Two isomers ofnitrochlorobenzene （o- andp-NCB） were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines ...Two isomers ofnitrochlorobenzene （o- andp-NCB） were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines （CAN） first through an amination process, and then rapidly dechlorinated to become aniline （AN） and CI^-, without the involvement of any other intermediate reaction products. The amination and dechlorination reaction are believed to take place predominantly on the surface site of the Pd/Fe catalysts. The dechlorination rate of the reductive degradation of the two isomers of nitrochlorobenzene （o-, and p-NCB） in the presence of Pd/Fe as a catalyst was measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy （correlation with the activation energy） of NCBs formation; the activation energy of each dechlorination reaction was measured to be 95.83 and 77.05 kJ/mol, respectively for o- and p-NCB. The results demonstrated that p-NCBs were reduced more easily than o-NCBs.展开更多
Proper design and preparation of high-performance and stable dual functional photocatalytic materials remains a significant objective of research. In this work, highly dispersed noble-metal nanoparticles （Au, Pd, Pt...Proper design and preparation of high-performance and stable dual functional photocatalytic materials remains a significant objective of research. In this work, highly dispersed noble-metal nanoparticles （Au, Pd, Pt） were immobilized on MIL-100（Fe） （denoted M@MIL-100（Fe）） using a facile room-temperature photodeposition technique. The resulting M@MIL-100（Fe） （M = Au, Pd, and Pt） nanocomposites exhibited enhanced photoactivities toward photocatalytic degradation of methyl orange （MO） and reduction of heavy-metal Cr（VI） ions under visible-light irradiation （A ≥ 420 nm） compared with blank-MIL-100（Fe）. Combining these results with photoelectrochemical analyses revealed that noble-metal deposition can effectively improve the charge-separation efficiency of MIL-100（Fe） under visible-light irradiation. This phenomenon in turn leads to the enhancement of visible-light-driven photoactivity of M@MIL-100（Fe） toward photocatalytic redox reactions. In particular, the Pt@MIL-100（Fe） with an average Pt particle size of 2 nm exhibited remarkably enhanced photoactivities compared with those of M@MIL-100（Fe） （M = Au and Pd）, which can be attributed to the integrative effect of the enhanced light absorption intensity and more efficient separation of the photogenerated charge carrier. In addition, possible photocatalytic reaction mechanisms are also proposed.展开更多
基金Project (No. 20407015) supported by the National Natural ScienceFoundation of China
文摘Two isomers ofnitrochlorobenzene （o- andp-NCB） were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines （CAN） first through an amination process, and then rapidly dechlorinated to become aniline （AN） and CI^-, without the involvement of any other intermediate reaction products. The amination and dechlorination reaction are believed to take place predominantly on the surface site of the Pd/Fe catalysts. The dechlorination rate of the reductive degradation of the two isomers of nitrochlorobenzene （o-, and p-NCB） in the presence of Pd/Fe as a catalyst was measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy （correlation with the activation energy） of NCBs formation; the activation energy of each dechlorination reaction was measured to be 95.83 and 77.05 kJ/mol, respectively for o- and p-NCB. The results demonstrated that p-NCBs were reduced more easily than o-NCBs.
基金This work was supported by the National Natural Science Foundation of China （Nos. 21273036 and 21177024） and Science ＆ Technology Plan Project of Fujian Province （No. 2014Y2003）.
文摘Proper design and preparation of high-performance and stable dual functional photocatalytic materials remains a significant objective of research. In this work, highly dispersed noble-metal nanoparticles （Au, Pd, Pt） were immobilized on MIL-100（Fe） （denoted M@MIL-100（Fe）） using a facile room-temperature photodeposition technique. The resulting M@MIL-100（Fe） （M = Au, Pd, and Pt） nanocomposites exhibited enhanced photoactivities toward photocatalytic degradation of methyl orange （MO） and reduction of heavy-metal Cr（VI） ions under visible-light irradiation （A ≥ 420 nm） compared with blank-MIL-100（Fe）. Combining these results with photoelectrochemical analyses revealed that noble-metal deposition can effectively improve the charge-separation efficiency of MIL-100（Fe） under visible-light irradiation. This phenomenon in turn leads to the enhancement of visible-light-driven photoactivity of M@MIL-100（Fe） toward photocatalytic redox reactions. In particular, the Pt@MIL-100（Fe） with an average Pt particle size of 2 nm exhibited remarkably enhanced photoactivities compared with those of M@MIL-100（Fe） （M = Au and Pd）, which can be attributed to the integrative effect of the enhanced light absorption intensity and more efficient separation of the photogenerated charge carrier. In addition, possible photocatalytic reaction mechanisms are also proposed.
