Low-Spin Fe Redox-Based Prussian Blue with excellent selective dual-band electrochromic modulation and energy-saving applications.

Dual-band electrochromic materials (DBEMs) are of utmost importance for smart windows to realize independent control of the visible (VIS) and near-infrared (NIR) light. However, very few single-component DBEMs are capable of independently and effectively controlling both VIS and NIR light. Here, we present Prussian blue (PB) with remarkable performance to replace the composite DBEMs that require deliberate design and complicated preparation. Excellent durability and capacity were achieved simultaneously due to the activated low-spin Fe in PB. A dual-band electrochromic device (DBED) by using PB thin films as electrochromic layers was constructed, exhibiting superior dual-band electrochromic performance, energy storage performance and memory effect. We show that the energy-saving DBED can be bleached without applying any external bias potential, and can be colored by using a commercial photovoltaic solar panel under ambient solar irradiation. The stored energy during coloration can be further used to light up the lights. Finally, the coloration mechanism of the DBED was studied by the density functional theory calculations, to shed light on the large optical transmittance modulation in both VIS and NIR regions. The new insights will advance the design of efficient and durable DBEMs and the development of bi-functional smart windows.

Zn/Al/Pb Mixed Oxides as Efficient Heterogeneous Catalysts for the Synthesis of Methyl N-Phenyl Carbamate.

Dimethyl carbonate aminolysis is an effective and green pathway for the synthesis of methyl N-phenyl carbamate (MPC), which is an important intermediate for the synthesis of polyurethanes and many other chemicals. In this work, we demonstrate the fabrication of Zn/Al/Pb mixed oxides as efficient and stable heterogeneous catalysts for MPC synthesis. The catalysts are prepared via facile coprecipitation and subsequent thermal annealing. Their micromorphology and physical-chemical properties are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning TEM (STEM), X-ray photoelectron spectroscopy (XPS), and NH3-TPD. The results show that rather than being doped into ZnO and/or Al2O3, PbO is highly dispersed in the ZnO/Al2O3 base forming ultrafine nanoparticles. Despite the weak interactions within the mixed oxides, the high density of active sites generates outstanding catalytic activity and cycling stability for MPC synthesis, with an aniline conversion of almost 100% and MPC yield of up to 90% during six repeated tests, providing great potential for their further application.

Methyl N-phenyl carbamate synthesis over Zn/Al/Ce mixed oxide derived from hydrotalcite-like precursors.

Methyl N-phenyl carbamate (MPC) is an important intermediate for the green synthesis of methylene diphenyl diisocyanate (MDI) as well as many other important products. In the present work, Zn/Al/Ce mixed oxides derived from hydrotalcite-like precursors were employed as effective and recoverable heterogeneous catalyst for MPC synthesis via DMC aminolysis. Zn/Al/Ce hydrotalcite-like precursors prepared via coprecipitation method and the resulting catalysts were characterized by means of XRD, BET, SEM and XPS. Strong interactions within the Zn/Al/Ce mixed oxides were observed via the addition of appropriate amount of cerium. The mixed oxides containing 2.5% cerium showed high DMC aminolysis activity giving aniline conversion of 95.8%, MPC selectivity of 81.6% and MPC yield of 78.2%. Moreover, as a heterogeneous catalyst, it also exhibited superiorities of easy recovery and recyclable stability for MPC synthesis.