The microporous material Cu-BTC (1,3,5-benzenetricarboxylic acid, BTC) is a prototype metal-organic framework (MOF). In situ combination of Cu-BTC and macro-/mesoporous silica monoliths lead to an efficient catalyst for selective oxidation. The catalytic activities for the oxidation of alkylbenzenes were examined using tert-butyl hydroperoxide as the oxidant, showing that low-cost macro-/mesoporous silica supported Cu-BTC is a highly efficentive and reusable heterogeneous catalyst for the selective oxidation from alkylbenzenes to ketones with moderate to excellent yields.Metal-organic frameworks (MOFs) are a class of crystalline materials having innite network structures built with multitopic organic ligands and metal ions. 1 The highly porous and extremely ordered materials can be used for a variety of applications ranging from gas storage over catalysis and sensing to drug release. 1-8 In particular, porous MOFs are ideally suited for heterogeneous asymmetric catalyses because they impose sizeand shape-selective restrictions through readily ne-tuned channels and pores and high enantioselectivity. 9 Actually, the great potential of MOFs in heterogeneous catalysis demonstrated by Kim and Lin promoted the design, synthesis, and catalytic properties of many MOFs during the past decades. 8,9 However, more progress has been hampered due to the lower chemical and mechanical stability of MOFs. To overcome this issue, immobilizing MOFs onto supports is very important for catalysis and also for other applications. 10 As a prototype MOF, [Cu 3 (BTC) 2 ] (Cu-BTC, BTC ¼ 1,3,5-benzenetricarboxylate) (named also HKUST-1 or MOF-199) has coordinatively unsaturated Cu 2+ sites, which induce attractive catalytic properties for reactions catalyzed by Lewis acids, such as Diels-Alder reactions, 11 esterication, 12 isomerisation of a-pinene oxide 13 and Friedländer reaction. 14 Recently, a well column-packing silica monolith-supported Cu-BTC catalyst was prepared and successfully applied in Friedländer reaction under continuous ow, 15 which inspired us to utilize such novel catalyst in selective oxidations. Meantime, Wu et al. reported a porous metalloporphyrinic framework containing manganese ions, 16 namely ZJU-18, with a 3-periodic, binodal, edge-transitive net of the same tbo topology 17 and larger pore sizes comparing with those in Cu-BTC. ZJU-18 showed highly efficient for the selective catalytic oxidation of alkylbenzenes, but it is hard to be scaled up partly because of the low productivity of ligand 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin. However, selective oxidation of alkylbenzenes is a very important industrial process for the production of aromatic alcohols, aldehydes, ketones, and carboxylic acids, 18 increasing the productivity and decreasing the cost of catalysts are essential for heterogeneous catalysis of such type selective oxidation.Given the fact that stated above, in the present study we studied the benet of combining the catalytic properties of nely divided MOF (Cu-BTC) with macro-/mesoporou...
