Citation:
Wei Chengqian, Zheng Xiangmiao, Yin Weizheng, Liu Zhenyi, Wang Dingyi, Zang Wanjing*, Lin Bihgxiong. STRUCTURAL AND ACIDIC STUDIES ON SAPO-5 MOLECULAR SIEVES[J]. Acta Physico-Chimica Sinica,
;1988, 4(05): 516-522.
doi:
10.3866/PKU.WHXB19880515
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The non-proportion substitutive SAPO-5 and the selective substitutive SAPO-5 were synthesized by taking triethylamine as the template under certain experimental conditions. They result from substituting Si for P, Al in non-proportion and partly replacing of P with Si in the framework of APO-5 respectively. The compositions are as follows:
H_(y-x) (Al_(12-x)Si_x) (P_(12-y)Si_y) O_(48)·zH_2O y-x=0.5~2.01 y+x=1.3~3.09 H_xAl_(12)(P_(12_x)Si_x) O_(48)·zH_2O x=0.7~2.66
The charge in framework and the acidity enhances considerably with the difference between P and Al in the framework. The area of NH_3-TPD of the sample of the difference 1.86 is 7.4 times as that of APO-5.
The crystal structures of two SAPO-5 containing Na~+ were determineted by powder X-ray diffraction at 400 ℃. Then the structure parameters were refined by Rietveld method. The unit cells of the two SAPO-5 contain Na_(y-x) (Al_(12-x)Si_x) and (P_(12-y)Si_y)O_(48) and Na_xAl_(12) (P_(12-x)Si_y)O_(48), respectively. The constructions of their framework are quite similar to APO-5. The space group is C_(6v)~2-P6cc. The lattice parameters: a=b=1.3761(5) nm, c=0.8402(3) nm; a=b=1.3805(7) nm, c=0.8428(4) nm respectively. The “ odness of fit” is shown in Table 1. The average bod lengths of P(Si)-O, Al(Si)-O are 1.494A, 1.695A respectively and their difference equals 0.196A for the non-proportional substitutive SAPO-5. The average bond lengths of P(Si)-O, Al-O are 1.504A, 1.702A respectively and their difference equals 0.198A for the selective substitutive SAPO-5. Both of the differences are much larger than that of the disordered APO-5 and the proportional substitutiue sAPO-5. It is concluded that the ordered degree of P and Al is fairly hight in the two frameworks of SAPO-5.
There is a 12-ring straight channel ca. 0.8 nm in diameter and Na~+ are located at center of the hexa nal prism in the framework. The Brönsted center or activative center in SAPO-5 and the unique disabsorption peak of NH_3 appears in TPD spectra. -
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