Methane exists in massive quantity on the Earth, and considerable efforts have been made to develop effective methods to convert chemically inert methane into value-added products. Recently, cobalt-exchanged ZSM-5 zeolite has been found to be a competent catalyst for non-oxidative methylation of benzene using methane as a methylation agent. Herein, cobalt-exchanged ZSM-11 zeolite, with close topological structure to that of ZSM-5 zeolite, was discovered to be capable of catalyzing non-oxidative methylation of benzene with methane for the first time. ZSM-5 and ZSM-11 zeolites both with Si/Al molar ratio of ca. 36 and 18 were synthesized. However, higher cobalt loadings were obtained on ZSM-11 zeolites, and cobalt-exchanged ZSM-11 catalysts displayed superior toluene production rates and turnover frequencies. In addition, low silica zeolite catalysts possessed higher methylation selectivity. Diffuse reflectance visible–near infrared spectra revealed that divalent cobalt cations on the ion exchange sites existed mainly in two different coordination states, and the cobalt cation on the α site, coordinating weakly to the framework oxygen atoms, was supposed to be the active site because of the positive correlation of its concentration and the methane activation performance. Since more α-type Co²⁺ could be created in ZSM-11 zeolites than in ZSM-5 zeolites with the same Si/Al molar ratio, it was concluded that cobalt-exchanged ZSM-11 catalyst was a promising candidate for the non-oxidative methylation of benzene with methane.

甲烷在地球上大量存在，并且已经做出了巨大的努力来开发有效的方法，以将化学惰性的甲烷转化为增值产品。近来，已发现钴交换的ZSM-5沸石是使用甲烷作为甲基化剂的苯的非氧化甲基化的有效催化剂。在此，发现与ZSM-5沸石具有紧密拓扑结构的钴交换的ZSM-11沸石能够首次催化苯与甲烷的非氧化甲基化。ZSM-5和ZSM-11沸石两者都具有的Si / Al摩尔比约合成了36和18。然而，在ZSM-11沸石上获得了更高的钴负载量，并且钴交换的ZSM-11催化剂显示出更高的甲苯生产率和周转频率。另外，低硅沸石催化剂具有较高的甲基化选择性。可见光-近红外光谱的漫反射表明，离子交换位点上的二价钴阳离子主要以两种不同的配位态存在，而α位上的弱阳离子与骨架氧原子配位的钴阳离子被认为是活性位点，因为浓度与甲烷活化性能的正相关关系。由于更多的α型Co ²⁺ 在相同的Si / Al摩尔比的情况下，ZSM-11沸石比ZSM-5沸石可以生成更多的苯，因此得出结论，钴交换的ZSM-11催化剂是苯与甲烷的非氧化甲基化的有前途的候选者。