A Novel Open‐Framework Copper Borovanadate with Enhanced Catalytic Performance for Oxidation of Benzylic C−H Bond

Abstract

A novel open-framework copper borovanadate, with a 6-connected topological net and 1D 8-membered ring channels, has been obtained for the first time. The compound not only exhibits a unique -B O (OH)-Cu-B(OH) linkage and features the largest ratio between TM (Cu ) and the borovanadate anion, but also possesses enhanced catalytic performance, high recyclability, and stability during the oxidation of benzylic C-H bonds.

A highly efficient heterogeneous catalyst for selective oxidation of sulfides derived from an open-framework copper borovanadate containing a unique crown-shaped anion

“…5b. 3 The above binding energies are in good agreement with those in previously reported related complexes containing V 4+ /V 5+ and Cu 2+ . In addition, the detected binding energies of 191.5 eV, 530.6 eV, 399.8 eV and 285.8 eV corresponded to the B 1s , O 1s , N 1s and C 1s regions, respectively (Fig.…”

“…Borovanadates have attracted extensive attention due to their abundant structural features and broad application prospects in the fields of catalysis, magnetism, adsorption, ion exchange and optics. 1–3 The flexible polyhedra of B φ x ( x = 3/4, φ = O/OH), VO y ( y = 5/6) and MO n ( n = 4–6) provide important structural units for the formation of metal borovanadates with new architectures. 4 Generally, vanadium always exhibits two oxidation states V 4+ /V 5+ in metal borovanadates, which also makes borovanadates exhibit significant catalytic activities.…”

“…4 Generally, vanadium always exhibits two oxidation states V 4+ /V 5+ in metal borovanadates, which also makes borovanadates exhibit significant catalytic activities. Recently, a series of borovanadates, typical examples of which are SUT-6-Zn, 2 [Cu(en) 2 ] 4 {Na(H 2 O)(μ-OH)[B(OH) 2 ]} 2 [(V V O) 2 (V IV O) 10 O 6 (B 18 O 36 (OH) 6 )]·7H 2 O (NNU-6) 5 and {[Cu(en) 2 ] 3 [Cu(en) 2 B(OH) 3 ] 2 [(V V O) 2 (V IV O) 10 O 6 (B 18 O 36 (OH) 6 )(H 2 O)]·13H 2 O, 3 exhibited attractive catalytic activities for the selective oxidation of the benzylic α-C–H bond. The cCadmium borovanadate [Cd II 3 (H 2 O) 6 ][(V IV O) 6 (V V O) 6 O 6 (B 18 O 36 (OH) 6 )]·10H 2 O (NNU-5) 6 showed excellent catalytic properties for the oxidation of cyclohexanol.…”

“…Meanwhile, the second TM n+ cations and the solvent molecular channels presented in the 3D open-framework structures will be more conducive to enhance catalytic activities. 2,3,5,6 Therefore, it is still a challenging and meaningful work to explore novel open-framework borovanadates with second TM n+ cations and improved catalytic properties.…”

“…4 In addition, the peaks at 489 and 450 cm −1 can be ascribed to the Cu-N and Cu-O bonds. 3 The thermal stability of 1 was studied in the range of 30-800 °C with a heating rate of 10 °C min −1 under a dynamic N 2 atmosphere with a gas flow of 0.02 L min −1 (Fig. S5 †).…”