Developing efficient and stable bimetallic Pdbased anode electrocatalysts toward formic acid oxidation(FAO)is of great significance for commercial applications of direct formic acid fuel cells(DFAFCs).Herein,we report...Developing efficient and stable bimetallic Pdbased anode electrocatalysts toward formic acid oxidation(FAO)is of great significance for commercial applications of direct formic acid fuel cells(DFAFCs).Herein,we report a facile synthesis approach to fabricate PdCu nanoclusters(NCs)catalysts with granular-film structure.The introduction of Cu can adjust the electronic structure and d-band center of Pd,which can improve the catalytic performance of the catalysts.Compared with Pd NCs catalyst,the catalytic durability and activity of PdCu NCs catalysts for FAO are greatly improved.The order for catalytic activity of NC metals is Pd_(85)Cu_(15)NCs>Pd_(70)Cu_(30)NCs>Pd NCs.The maximum mass activity can be acquired with the Pd_(85)Cu_(15)NCs catalyst,which is about1.7 times that of the Pd NCs catalyst.And Pd_(85)Cu_(15)NCs catalyst still maintains the highest catalytic current density after 50 cycles,indicating that Pd_(85)Cu_(15)NCs catalyst has the best durability and electrocatalytic activity for FAO.Our work provides a new prospect for the design of highly efficient anode catalysts materials for DFAFCs.展开更多
如何构筑高性能的电催化剂是提高卤代有机污染物电催化还原去除的关键.本研究通过化学共还原的方法制备出钯铜(PdCu)纳米合金催化剂,通过扫描电子显微镜(SEM)、高分辨率透射电子显微镜(HRTEM)、能量色散X射线光谱(EDX)、X射线衍射(XRD)...如何构筑高性能的电催化剂是提高卤代有机污染物电催化还原去除的关键.本研究通过化学共还原的方法制备出钯铜(PdCu)纳米合金催化剂,通过扫描电子显微镜(SEM)、高分辨率透射电子显微镜(HRTEM)、能量色散X射线光谱(EDX)、X射线衍射(XRD)、X射线光电子能谱(XPS)、线性扫描伏安法(LSV)和电化学阻抗谱(EIS)等方法对其微观结构和电化学性能进行表征,并探究PdCu纳米合金催化剂对抗生素氟苯尼考(Florfenicol,FLO)电催化还原的降解机理.实验结果表明,所制备的PdCu纳米合金催化剂中Pd、Cu纳米颗粒分布均匀,具有优异的电化学还原性能和动力学性能以及快速的电子转移速率.PdCu纳米合金催化剂在-1.3 V vs.Hg/Hg_(2)SO_(4)下,120 min内对FLO的去除率高达97.5%,远高于纯Pd(82.9%)、纯Cu(67.4%)金属纳米颗粒催化剂的去除率,中性pH更有利于FLO的降解.叔丁醇淬灭实验表明,吸附态原子氢在电催化还原去除FLO过程中起重要作用.使用液质联用仪(LC-MS/MS)对FLO降解后的产物进行半定量分析表明,在PdCu纳米合金催化剂上FLO的电催化还原是一个逐步脱卤的过程,在实现完全脱氯后再进行脱氟.本研究为电催化高效还原卤代有机污染物提供了一种具有应用潜力的催化剂方案.展开更多
Suzuki-Miyaura reactions, involving the activation of carbon-halogen bonds, especially C-C1 bonds, have drawn widespread attention because of their huge industrial potential. However, these reactions are dependent on ...Suzuki-Miyaura reactions, involving the activation of carbon-halogen bonds, especially C-C1 bonds, have drawn widespread attention because of their huge industrial potential. However, these reactions are dependent on the development of highly active and stable catalysts. Herein, we developed a convenient one-pot wet route to synthesize PdxCuy bimetallic nanocrystals for the Suzuki-Miyaura reaction. By introducing Cu, an earth-abundant element, the catalytic activity was greatly enhanced while the amount of Pd required was reduced. PdxCuy nanocrystals of different compositions, including PdBCu, Pd2Cu, PdCu, PdCu2, and PdCu3, were successfully synthesized by tuning the Pd：Cu ratio. Their catalytic performance in Suzuki-Miyaura reactions between phenylboronic acid and halobenzenes （iodo-, bromo-, or chlorobenzene） showed that PdCua nanocatalyst demonstrated the best efficacy.展开更多
基金financially supported by the National Natural Science Foundation of China (No.51901197, 51971184 and 51771157)the Open Fund of Fujian Provincial Key Laboratory of Eco-Industrial Green Technology in Wuyi University (No.WYKF-EIGT2021-6)
文摘Developing efficient and stable bimetallic Pdbased anode electrocatalysts toward formic acid oxidation(FAO)is of great significance for commercial applications of direct formic acid fuel cells(DFAFCs).Herein,we report a facile synthesis approach to fabricate PdCu nanoclusters(NCs)catalysts with granular-film structure.The introduction of Cu can adjust the electronic structure and d-band center of Pd,which can improve the catalytic performance of the catalysts.Compared with Pd NCs catalyst,the catalytic durability and activity of PdCu NCs catalysts for FAO are greatly improved.The order for catalytic activity of NC metals is Pd_(85)Cu_(15)NCs>Pd_(70)Cu_(30)NCs>Pd NCs.The maximum mass activity can be acquired with the Pd_(85)Cu_(15)NCs catalyst,which is about1.7 times that of the Pd NCs catalyst.And Pd_(85)Cu_(15)NCs catalyst still maintains the highest catalytic current density after 50 cycles,indicating that Pd_(85)Cu_(15)NCs catalyst has the best durability and electrocatalytic activity for FAO.Our work provides a new prospect for the design of highly efficient anode catalysts materials for DFAFCs.
文摘如何构筑高性能的电催化剂是提高卤代有机污染物电催化还原去除的关键.本研究通过化学共还原的方法制备出钯铜(PdCu)纳米合金催化剂,通过扫描电子显微镜(SEM)、高分辨率透射电子显微镜(HRTEM)、能量色散X射线光谱(EDX)、X射线衍射(XRD)、X射线光电子能谱(XPS)、线性扫描伏安法(LSV)和电化学阻抗谱(EIS)等方法对其微观结构和电化学性能进行表征,并探究PdCu纳米合金催化剂对抗生素氟苯尼考(Florfenicol,FLO)电催化还原的降解机理.实验结果表明,所制备的PdCu纳米合金催化剂中Pd、Cu纳米颗粒分布均匀,具有优异的电化学还原性能和动力学性能以及快速的电子转移速率.PdCu纳米合金催化剂在-1.3 V vs.Hg/Hg_(2)SO_(4)下,120 min内对FLO的去除率高达97.5%,远高于纯Pd(82.9%)、纯Cu(67.4%)金属纳米颗粒催化剂的去除率,中性pH更有利于FLO的降解.叔丁醇淬灭实验表明,吸附态原子氢在电催化还原去除FLO过程中起重要作用.使用液质联用仪(LC-MS/MS)对FLO降解后的产物进行半定量分析表明,在PdCu纳米合金催化剂上FLO的电催化还原是一个逐步脱卤的过程,在实现完全脱氯后再进行脱氟.本研究为电催化高效还原卤代有机污染物提供了一种具有应用潜力的催化剂方案.
基金This research was supported in part by the National Natural Science Foundation of China （Nos. 21475007, 21275015 and 21505003）, and the Fundamental Research Funds for the Central Universities （Nos. YS1406, buctrc201507 and buctrc201608）. We also thank the support from the Innovation and Promotion Project of Beijing University of Chemical Technology, the Public Hatching Platform for Recruited Talents of Beijing University of Chemical Technology, the High- Level Faculty Program of Beijing University of Chemical Technology （No. buctrc201325）, and BUCT Fund for Disciplines Construction and Development （No. XK1526）.
文摘Suzuki-Miyaura reactions, involving the activation of carbon-halogen bonds, especially C-C1 bonds, have drawn widespread attention because of their huge industrial potential. However, these reactions are dependent on the development of highly active and stable catalysts. Herein, we developed a convenient one-pot wet route to synthesize PdxCuy bimetallic nanocrystals for the Suzuki-Miyaura reaction. By introducing Cu, an earth-abundant element, the catalytic activity was greatly enhanced while the amount of Pd required was reduced. PdxCuy nanocrystals of different compositions, including PdBCu, Pd2Cu, PdCu, PdCu2, and PdCu3, were successfully synthesized by tuning the Pd：Cu ratio. Their catalytic performance in Suzuki-Miyaura reactions between phenylboronic acid and halobenzenes （iodo-, bromo-, or chlorobenzene） showed that PdCua nanocatalyst demonstrated the best efficacy.
