Anti-CO poisoning ability is significant in formic acid oxidation in the fuel cell technique.Herein,Pd Ni alloy supported on N-doped graphene aerogel(Pd Ni/GA-N)was found to have catalytic ability toward formic acid e...Anti-CO poisoning ability is significant in formic acid oxidation in the fuel cell technique.Herein,Pd Ni alloy supported on N-doped graphene aerogel(Pd Ni/GA-N)was found to have catalytic ability toward formic acid electrooxidation over a wide potential range because of the improved anti-CO poisoning ability.This catalyst was fabricated by simple freeze-drying of mixture solution of graphene aerogel,polyvinylpyrrolidone,Pd^(2+)and Ni^(2+)and the subsequent thermal annealing reduction approach in the N2/H2 atmosphere.Pd-Ni alloy particles anchored over the folding N-doped graphene surface with a porous hierarchical architecture structure in the 3 D directions.It showed the catalytic performance of its maximum mass activity of 836 m A mg^(-1)in a broad potential range(0.2-0.6 V)for formic acid oxidation.The CO stripping experiment demonstrated its largely improved anti-CO poisoning ability with the peak potential of 0.67 V,approximately 60 and 40 m V less compared to those of Pd/GA-N and Pd/C samples.The high anti-CO poisoning ability and strong electronic effect resulting from the interaction between the3 D GA-N support and the Pd-Ni alloy makes it a promising catalyst for application in direct formic acid fuel cells.展开更多
The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for th...The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for the development of direct methanol fuel cells(DMFCs). In this work, we develop a cyanogel-reduction method to synthesize reduced graphene oxide(rGO) supported highly dispersed PdNi alloy nanocrystals(PdNi/rGO) with high alloying degree and tunable Pd/Ni ratio. The large specific surface area and the d-band center downshift of Pd result in excellent activity of Pd4 Ni1/rGO nanohybrids for the ORR. The modification of Pd electronic structure can facilitate the adsorption of CH3 OH on Pd surface and the highly oxophilic property of Ni can eliminate/mitigate the COadsintermediates poisoning, which make PdNi/r GO nanohybrids possess superior MOR activity. In addition, rGO improve the stability of PdNi alloy nanocrystals for the ORR and MOR. Due to high activity and stability for the ORR and MOR, PdNi/rGO nanohybrids are promising to be an available bifunctional electrocatalyst in DMFCs.展开更多
The solubility of Pd(NO_(3))_(2) in water is moderate whereas it is completely soluble in diluted HNO_(3) solution. Pd/MIL-101(Cr) and Pd/MIL-101-NH_(2)(Cr) were synthesized by aqueous solution of Pd(NO_(3))_(2) and P...The solubility of Pd(NO_(3))_(2) in water is moderate whereas it is completely soluble in diluted HNO_(3) solution. Pd/MIL-101(Cr) and Pd/MIL-101-NH_(2)(Cr) were synthesized by aqueous solution of Pd(NO_(3))_(2) and Pd(NO_(3))_(2) solution in dilute HNO_(3) and used for CO oxidation reaction. The catalysts synthesized with Pd(NO_(3))_(2) solution in dilute HNO_(3) showed lower activity. The aqueous solution of Pd(NO_(3))_(2) was used for synthesis of mono-metal Ni, Pd and bimetallic PdNi nanoparticles with various molar ratios supported on MOF. Pd_(70)Ni_(30)/MIL-101(Cr) catalyst showed higher activity than monometallic counterparts and Pd+ Ni physical mixture due to the strong synergistic effect of PdNi nanoparticles, high distribution of PdNi nanoparticles, and lower dissociation and desorption barriers. Comparison of the catalysts synthesized by MIL-101(Cr) and MIL-101-NH_(2)(Cr) as the supports of metals showed that Pd/MIL-101-NH_(2)(Cr) outperforms Pd/MIL-101-(Cr) because of the higher electron density of Pd resulting from the electron donor ability of the NH_(2) functional group. However, the same activities were observed for Pd_(70)Ni_(30)/MIL-101(Cr) and Pd_(70)Ni_(30)/MIL-101-NH_(2)(Cr), which is due to a less uniform distribution of Pd nanoparticles in Pd_(70)Ni_(30)/MIL-101-NH_(2)(Cr) originated from amorphization of MIL-101-NH_(2)(Cr) structure during the reduction process. In contrast, Pd_(70)Ni_(30)/MIL-101(Cr) revealed the stable structure and activity during reduction and CO oxidation for a long time.展开更多
基金supported by the National Natural Science Foundation of China(21972124,21603041)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institution+1 种基金the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University(2019FY003025)the Research Foundation of Department of Education of Yunnan Province(2020Y0018)。
文摘Anti-CO poisoning ability is significant in formic acid oxidation in the fuel cell technique.Herein,Pd Ni alloy supported on N-doped graphene aerogel(Pd Ni/GA-N)was found to have catalytic ability toward formic acid electrooxidation over a wide potential range because of the improved anti-CO poisoning ability.This catalyst was fabricated by simple freeze-drying of mixture solution of graphene aerogel,polyvinylpyrrolidone,Pd^(2+)and Ni^(2+)and the subsequent thermal annealing reduction approach in the N2/H2 atmosphere.Pd-Ni alloy particles anchored over the folding N-doped graphene surface with a porous hierarchical architecture structure in the 3 D directions.It showed the catalytic performance of its maximum mass activity of 836 m A mg^(-1)in a broad potential range(0.2-0.6 V)for formic acid oxidation.The CO stripping experiment demonstrated its largely improved anti-CO poisoning ability with the peak potential of 0.67 V,approximately 60 and 40 m V less compared to those of Pd/GA-N and Pd/C samples.The high anti-CO poisoning ability and strong electronic effect resulting from the interaction between the3 D GA-N support and the Pd-Ni alloy makes it a promising catalyst for application in direct formic acid fuel cells.
基金the National Natural Science Foundation of China (21473111)the Fundamental Research Funds for the Central Universities (GK201701007)
文摘The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for the development of direct methanol fuel cells(DMFCs). In this work, we develop a cyanogel-reduction method to synthesize reduced graphene oxide(rGO) supported highly dispersed PdNi alloy nanocrystals(PdNi/rGO) with high alloying degree and tunable Pd/Ni ratio. The large specific surface area and the d-band center downshift of Pd result in excellent activity of Pd4 Ni1/rGO nanohybrids for the ORR. The modification of Pd electronic structure can facilitate the adsorption of CH3 OH on Pd surface and the highly oxophilic property of Ni can eliminate/mitigate the COadsintermediates poisoning, which make PdNi/r GO nanohybrids possess superior MOR activity. In addition, rGO improve the stability of PdNi alloy nanocrystals for the ORR and MOR. Due to high activity and stability for the ORR and MOR, PdNi/rGO nanohybrids are promising to be an available bifunctional electrocatalyst in DMFCs.
基金supported by Sharif University of Technology,Nuclear Science and Technology Research Institute,and Iran National Science Foundation.
文摘The solubility of Pd(NO_(3))_(2) in water is moderate whereas it is completely soluble in diluted HNO_(3) solution. Pd/MIL-101(Cr) and Pd/MIL-101-NH_(2)(Cr) were synthesized by aqueous solution of Pd(NO_(3))_(2) and Pd(NO_(3))_(2) solution in dilute HNO_(3) and used for CO oxidation reaction. The catalysts synthesized with Pd(NO_(3))_(2) solution in dilute HNO_(3) showed lower activity. The aqueous solution of Pd(NO_(3))_(2) was used for synthesis of mono-metal Ni, Pd and bimetallic PdNi nanoparticles with various molar ratios supported on MOF. Pd_(70)Ni_(30)/MIL-101(Cr) catalyst showed higher activity than monometallic counterparts and Pd+ Ni physical mixture due to the strong synergistic effect of PdNi nanoparticles, high distribution of PdNi nanoparticles, and lower dissociation and desorption barriers. Comparison of the catalysts synthesized by MIL-101(Cr) and MIL-101-NH_(2)(Cr) as the supports of metals showed that Pd/MIL-101-NH_(2)(Cr) outperforms Pd/MIL-101-(Cr) because of the higher electron density of Pd resulting from the electron donor ability of the NH_(2) functional group. However, the same activities were observed for Pd_(70)Ni_(30)/MIL-101(Cr) and Pd_(70)Ni_(30)/MIL-101-NH_(2)(Cr), which is due to a less uniform distribution of Pd nanoparticles in Pd_(70)Ni_(30)/MIL-101-NH_(2)(Cr) originated from amorphization of MIL-101-NH_(2)(Cr) structure during the reduction process. In contrast, Pd_(70)Ni_(30)/MIL-101(Cr) revealed the stable structure and activity during reduction and CO oxidation for a long time.
基金financially supported by the National Natural Science Foundation of China (22005002)the Natural Science Foundation of Anhui Province (2208085Y03)+1 种基金Anhui University Scientific Research Start-up Fundsupported by the advanced computing resources provided by the Supercomputing Center of the University of Science and Technology of China。
