ABSTRACT
Vanadium catalysts offer unique selectivity in olefin polymerization, yet are underutilized industrially owing to their poor stability and productivity. Reported here is the immobilization of vanadium by cation exchange in MFU-4l, thus providing a metal-organic framework (MOF) with vanadium in a molecule-like coordination environment. This material forms a single-site heterogeneous catalyst with methylaluminoxane and provides polyethylene with low polydispersity (PDI≈3) and the highest activity (up to 148 000â h-1 ) reported for a MOF-based polymerization catalyst. Furthermore, polyethylene is obtained as a free-flowing powder as desired industrially. Finally, the catalyst shows good structural integrity and retains polymerization activity for over 24â hours, both promising attributes for the commercialization of vanadium-based polyolefins.
ABSTRACT
Bose-Einstein condensates (BECs) composed of polarons would be an advance because they would combine coherently charge, spin, and a crystal lattice. Following our earlier report of unique structural and spectroscopic properties, we now identify potentially definitive evidence for polaronic BECs in photo- and chemically doped UO2(+x) on the basis of exceptional coherence in the ultrafast time dependent terahertz absorption and microwave spectroscopy results that show collective behavior including dissipation patterns whose precedents are condensate vortex and defect disorder and condensate excitations. That some of these signatures of coherence in an atom-based system extend to ambient temperature suggests a novel mechanism that could be a synchronized, dynamical, disproportionation excitation, possibly via the solid state analog of a Feshbach resonance that promotes the coherence. Such a mechanism would demonstrate that the use of ultra-low temperatures to establish the BEC energy distribution is a convenience rather than a necessity, with the actual requirement for the particles being in the same state that is not necessarily the ground state attainable by other means. A macroscopic quantum object created by chemical doping that can persist to ambient temperature and resides in a bulk solid would be revolutionary in a number of scientific and technological fields.