Nitrogen-doped carbon materials encapsulating 3 d transition metals are promising alternatives to replace noble metal Pt catalysts for efficiently catalyzing the oxygen reduction reaction(ORR). Herein, we use cobalt s...Nitrogen-doped carbon materials encapsulating 3 d transition metals are promising alternatives to replace noble metal Pt catalysts for efficiently catalyzing the oxygen reduction reaction(ORR). Herein, we use cobalt substituted perfluorosulfonic acid/polytetrafluoroethylene copolymer and dicyandiamide as the pyrolysis precursor to synthesize nitrogen-doped carbon nanotube(N–CNT) encapsulating cobalt nanoparticles hybrid material. The carbon layers and specific surface area of N–CNT have a critical role to the ORR performance due to the exposed active sites, determined by the mass ratio of the two precursors. The optimum hybrid material exhibits high ORR activity and stability, as well as excellent performance and durability in zinc–air battery.展开更多
The permanent magnetic nanocomposite PrNdFeB/Fe7Co3 ribbons were prepared by directly quenching, and the microstructure and magnetic influence of composite materials with Co substitution were studied. The phase identi...The permanent magnetic nanocomposite PrNdFeB/Fe7Co3 ribbons were prepared by directly quenching, and the microstructure and magnetic influence of composite materials with Co substitution were studied. The phase identification and the magnetic properties were measured by X-ray diffraction(XRD) and vibrating sample magnetometry(VSM). Microstructure observation was performed using scanning electron microscopy(SEM). The crystallization temperatures of the hard magnetic phase and the soft magnetic phase were measured using differential scanning calorimetry(DSC). The experimental results showed that Co addition improved the Curie temperature of magnets. When the ribbons were melt-spun at 35 m/s, the added content of Co was 4 at.%, and the magnetic properties were the best, which were remanence(Br) of 0.379 T, coercivity(Hci) of 344.4 kA/m, the maximum magnetic energy product(BH)max of 32.6 kJ/m^3. Besides, the activation energy of each phase was calculated by Kissinger equation, which was 310.4 kJ/mol of Fe7Co3 phase and 510.2 kJ/mol of 2:14:1 phase, respectively.展开更多
A novel magnetically recoverable thioporphyrazine catalyst(CoPz(S-Bu)8/SiO2@Fe3O4) was prepared by immobilization of the cobalt octkis(butylthio) porphyrazine complex(CoPz(S-Bu)8) on silica-coated magnetic n...A novel magnetically recoverable thioporphyrazine catalyst(CoPz(S-Bu)8/SiO2@Fe3O4) was prepared by immobilization of the cobalt octkis(butylthio) porphyrazine complex(CoPz(S-Bu)8) on silica-coated magnetic nanospheres(SiO2@Fe3O4). The composite CoPz(S-Bu)8/SiO2@Fe3O4appeared to be an active catalyst in the oxidation of benzyl alcohol in aqueous solution using hydrogen peroxide(H2O2) as oxidant under Xe-lamp irradiation,with 36.4% conversion of benzyl alcohol, about 99% selectivity for benzoic acid and turnover number(TON) of 61.7 at ambient temperature. The biomimetic catalyst CoPz(S-Bu)8was supported on the magnetic carrier SiO2@Fe3O4 so as to suspend it in aqueous solution to react with substrates, utilizing its lipophilicity. Meanwhile the CoPz(S-Bu)8can use its unique advantages to control the selectivity of photocatalytic oxidation without the substrate being subjected to deep oxidation. The influence of various reaction parameters on the conversion rate of benzyl alcohol and selectivity of benzoic acid was investigated in detail. Moreover, photocatalytic oxidation of substituted benzyl alcohols was obtained with high conversion and excellent selectivity, specifically conversion close to 70%, selectivity close to 100% and TON of 113.6 for para-position electron-donating groups. The selectivity and eco-friendliness of the biomimetic photocatalyst give it great potential for practical applications.展开更多
Cyclopentadienyl cobalt complexes (n5-C5H4R)CoLI2 [L = CO,R=-COOCH2CH=CH2 (3); L=PPh3,R=-COOCH2-CH=CH2 (6); L= P(p-C6H4CH3)3,R=-COOC(CH3) = CH2 (7),-COOCH2C6H5(8),-COOCH2CH = CH2 (9)] were prepared and characterized b...Cyclopentadienyl cobalt complexes (n5-C5H4R)CoLI2 [L = CO,R=-COOCH2CH=CH2 (3); L=PPh3,R=-COOCH2-CH=CH2 (6); L= P(p-C6H4CH3)3,R=-COOC(CH3) = CH2 (7),-COOCH2C6H5(8),-COOCH2CH = CH2 (9)] were prepared and characterized by elemental analyses,1H NMR,IR and UV-vis spectra.The reaction of complexes (n5-C5H4R)CoLI2[L=CO,R=-COOC(CH3)=CH2 (1) ,-COOCH2C6H5(2):L=PPh3,R =-COOC(CH3)=CH2 (4),-COOCH2C6H5(5)] with Na-Hg resulted in the formation of their corresponding substituted cobaltocene (n5-C5H4R)2Co [R= -COOC(CH3) = CH2 (10),-COOCH2C6H5 (11) ].The electrochemical properties of these complexes 1-11 were studied by cyclic voltammetry.It was found that as the ligand (L) of the cobalt (Ⅲ) complexes changing from CO to PPh3 and P(p-tolyl)3,their oxidation potentials increased gradually.The cyclic voltammetry of α,α'-substituted cobaltocene showed reversible oxidation of one electron pro-展开更多
基金financial support from the Ministry of Science and Technology of China(Grants 2016YFB0600901 and 2013CB933100)the National Natural Science Foundation of China(Grants 21573222 and 91545202)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB17020200)financial support from CAS Youth Innovation Promotion(Grant No.2015145)
文摘Nitrogen-doped carbon materials encapsulating 3 d transition metals are promising alternatives to replace noble metal Pt catalysts for efficiently catalyzing the oxygen reduction reaction(ORR). Herein, we use cobalt substituted perfluorosulfonic acid/polytetrafluoroethylene copolymer and dicyandiamide as the pyrolysis precursor to synthesize nitrogen-doped carbon nanotube(N–CNT) encapsulating cobalt nanoparticles hybrid material. The carbon layers and specific surface area of N–CNT have a critical role to the ORR performance due to the exposed active sites, determined by the mass ratio of the two precursors. The optimum hybrid material exhibits high ORR activity and stability, as well as excellent performance and durability in zinc–air battery.
基金Project supported by the National Natural Science Foundation of China(51271070)Chinese Ministry of Education Doctoral Program(20131317110002)+1 种基金Natural Science Foundation Key Project(E2016202406)Natural Science Foundation of Tianjin(14JCYBJC17900)
文摘The permanent magnetic nanocomposite PrNdFeB/Fe7Co3 ribbons were prepared by directly quenching, and the microstructure and magnetic influence of composite materials with Co substitution were studied. The phase identification and the magnetic properties were measured by X-ray diffraction(XRD) and vibrating sample magnetometry(VSM). Microstructure observation was performed using scanning electron microscopy(SEM). The crystallization temperatures of the hard magnetic phase and the soft magnetic phase were measured using differential scanning calorimetry(DSC). The experimental results showed that Co addition improved the Curie temperature of magnets. When the ribbons were melt-spun at 35 m/s, the added content of Co was 4 at.%, and the magnetic properties were the best, which were remanence(Br) of 0.379 T, coercivity(Hci) of 344.4 kA/m, the maximum magnetic energy product(BH)max of 32.6 kJ/m^3. Besides, the activation energy of each phase was calculated by Kissinger equation, which was 310.4 kJ/mol of Fe7Co3 phase and 510.2 kJ/mol of 2:14:1 phase, respectively.
基金supported by the National Natural Science Foundation of China (Nos. 21272281 and 20977115)Natural Science Foundation of Hubei Province (2014CFB919)+1 种基金"the Fundamental Research Funds for the Central Universities", South-Central University for Nationalities (CZY14003)the Science and Technology Plan Innovation Team of Wuhan City (2015070504020220)
文摘A novel magnetically recoverable thioporphyrazine catalyst(CoPz(S-Bu)8/SiO2@Fe3O4) was prepared by immobilization of the cobalt octkis(butylthio) porphyrazine complex(CoPz(S-Bu)8) on silica-coated magnetic nanospheres(SiO2@Fe3O4). The composite CoPz(S-Bu)8/SiO2@Fe3O4appeared to be an active catalyst in the oxidation of benzyl alcohol in aqueous solution using hydrogen peroxide(H2O2) as oxidant under Xe-lamp irradiation,with 36.4% conversion of benzyl alcohol, about 99% selectivity for benzoic acid and turnover number(TON) of 61.7 at ambient temperature. The biomimetic catalyst CoPz(S-Bu)8was supported on the magnetic carrier SiO2@Fe3O4 so as to suspend it in aqueous solution to react with substrates, utilizing its lipophilicity. Meanwhile the CoPz(S-Bu)8can use its unique advantages to control the selectivity of photocatalytic oxidation without the substrate being subjected to deep oxidation. The influence of various reaction parameters on the conversion rate of benzyl alcohol and selectivity of benzoic acid was investigated in detail. Moreover, photocatalytic oxidation of substituted benzyl alcohols was obtained with high conversion and excellent selectivity, specifically conversion close to 70%, selectivity close to 100% and TON of 113.6 for para-position electron-donating groups. The selectivity and eco-friendliness of the biomimetic photocatalyst give it great potential for practical applications.
基金Project (No. 29771008) supported by the National Natural Science Foundation of ChinaA research grant from the State Educational Committee of Chinaa Fudan University Faculty Research Grant for partial support of this work are greatly acknowledged. Tif
文摘Cyclopentadienyl cobalt complexes (n5-C5H4R)CoLI2 [L = CO,R=-COOCH2CH=CH2 (3); L=PPh3,R=-COOCH2-CH=CH2 (6); L= P(p-C6H4CH3)3,R=-COOC(CH3) = CH2 (7),-COOCH2C6H5(8),-COOCH2CH = CH2 (9)] were prepared and characterized by elemental analyses,1H NMR,IR and UV-vis spectra.The reaction of complexes (n5-C5H4R)CoLI2[L=CO,R=-COOC(CH3)=CH2 (1) ,-COOCH2C6H5(2):L=PPh3,R =-COOC(CH3)=CH2 (4),-COOCH2C6H5(5)] with Na-Hg resulted in the formation of their corresponding substituted cobaltocene (n5-C5H4R)2Co [R= -COOC(CH3) = CH2 (10),-COOCH2C6H5 (11) ].The electrochemical properties of these complexes 1-11 were studied by cyclic voltammetry.It was found that as the ligand (L) of the cobalt (Ⅲ) complexes changing from CO to PPh3 and P(p-tolyl)3,their oxidation potentials increased gradually.The cyclic voltammetry of α,α'-substituted cobaltocene showed reversible oxidation of one electron pro-