On the basis of the unique chaotropic supramolecular assembly of cucurbit[5]­uril (CB5) and dodecahydro-closo-dodecaborate anion [closo-B12H12]2–, we have developed an efficient and universal platform to fabricate shape-controlled dodecaborate-based supramolecular organic frameworks (BOFs) decorated with ultrafine monodispersed trimetallic alloys. Simply by regulating the molar ratio of CB5 and [closo-B12H12]2–, a series of fascinating morphologies, such as flowerlike structures, nanorods, nanocubes, and nanosheets, were successfully constructed. These obtained BOFs were proved to be good substrate supports for in situ synthesis of trimetallic PtCoNi nanoalloys, where the final PtCoNi–BOFs materials were obtained efficiently as a precipitate from aqueous solutions, and showed excellent catalytic performance in ammonia borane hydrolysis with a high turnover frequency of 1490 molH2 molPt –1 min–1 and a low activation energy of 15.79 kJ mol–1.

The increasing global demands for eco-friendly and low-cost catalysts have propelled the advent of nanosized non-noble-metal catalysts to replace traditional noble metals. In this work, ultrafine NiO nanoparticles were prepared rapidly in situ by the strategy of transforming three-dimensional (3D) metal boron organic polymers (BOPs@Ni2+) to one-dimensional (1D) boron organic polymers (BOPs@Ni) nanorod arrays at room temperature. The 3D BOPs@Ni2+ can be quickly obtained by the interaction of 4,4′-bipyridine with Ni2+ and dodecaborate (B12H12 2–) in an aqueous solution. When Ni2+ is converted into NiO in situ, 1D BOPs@Ni nanostructure transformation from the 3D BOPs@Ni2+ framework was achieved due to the B–H···π interaction between B12H12 2– and 4,4′-bipyridine. Furthermore, BOPs@Ni exhibits high catalytic activity and rapid kinetics in the conversion of 4-nitrophenol to 4-aminophenol, and the high stability of 1D nanorod arrays guarantees the catalytic activity of BOP@Ni to barely change under recycling for at least 10 times. BOPs@Ni also exhibits good catalytic performance and high selectivity characteristics in the catalytic reduction of a series of nitrobenzene derivatives. This strategy of using BOPs@Ni2+ for loading self-supporting nanometal not only exhibits a highly efficient catalytic hydrogenation of nitrobenzene and its derivative but also provides an effective technical route for designing self-supported nanometal materials.

The maximized metal dispersity provided by single-atom (SA) catalysts offers high catalytic activity, selectivity, and maximum metal utilization. However, the lack of adjacent metal atoms in these systems prevents further...