Integrating photothermal and plasmonic catalysis induced by near-infrared light for efficient reduction of 4-nitrophenol.

The reduction of 4-nitrophenol (4-NP) into 4-aminophenol (4-AP) is an important reaction in both chemical manufacturing and environmental protection. The design of a highly active, multifunctional and reusable catalyst for efficient 4-NP decontamination/valorization is therefore crucial to bring in economic and societal benefits. Herein, we achieve an efficient plasmonic-photothermal catalyst of Pd nanoparticles by growing them on graphene-polyelectrolytes self-assembly nanolayers via an in situ green reduction approach using polyelectrolyte as the reductant. The as-fabricated catalyst shows high catalytic behaviors and good stability (maintained over 92.5 % conversion efficiency after ten successive cycles) for 4-NP reduction under ultra-low catalyst dose. The rate constant and turnover frequency were calculated at 0.197 min-1 and 7.79 mmol g-1 min-1, respectively, which were much higher than those of most reported catalysts. Moreover, the as-prepared catalyst exhibited excellent photothermal conversion efficiency of ∼77 % and boosted 4-NP reduction by ∼2-fold under near-infrared irradiation (NIR). This study provides valuable insights into the design of greener catalytic materials and facilitates the development of multifunctional plasmonic-photothermal catalysts for diverse environmental, chemical, and energy applications using NIR.

[UV/Visible spectroscopic study of the beta-diketonate zirconium active species for olefin polymerization].

The method of UV/Visible absorption spectroscopy for olefin catalytic system was introduced in this paper, whose testing condition was much closer to the polymerization conditions. The actions of olefin polymerization catalyst (dbm)2 ZrCl2 with cocatalyst AlEt2 Cl (or MAO) were investigated by UV/visible absorption spectroscopy at atmosphere temperature. It was shown that the UV/Visible main absorption band of the zirconocenium, which can be related to the ligand to metal charge transfer bands (LMCT), varies greatly upon incremental addition of AlEt2 Cl or MAO. For the low molar ratios of Al/Zr in the catalytic system, there was the substitution of an electron withdrawing chlorine atom by a donating alkyl group. Then a hypsochromic shift of the initial catalyst absorption band, corresponding to the monomethylation of the catalyst, was observed in each catalytic system (dbm)2 ZrCl2/AlEt2 Cl (or (dbm)2 ZrCl2/MAO). On the contrary, further addition of AlEt2 Cl (or MAO) was accompanied by a continuous bathochromic shift of the maximal wavelength, which corresponding to the formation of more dissociated ionic active species. Then, there would be a coordination of monomer to the ionic active species.