Wu Haoran, Song Jinliang, Xie Chao, Hu Yue, Zhang Pei, Yang Guanying, Han Buxing
Beijing National Laboratory for Molecular Science , CAS Key Laboratory of Colloid and Interface and Thermodynamics , CAS Research/Education Center for Excellence in Molecular Sciences , Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190 , China . Email:
School of Chemistry and Chemical Engineering , University of Chinese Academy of Sciences , Beijing 100049 , China.
Chem Sci. 2018 Dec 3;10(6):1754-1759. doi: 10.1039/c8sc03161d. eCollection 2019 Feb 14.
Development of mild and efficient strategies for biomass conversion is of great significance, and design of advanced catalysts is crucial for biomass valorization. Herein, we designed PbS-based electrocatalysts through a surface engineering strategy partial oxidation, and the degree of surface oxidation of PbS to PbSO could be easily tuned by calcination temperature. It was discovered that the prepared electrocatalysts could efficiently catalyze reduction of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) using water as the hydrogen source. Especially, the electrocatalyst calcined at 400 °C (PbS-400) showed outstanding performance with a current density of 13.5 mA cm and a GVL faradaic efficiency of 78.6%, which was far higher than the best results reported up to date. Moreover, GVL was the only product from LA reduction, indicating the excellent selectivity. Mechanism investigation showed that LA was converted through electrocatalytic hydrogenation of carbonyl groups of LA and subsequent intramolecular esterification.
开发温和且高效的生物质转化策略具有重要意义，而设计先进的催化剂对于生物质增值至关重要。在此，我们通过表面工程策略——部分氧化，设计了基于硫化铅的电催化剂，并且硫化铅表面氧化为硫酸铅的程度可通过煅烧温度轻松调节。研究发现，所制备的电催化剂能够以水作为氢源，高效催化生物质衍生的乙酰丙酸（LA）还原为γ-戊内酯（GVL）。特别是，在400℃煅烧的电催化剂（PbS-400）表现出优异的性能，电流密度为13.5 mA cm，GVL的法拉第效率为78.6%，这远远高于迄今为止报道的最佳结果。此外，GVL是LA还原的唯一产物，表明具有出色的选择性。机理研究表明，LA是通过LA羰基的电催化氢化以及随后的分子内酯化反应进行转化的。
