| It is very important to study synthesis, characterization, intercalation and catalysis of zirconium phosphonates and hybrid zirconium phosphates for host-guest supermolecule chemistry, property, preparation, application and development of multifunctional materials.In this paper, 10 kinds ofα-aminomethylphosphonic acid derivitives were synthesized by the Mannich-type reaction. The property and structure ofα-aminomethylphosphonic acid derivitives were characterized and discussed by elemental analysis, Fourier Transform Infrared Transmission-absorption Spectra (FTIR), Nuclear Magnetic Resonance (1H NMR and 31P NMR) in detail.12 kinds of layered zirconium dimethylphosphonates and aniline intercalation compounds were synthesized and characterized by elemental analysis, Inductive Coupled Plasma Emission Spectrum (ICP), X-ray Powder Diffraction (XRD), FTIR, Laser Raman Spectra (Raman Spectra), Scanning Electron Microscope (SEM), Thermogravimetry and Differential Scanning Calorimetry (TG-DSC). The results demonstrated that the compositions of zirconium phosphonates were Zr(O3PCH2)2N(CH2)nCH3·xH2O (n=0, 1, 2, 3, 6, 9) with the interlayer distances of 1.046 nm to 1.962 nm, two dimethylphosphonates might bind to the same layer. The compositions of aniline intercalation compounds were Zr(O3PCH2)2N(CH2)nCH3·xC6H5NH2·yH2O with the interlayer distances of 1.097 nm to 2.526 nm, and anilines arranged as monomolecular layers in the gallery of these hosts. The polymerization of aniline showed that polyaniline was not inserted between the layers of host, but diffused in the particles of host.2 kinds of layered crystalline and amorphous zirconium proline-N-methylphosphonate-phosphates (α-ZLPMPAx=1 and ZLPMPAx=1) were synthesized and characterized by the above methods, the results indicated that the composition ofα-ZLPMPAx=1 was Zr(O3PG)(HPO4)·H2O with the interlayer distance of 1.520 nm, the N-methylproline groups and P-OH arranged alternatively. The intercalations of butylamine (BA), heptylamine (HA), decylamine (DA), arginine (Arg), lysine (Lys) and histidine (His) withα-ZLPMPAx=1 host had been studied by shaking, refluencing and microwave irradiation, 0.43 BA, 0.34 HA, 0.33 DA, 0.20 Arg, 0.54 Lys and 0.39 His inserted into in the gallery of one moleculeα-ZLPMPAx=1 host, respectively. The intercalation compoundsα-ZLPMPAx=1-BA,α-ZLPMPAx=1-HA andα-ZLPMPAx=1-DA had successfully adsorbed phenol, 4-chlorophenol and 2,4-dichlorophenol.4 kinds of layered crystalline and amorphous zirconium glycine-N,N-dimethylphosphonate-phosphate (α-ZGMDPAx=0.66,α-ZGMDPAx=2, ZGMDPAx=0.66 and ZGMDPAx=2) had been prepared and characterized by the above methods. The compositions ofα-ZGMDPAx=0.66 andα-ZGMDPAx=2 were Zr[(O3PCH2)2NCH2COOH]0.33 (HPO4)1.34·0.70 H2O and Zr[(O3PCH2)2NCH2COOH]·H2O, the interlayer distances of them were 1.542 nm and 1.271 nm, respectively. It was found that the intercalations of alkylmonoamines (methylamine (MA), ethylamine (EA), propylamine (PA), BA, HA, DA), polyamines (ethylenediamine (1E2A), diethylenetriamine (2E3A), triethylenetetramine (3E4A), tetrathylenepentamine (4E5A), 1,3-propyldiamine (PDA)), hexahydropyridine (HHP) withα-ZGMDPAx=0.66 andα-ZGMDPAx=2 hosts, alkylmonoamines and heterocyclic compounds arranged as bimolecular layers in the gallery ofα-ZGMDPAx=0.66, polyamines formed multi-array in the gallery ofα-ZGMDPAx=0.66 andα-ZGMDPAx=2.The solid bases with H-=9.3 to 15.0 were prepared by the amorphous supports ZLPMPAx=1, ZGMDPAx=0.66 and ZGMDPAx=2. The Knoevenagel condensations of aromatic aldehydes with active methylene compounds were catalyzed by the solid base in yield of 76.4 % to 91.1 % under microwave irradiation and solvent-free, or heating, the solid base could be reused four times. The solid base is a new type of environmentally benign catalyst. On the meanwhile the palldium complex supported on ZGMDPAx=0.66 exhibited a yield of 81.4 % for Suzuki cross-coupling reaction.6 kinds of layered crystalline and amorphous zirconium benzyl-N,N-dimethylphosphonate-phosphates (α-ZBMDPA, ZBMDPA) were also prepared and characterized by the above methods. The composition ofα-ZBMDPAx=1.0 with the interlayer distance of 2.034 nm was Zr(HPO4)(C6H5CH2N(CH2PO3)2)0.5?2.1 H2O, and two phenyl ofα-ZBMDPAx=1.0 double layers faced to face each other. Alkylmonoamines (MA, dimethylamine (DMA), trimethylamine (TMA), EA, diethylamine (DEA), triethylamine (TEA), PA, BA, dibutylamine (DBA), tributylamine (TBA), HA, DA), polyamines (1E2A, 2E3A, 3E4A, 4E5A, PDA), heterocyclic compounds (pyrrolidine (TPR), HHP, morpholine (ML), piperazine(PH)) had successfully inserted into the gallery ofα-ZBMDPAx=1 host, alkylmonoamines and heterocyclic compounds arranged as monomolecular layers in the gallery ofα-ZBMDPAx=1, polyamines also formed multi-array in the gallery of.α-ZBMDPAx=1. The intercalation compoundsα-ZBMDPAx=1-BA,α-ZBMDPAx=1-HA andα-ZBMDPAx=1-DA adsorbed phenol, 4-chlorophenol and 2,4-dichlorophenol,α-ZBMDPAx=1-3E4A andα-ZBMDPAx=1-4E5A adsorbed formaldehyde.Series of pallidum complexes were prepared by introducing the ligand polyamines (1E2A, 2E3A, 3E4A and 4E5A) into the support ZBMDPA. These pallidum complexes supported on ZBMDPA polyamines were characterized by FTIR, Atomic Absorption Spectra (AAS), X-ray Photoelectron Spectra (XPS) and XRD. The pallidum complexes catalyzed Suzuki cross-coupling reaction of aryl halides with aryl boronic acids, compared with aryl bromides and aryl chloride, aryl iodide obtained better yield (92.1%), the catalyst could be easily recovered and reused more than five times.In addition, the intercalations of His, Arg, Lys withα-Zr(HPO4)2·H2O (α-ZrP) had been studied under microwave irradiation, ultrasound and refluencing, these amino acids arranged as monomolecular layers, 0.50 His, 0.13 Arg and 0.84 Lys inserted into the gallery of one moleculeα-ZrP, respectively. The intercalation compoundα-ZrP-His catalyzed Aldol reaction of acetone with 4-nitrobenzaldehyde in proper yield and could be reused. It is necessary to researchα-ZrP-His as multiphase catalysis materials.
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