Sr2Pb(BeB5O10)(BO3): An Excellent Ultraviolet Nonlinear-Optical Beryllium Borate by the Pb-Modified Construction of a Conjugated System and Lone-Pair Effect.

The design of material by chemical and/or crystalline modification of a classic structure model benefits not only the optimized physical properties but also the controllability and efficiency. Herein, a new nonlinear-optical (NLO) beryllium borate crystal, Sr2Pb(BeB5O10)(BO3) (SPBBO), is successfully designed and synthesized by chemical and crystalline modification of the perovskite-like K3B6O10Cl NLO crystal. SPBBO displays a 3D BeB5O103- open-framework structure composed of interconnecting BeB5O13 groups with filled cationic Sr/Pb and anionic BO3 groups, which exhibits the striking enhancement of the second-harmonic-generation (SHG) response (8 × KDP) and birefringence (0.10) compared to the parent model. Replacement of K by Sr and Pb with a lone pair and replacement of Cl by conjugated BO3 result in the synergistic conjugation of Pb with host BeB5O103- and filled BO3 groups, contributing to the striking enhancement of the SHG and birefringence. Single-crystal measurements show that SPBBO has a short UV absorption edge of 280 nm with a wide energy band gap of 4.35 eV and an outstanding laser-induced resistant behavior with a remarkably high laser-induced damage threshold of 2100 MW cm-2. The excellent properties indicate that the SPBBO crystal is a very promising UV NLO functional material.

One-step alcoholysis of lignin into small-molecular aromatics: Influence of temperature, solvent, and catalyst.

Lignin valorization is a challenge because of its complex structure and high thermal stability. Supercritical alcoholysis of lignin without external hydrogen in a self-made high-pressure reactor is investigated under different temperatures (450-500 °C) and solvents as well as catalysts by using a reactant suspension mode. Small-molecular arenes and mono-phenols (C7-C12) are generated under short residence time of 30 min. High temperature (500 °C) favors efficient deoxy-liquefaction of lignin (70%) and formation of small-molecular arenes (C6-C9). Solvents methanol and ethanol demonstrate much more synergistic effect on efficient deoxy-liquefaction of lignin than propanol. The catalyst Cu-C has the optimal activity and selectivity in methanol (70% of conversion, 83.93% of arenes), whereas Fe-SiC possesses the optimal catalytic deoxygenation in ethanol, resulting in the formation of arenes other than phenols. Further analysis indicates that lignin is converted into arenes by efficient cleavages of C-O ether bonds and C-C bonds under high temperature and pressure.