UFR Sciences & Techniques, 64053 Pau Cedex 9, France.
Chemphyschem. 2013 Jan 14;14(1):244-51. doi: 10.1002/cphc.201200568. Epub 2012 Sep 23.
A detailed FTIR study of the effects of steaming and acid leaching on protonated Y faujasite (FAU) and EMT zeolites is provided and the results are thoroughly analysed. In particular, emphasis is placed on the Brønsted acidic evolution and acidic strength measurements for a large series of as-modified zeolites using CO as a sensitive probe to distinguish various protonic sites. While an increase of acidity for framework OH groups is observed during the strengthening of dealumination for both FAU and EMT series, the steaming process also generates a large variety of additional Brønsted acidic groups. Regarding acidic strength, these heterogeneous OH groups are sensitive to post-treatments and their existence strongly depends on the initial composition of the zeolites. The presence of residual Na(+) cations in the starting materials induces dramatic Brønsted acidic changes after steaming. As a result, steamed zeolites that initially contain traces of sodium possess unusual acidic Brønsted groups with low acidity. This result contradicts the trend generally observed with framework OH groups, for which steaming results in an increase of Brønsted acidic strength. The study reveals that the situation is indeed more complex, as some compositions and post-treatments strongly influence the Brønsted acidity of as-steamed zeolites both in their nature and their corresponding acidic strength. By linking these IR-compiled features to the as-exposed modifications, a large acidity scale better suited to characterizing catalysts having Brønsted acidity expanding from lowest to highest strength is proposed.
提供了对质子化 Y 型沸石(FAU)和 EMT 沸石在蒸汽处理和酸浸过程中影响的详细傅里叶变换红外光谱(FTIR)研究,并对结果进行了深入分析。特别是,使用 CO 作为敏感探针,强调了一系列经过修饰的沸石的 Brønsted 酸性演变和酸性强度测量,以区分各种质子化位。虽然 FAU 和 EMT 系列脱铝过程中骨架 OH 基团的酸度增加,但蒸汽处理过程也会产生大量额外的 Brønsted 酸性基团。就酸性强度而言,这些非均相 OH 基团对后处理敏感,其存在强烈依赖于沸石的初始组成。起始材料中残留的 Na(+)阳离子在蒸汽处理后会引起显著的 Brønsted 酸性变化。结果,最初含有痕量钠的蒸汽处理沸石具有异常低酸度的独特 Brønsted 酸性基团。这一结果与通常观察到的骨架 OH 基团的趋势相矛盾,因为蒸汽处理会导致 Brønsted 酸性强度增加。研究表明,情况确实更加复杂,因为一些组成和后处理会强烈影响蒸汽处理沸石的 Brønsted 酸性,无论是在其性质还是相应的酸性强度方面。通过将这些 IR 编译的特征与暴露的改性联系起来,提出了一个更大的酸度范围,更适合于表征具有从最低到最高强度扩展的 Brønsted 酸性的催化剂。