†Department of Chemistry, University of California, Riverside, California 92521, United States.
‡Department of Chemistry and Biochemistry, California State University, Long Beach, California 90840, United States.
J Am Chem Soc. 2015 May 20;137(19):6184-7. doi: 10.1021/jacs.5b03550. Epub 2015 May 7.
High-silica zeolites, as exemplified by ZSM-5, with excellent chemical and thermal stability, have generated a revolution in industrial catalysis. In contrast, prior to this work, high-silica-zeolite-like chalcogenides based on germanium/tin remained unknown, even after decades of research. Here six crystalline high-germanium or high-tin zeolite-type sulfides and selenides with four different topologies are reported. Their unprecedented framework compositions give these materials much improved thermal and chemical stability with high surface area (Langmuir surface area of 782 m(2)/g(-1)) comparable to or better than zeolites. Among them, highly stable CPM-120-ZnGeS allows for ion exchange with diverse metal or complex cations, resulting in fine-tuning in porosity, fast ion conductivity, and photoelectric response. Being among the most porous crystalline chalcogenides, CPM-120-ZnGeS (exchanged with Cs(+) ions) also shows reversible adsorption with high capacity and affinity for CO2 (98 and 73 cm(3) g(-1) at 273 and 298 K, respectively, isosteric heat of adsorption = 40.05 kJ mol(-1)). Moreover, CPM-120-ZnGeS could also function as a robust photocatalyst for water reduction to generate H2. The overall activity of H2 production from water, in the presence of Na2S-Na2SO3 as a hole scavenger, was 200 μmol h(-1)/(0.10 g). Such catalytic activity remained undiminished under illumination by UV light for as long as measured (200 h), demonstrating excellent resistance to photocorrosion even under intense UV radiation.
高硅沸石，例如 ZSM-5，具有优异的化学和热稳定性，在工业催化中引发了一场革命。相比之下，在这项工作之前，基于锗/锡的高硅沸石类似的硫属化物尽管经过了几十年的研究，但仍然未知。在这里，我们报道了六种具有四种不同拓扑结构的结晶高锗或高锡沸石型硫化物和硒化物。它们前所未有的骨架组成赋予了这些材料更高的热稳定性和化学稳定性，同时具有高表面积（朗缪尔表面积为 782 m²/g），可与沸石相媲美或优于沸石。其中，高度稳定的 CPM-120-ZnGeS 允许与各种金属或复杂阳离子进行离子交换，从而可以精细调整孔隙率、快速离子电导率和光电响应。作为最具多孔性的结晶硫属化物之一，CPM-120-ZnGeS（与 Cs(+)离子交换）对 CO2 也表现出高容量和高亲和力的可逆吸附（在 273 和 298 K 时分别为 98 和 73 cm³/g，吸附等焓为 40.05 kJ/mol）。此外，CPM-120-ZnGeS 还可以用作水还原的高效光催化剂，用于生成 H2。在 Na2S-Na2SO3 作为空穴清除剂的存在下，水还原生成 H2 的总体活性为 200 μmol h(-1)/(0.10 g)。在长达 200 h 的测量时间内，在紫外光照射下，其催化活性仍然没有降低，即使在强烈的紫外辐射下，也表现出极好的抗光腐蚀性。
