物理化学学报 >> 1989, Vol. 5 >> Issue (05): 558-564.doi: 10.3866/PKU.WHXB19890510

研究论文 上一篇    下一篇

Y沸石中的正电子湮没

高滋; 杨雪敏; 潘思忠; 高本祥; 戚盛勇; 王煜   

  1. 复旦大学化学系; 复旦大学物理系
  • 收稿日期:1988-01-25 修回日期:1988-09-20 发布日期:1989-10-15
  • 通讯作者: 高滋

POSITRON ANNIHILATION IN ZEOLITE Y

Gao Zi*; Yang Xuemin; Pan Sizhong; Gao Benxiang; Qi Shengyong; Wang Yu   

  1. Department of Chemistry; Fndan University; Department of Physics; Fudan University
  • Received:1988-01-25 Revised:1988-09-20 Published:1989-10-15
  • Contact: Gao Zi

摘要:

本文测量了NaY、HY和NH_4Y在不同抽空温度下的正电子寿命谱, 得到了四个寿命组份, 并对它们的归属进行了讨论。其中两个长寿命组份τ_s和τ_4归结为沸石内表面和笼内o-Ps的湮没。o-Ps容易被沸石内的质子酸氧化, 而使其湮没寿命τ_3和τ_4缩短。利用正电子寿命谱可以监测NH_4Y沸石的脱氨过程。质子酸的存在对o-Ps的形成并无影响, 但随着质子酸浓度增加, o-Ps在沸石内表面湮没的几率大于笼内, 故I_3大于I_4。o-Ps的在沸石内表面和笼内的湮没速率与质子酸浓度成线性关系, 以一级反应动力学处理得到的o-Ps在沸石内表面和笼内的氧化反应表观速率常数分别为9.67×10~7(mmol/g)_~(-1)s~(-1)和2.36×10~7(mmol/g)~(-1)s~(-1)。

Abstract:

Positron annihilation lifetime measurements were carried out under different evacuation temperatures for zeolite NaY, HY and NH_4Y. Four lifetime components have been observed in these systems. The two shorter ones, τ_1 and τ_2, were assigned to positron annihilation in the bulk, self-annihilation of ρ-Ps, pick-off annihilation of ο-Ps in the bulk and annihilation of positron trapped in the cages. The two longer ones, τ_3 and τ_4, were assigned to annihilation of ο-Ps on the surface and in the cages of the zeolites respectively. The Brönsted acid in the zeolites oxidized o-Ps readily, so that the o-Ps lifetime τ_3 and τ_4 were reduced significantly in zeolite HY. The deammoniation of NH_4Y at higher evacuation temperatures can be monitored through measurements of o-Ps lifetimes. Brönsted acid in the zeolites does not inhibit the formation of o-Ps. However, o-Ps annihilates more readily on the surface as the concentration of Brönsted acid is increased, and hence the value of I_3 much largerthan I_4 in HY. The o-Ps annililation rates on the surface and in the cages, λ_3 and λ_4, are linearly proportional to the concentration of of Brönsted acid in the zeolites. First-order kinetics has been applied to the oxidation reactions of o-Ps and apparent rate constants k_3 and k_4, are 9.67×10~7 (mmol/g)s~(-1) and 2.36×10~7 (mmol/g)~(-1) s~(-1) respectively. The experimental results obtained demonstrate that positron annihilation spectroscopy is a sensitive technique to probe thesurface properties and pore structure of porous materials