State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China; University of Chinese Academy of Sciences, Beijing, 100049, China.
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085, China; University of Chinese Academy of Sciences, Beijing, 100049, China.
J Hazard Mater. 2019 Mar 15;366:338-345. doi: 10.1016/j.jhazmat.2018.12.009. Epub 2018 Dec 3.
Reductive transformation of nitroaromatic compounds is a central step in its remediation in wastewater, and therefore has invoked extensive catalytical research with rare metals such as palladium (Pd). Herein, we report Pantoea sp. IMH assisted biosynthesis for Pd@NC as an efficient catalyst for the reduction of nitroaromatics. Multiple complementary characterization results for Pd@NC evidenced the evenly dispersed Pd NPs on an N-doped carbon support. Pd@NC exhibited the superior catalytic activity in the reduction of nitroaromatic compounds (4-nitrophenol, 2-nitroaniline, 4-nitroaniline, and 2,6-dichloro-4-nitroaniline). The origin of the catalytic activity was explained by its unique electronic structure, as explored with X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory (DFT) calculations. XANES analysis revealed an increase of 25.6% in the d-hole count in Pd@NC compared with Pd°, as the result of pd hybridization. In agreement with our experimental observations, DFT calculations suggested the formation of Pd-C bonds and charge re-distribution between Pd and the carbon layer, which contributed to the superior catalytic activity of Pd@NC.
还原转化硝基芳香族化合物是废水修复过程中的一个核心步骤,因此,人们广泛地研究了稀有金属(如钯(Pd))的催化作用。本文报道了 Pantoea sp. IMH 辅助生物合成 Pd@NC,该催化剂可有效还原硝基芳香族化合物。多种互补的 Pd@NC 特征化结果表明,Pd NPs 均匀分散在 N 掺杂碳载体上。Pd@NC 在还原硝基芳香族化合物(对硝基苯酚、邻硝基苯胺、对硝基苯胺和 2,6-二氯-4-硝基苯胺)方面表现出优异的催化活性。通过 X 射线吸收近边结构(XANES)光谱和密度泛函理论(DFT)计算研究了其独特的电子结构,解释了其催化活性的起源。XANES 分析表明,与 Pd°相比,Pd@NC 中的 d 空穴数增加了 25.6%,这是 pd 杂化的结果。与我们的实验观察结果一致,DFT 计算表明形成了 Pd-C 键和 Pd 与碳层之间的电荷再分布,这有助于 Pd@NC 具有优异的催化活性。