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氮气吸附等温线分析PFSA/SiO2复合催化剂孔结构 被引量:5
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作者 袁海宽 马晓华 许振良 《中国科学:化学》 CAS CSCD 北大核心 2011年第6期1094-1094,共1页
采用溶胶-凝胶法制备了全氟磺酸/二氧化硅(PFSA/SiO2)复合催化剂.调整PFSA与TEOS的配比,可制得不同PFSA负载量的复合催化剂.将PFSA含量分别为5%,13%,20%和40%的催化剂记为PFSA-5,PFSA-13,PFSA-20和PFSA-40.四种催化剂的等温线均属于Ⅳ... 采用溶胶-凝胶法制备了全氟磺酸/二氧化硅(PFSA/SiO2)复合催化剂.调整PFSA与TEOS的配比,可制得不同PFSA负载量的复合催化剂.将PFSA含量分别为5%,13%,20%和40%的催化剂记为PFSA-5,PFSA-13,PFSA-20和PFSA-40.四种催化剂的等温线均属于Ⅳ型等温线,PFSA-5,PFSA-13和PFSA-20催化剂属H1型滞后环,而PFSA-40催化剂属H2型滞后环.采用BET法确定比表面积,BJH法计算孔径分布.结果显示,在PFSA/SiO2催化剂内形成了较为发达的圆柱状中孔,且分布较为均一.随着催化剂内PFSA负载量的增大,表面积和孔容逐渐减小.PFSA-40催化剂的表面积和孔容急剧降低,主要是由于过多的PFSA负载量使SiO2孔网络的连续性受到破坏,或部分孔道被堵塞所造成的.总的来说,高度分散和多孔的结构使催化剂的比表面积增大,提高了活性中心的可接近程度,同时也降低催化剂的成本.中孔材料的吸附脱附等温线中存在吸附滞后,滞后环的形状反映了孔结构类型.PFSA-5,PFSA-13和PFSA-20催化剂的吸附滞后环属于H1型,一般由大小均一且形状规则的孔造成.而PFSA-40催化剂的滞后环变成了H2型,催化剂内形成具有瓶颈状的圆柱状孔,且分布不均一.采用对比曲线法(t曲线)可修正由BJH方法得到的PFSA/SiO2催化剂的孔径分布.PFSA-5,PFSA-13和PFSA-20催化剂的t曲线有三个阶段构成,分别命名为Stage A,StageB,Stage C.Stage A,孔壁内N2多层吸附;StageC,N2外表面吸附;StageB中,PFSA-5,PFSA-13和PFSA-20催化剂的t曲线非常陡,表明孔内毛细管凝聚的发生,同时也预示中孔结构形成.PFSA-40催化剂的t曲线StageB的水平偏离表明其内有微孔存在,即PFSA-40催化剂内部并不是分布均一的中孔,这与氮气吸附滞后的分析结果相一致.另外,t曲线的微分形状与多孔材料的孔径分布非常相似,能定性反映PFSA/SiO2催化剂的孔径分布.PFSA-5,PFSA-13和PFSA-20催化剂的微分曲线在t=0.6~1.0nm存在较为尖锐的峰,意味着均一孔结构的形成.PFSA-40催化剂的微分曲线上所形成的峰并不明显,表明PFSA-40催化剂具有较宽的孔径分布,与吸附滞后的分析结果一致.因此,使用t曲线及其微分曲线来分析PFSA/SiO2催化剂的孔径分布是对BJH法很好的补充. 展开更多
关键词 孔结构 pfsa/sio2复合催化剂 吸附-脱附等温线 吸附滞后 t曲线
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Pore structure analysis of PFSA/SiO_2 composite catalysts from nitrogen adsorption isotherms 被引量:7
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作者 YUAN HaiKuan MA XiaoHua XU ZhenLiang 《Science China Chemistry》 SCIE EI CAS 2011年第1期257-262,共6页
The perfluorosulfonic acid (PFSA)/SiO2 composite catalysts were prepared by sol-gel method. Differences concerning pore structure analysis of PFSA/SiO2 catalysts were discussed on the basis of nitrogen adsorption. T... The perfluorosulfonic acid (PFSA)/SiO2 composite catalysts were prepared by sol-gel method. Differences concerning pore structure analysis of PFSA/SiO2 catalysts were discussed on the basis of nitrogen adsorption. Their surface area and pore size distributions were evaluated by Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) methods, respectively. The nitrogen adsorption-desorption isotherms associated with adsorption hysteresis of PFSA/SiO2 catalysts were analyzed in detail. The adsorption isotherms of PFSA/SiOe catalysts belonged to Type IV isotherms accompanied by hysteresis loops of Type H1 for PFSA/SiO2 catalysts with content of 5%, 13% and 20% PFSA (PFSA-5, PFSA-13 and PFSA-20), and the hysteresis loop of Type H2 for PFSA/SiO2 catalyst with 40% PFSA content (PFSA-40). It indicated that PFSA-5, PFSA-13 and PFSA-20 catalysts had narrow pore size distributions and the well-defined cylindrical pores, while PFSA-40 catalyst had wide pore size distribution and inkbottle-like pores. The pore structure of PFSA-40 catalyst from the analysis of the hysteresis loop was not in agreement with that from BJH method. As an emendation for evaluation of pore size distributions of PFSA/SiOz catalysts, the comparison plots method was introduced, which was helpful to evaluate the pore structure of PFSA/SiO2 catalysts more factually. 展开更多
关键词 pore structure pfsa/sio2 composite catalysts adsorption-desorption isotherms adsorption hysteresis t-plot
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