the nature of the metal. The basicity was increased compared to AlP. All the materials were X-ray amorphous and powder X-ray diffraction studies indicated the absence of metal oxide phases. The Fourier transform infrared analysis confirmed the presence of phosphate groups and also the absence of any M-O moieties in the materials. The selected organic reaction occurred only in the presence of the AlP and MAlPs. The selectivity for the jasminaldehyde product was up to 75% with a yield of 65%. The best conversion of nheptanal with a high selectivity to jasminaldehyde was obtained with FeAlP as the catalyst, and this material was characterized to have less weak acid sites and more basic sites.

Effect of Various Alkaline Oxides on Broadband Near-infrared Luminescence from Bismuth-Doped Muminophosphate Glasses

We reported effect of various alkaline oxides on the broadband infrared luminescence from bismuth-doped aluminophosphate glasses. The samples of （99-x）P2O3-17Al2O3-xR2O-IBi2O3 （R=Li, Na and K, x=0 and 10 in mol%） were prepared under reducing condition controlled by additional carbon powders. The fluorescent intensity decreased with increasing content of alkaline oxides and basicity of host glasses. The 1/e fluorescence lifetime of the 72P2O3-17Al2O3-10R2O-1Bi2O3 （R=Li, Na and K） glasses decreased from 461 to 316 μs, as alkaline ions changed from Li^＋ to K^＋.

Synthesis of a Chain Aluminophosphate Containing Racemic 1, 2-Diaminopropane

A one-dimensional chain aluminophosphate C1.5H7.5N1.5Al0.5PO4 containing diprotonated racemic 1, 2-diaminopropane cations was synthesized from an alcoholic system. The compound consists of infinite inorganic [AlP2O8] chains of alternately connected AlO4 and PO2(=O)2 tetrahedral units and the racemic template molecules. The macroanionic chains contain corner-shared double four-membered rings.

The Syntheses of 1-Dimensional(1-D)Chain,2-D Layered,and 3-D Microporous Alumino-phosphates with Occluded Amine or Ammonium Templates from Alcoholic Systems

The present paper covers the syntheses of 1 D chain, 2 D layered and 3 D microporous aluminophosphates containing organic amines or ammonium in the presence of various amines from alcoholic systems. The rule for the crystallization of the above three families of microporous aluminophosphates was summarized and the effects of organic amine, P/Al ratio, sources of aluminum and phosphorous and temperature on the resulted structures were investigated.

Synthesis and Characterization of the Large Pore Molecular Sieves VPI-5 and Si-VPI-5

The large pore molecular sieves VPI-5 and Si VPI-5 were synthesized by using three organic amines (dipropylamine, diisopropylamine and dipentylamine) as the structure-directing agents. Compared with general alumlnophosphate molecular sieves, the synthesis of the molecular sieves of VPI-5 type ls of many unique features. Both VPI-5 and Si-VPI-5 were characterized by XRD, IR, TG-DTA, and MAS-NMR.

Uncovering the Phase Transition of Berlinite (α-AlPO_(4)) under High Pressure:Insights from First-principles Calculations

We investigated the mechanism of crystalline-to-amorphous phase transition(CAPT)for amorphous berlinite(a-AlPO_(4))under high pressure using ab initio constant-pressure techniques.Our results show that the pressure to the change in phase transition takes place at around 20 GPa,which is inconsistent with the previous results of around 15 GPa.To confirm the feasibility of our model,the calculated X-ray powder diffraction for crystal berlinite is concordant with the standard PDF card.By assessing a full spectrum of properties including atomic structure,bonding characteristics,electron density of states and real-space pair distribution function at each pressure,we reveal the details of phase transition.Importantly,all the information from our present results elucidates that Al-O bonds play an irreplaceable role during the process of phase transition to uncover the structural and electronic properties of berlinite.Overall,our work substantiates that it is essential to utilize a wide range of changes in order to provide a comprehensive understanding on the nature of the CAPT in other inorganic oxides.

Computational investigation into the phase transitions from AlPO_(4)-H_(3)

Molecular dynamics simulation approach has been used to investigate the phase transitions from aluminophosphate AlPO4-H3. Derived from AlPO4-H3, several hypothetical models of its high-temperature phases are designed through removing the bridged water molecules and changing the up-down connected sequences of T-sites in the 4-membered rings. Full geometry optimizations are performed to obtain structural parameters for the models that are compared to the reported data, and their structure features and thermodynamic stabilities have been discussed. The simulation study suggests that AIPO4-H3 is energetically favored to transform to AIPO4-C, and then to AIPO4-D as well as to other novel hypothetical 3D open-frameworks.

Database of open-framework aluminophosphate syntheses:introduction and application(Ⅰ)

The database of open-framework aluminophosphate(AlPO) syntheses has been established,which includes about 1600 synthetic records.Data analysis has been done on the basis of the framework composition,structure dimension,pore ring,and organic template.This database will serve as useful guidance for the rational synthesis of microporous functional materials.

Synthesis of bifunctional Pt/MgAPO-5 catalysts and their catalytic performance in the hydrogenation of nitrobenzene to p-aminophenol

MgAPO-5 molecular sieves have been synthesized using diethylaminoethanol as the templating agent in a wide range of the MgO/Al2O3 ratio.The samples were characterized by XRD,SEM,solid state NMR,FT-IR and NH3-TPD.Using MgAPO-5 as acidic supports,bifunctional Pt/MgAPO-5 catalysts were prepared for hydrogenation of nitrobenzene to p-aminophenol (PAP).The results showed that the MgO/Al2O3 ratios influenced the Mg content and the acidity of MgAPO-5 samples,thereby greatly affecting the catalytic performance of Pt/MgAPO-5 catalysts.The selectivity to PAP over Pt/MgAPO-5 was dependent on the amount of strong acid sites of MgAPO-5.When the MgO/Al2O3 molar ratio was 0.5,the synthesized MgAPO-5 sample exhibited the largest amount of strong acid and a highest PAP yield of 41.1% was achieved over Pt/MgAPO-5 catalyst.

Immobilization of simulated radioactive fluoride waste in phosphate glass

Radioactive alkali fluoride salts are generated during the operation of molten salt reactors(MSRs) and reprocessing of their spent fuel, and appear in the formof fluidity granule, or powder. In order to prevent the radionuclides from being released into the environment(especially, via exposure to water), it is necessary to develop a new technology for the temporary storage or final disposal of wastes containing radioactive fluorides. The immobilization of alkali fluoride wastes in phosphate glasses has been proposed. In this study, iron phosphate(IP) glasses and sodium aluminophosphate(NaAlP) glasses were evaluated for the immobilization of simulated radioactive fluoride wastes. IP and NaAlP glass matrixes were mixed with simulated wastes and reacted in air at temperatures in the range of 950–1200°C. A high waste loading was obtained in the experiment. The properties of the waste forms were characterized by X-ray diffraction and Raman spectroscopy. The latter indicated that IP glass contains less Q^2 without Q^3(2 and 3 represent the number of bridging oxygens on a PO_4 tetrahedron), and it is concluded that IP glass is more stable than NaAlP glass. Leaching tests were performed in deionized water by using the product consistency test A(PCT-A method), and the result shows that the leaching resistance of IP waste forms is better than that of NaAlP waste forms. This study demonstrates the potential of IP glass for the stabilization and immobilization of radioactive fluoride wastes from MSRs.

[Cu(en)_2]_(0.5)[Al_3P_3O_(12)(OH)]-aluminophosphate with zeotype AWO:Synthesis,crystal structure and phase transformation

A new aluminophosphate [Cu(en)2]0.5[Al3P3O12(OH)] (denoted as AlPO-CJ53; en = ethylenediamine) with zeotype AWO topology has been synthesized under hydrothermal conditions in which the self-assembled Cu(en)22+ cations in the reaction system act as the template. AlPO-CJ53 crystallizes in the monoclinic space group P21/n (No. 14) with a = 0.85547(11) nm, b = 1.7671(2) nm, c = 0.90500(12) nm, β= 107.725(2)°, V = 1.3031(3) nm3. Its framework consists of AlO4(OH)/AlO4 and PO4 units forming 8-ring channels along the c direction, where the copper complex cations Cu(en)22+ are located to neutralize the negative charges of the framework. AlPO-CJ53 transforms to AlPO4-25 with zeotype ATV upon calcination at 400 °C.

Synthesis of Zn-containing Aluminophosphate with ERI Topology

A Zn-containing aluminophosphate with ERI-zeotype structure was hydrothermally synthsized with 1,2-diaminocyclohexane（DACH） as the template. The result of the structural analysis indicates that the Zn-containing aluminosphate crystallized in the hexagonal space group of P63/m was constituted up by the alternating AI（Zn）O4 and PO4 tetrahedra. The organic amine DACH located in the ERI cages was used to balance the negative charge of the framework.