Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly...Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly efficient Fe-N-C porous ORR electrocatalyst with FeNx moieties promoted by Fe2N nanoparticles derived from Fe-doped zeolitic imidazolate framework.The best-performing Fe-N-C/HPC-NH3 catalyst exhibits a superior ORR activity with an onset (E0) and half-wave (E1/2) potential of 0.945 and 0.803 V (RHE),respectively,which is comparable to those of the commercial Pt/C in acidic media.Probing and acid-leaching experiments prove that FeNx moieties play an important role in the ORR and the Fe2N can further improve the ORR activity.Density functional theory calculation reveals a synergistic effect that the existence of Fe2N weakens the adsorption of ORR intermediates on active sites and lowers the reaction free energy of the potential limiting step,thus facilitating the ORR.Both experimental evidence and theoretical analysis for the enhancement of ORR activity by Fe2N decoration in Fe-N-C catalyst might inspire a new strategy for rational design of high performance non-precious metal catalysts.展开更多
A novel coordination polymer, [Fe(C 5H 4NCOO) 2] n, was synthesized by hydrothermal reaction and characterized by elemental analysis as well as IR spectroscopy. The crystal structure (with a novel 3-D network) of this...A novel coordination polymer, [Fe(C 5H 4NCOO) 2] n, was synthesized by hydrothermal reaction and characterized by elemental analysis as well as IR spectroscopy. The crystal structure (with a novel 3-D network) of this compound belongs to monoclinic, space group P2 1/n, a=0.49544(1) nm, b=1.32443(2) nm, c=1.04983(1) nm, β=101.586(1)°. The diffuse reflectance spectra (200～2500 nm) showed that the polymer had strong absorbance in 375～563 nm (E g≈2.5 eV) region and weak absorbance from 720 to 2500 nm (near infrared spectra).展开更多
A series of new biochar-supported composite based on the combination of biochar and metallic nanoparticles(NPs)were produced through single-step pyrolysis of FeCl_3–Ti(OBu)_4 laden agar biomass under NH_3 environment...A series of new biochar-supported composite based on the combination of biochar and metallic nanoparticles(NPs)were produced through single-step pyrolysis of FeCl_3–Ti(OBu)_4 laden agar biomass under NH_3 environment.The physiochemical properties of composites were characterized thoroughly.It has found that heating temperature and N-doping through NH_3-ambiance pyrolysis significantly influence the visible-light sensitivity and bandgap energy of composites.The catalytic activities of composites were measured by degradation of Methylene Blue(MB)in the presence or absence of H_2O_2 and visible-light irradiation.Our best catalyst(N–TiO_2–Fe_3O_4-biochar)exhibits rapid and high MB removal competency(99.99%)via synergism of adsorption,photodegradation,and Fenton-like reaction.Continuous production of O_2U^-and UOH radicles performs MB degradation and mineralization,confirmed by scavenging experiments and degradation product analysis.The local trap state Ti^(3+),Fe_3O_4,and N-carbon of the catalyst acted as active sites.It has suggested that the Ti^(3+)and N-doped dense carbon layer improve charge separation and shuttle that prolonged photo-Fenton like reaction.Moreover,the catalyst is highly stable,collectible,and recyclable up to 5 cycles with high MB degradation efficiency.This work provides a new insight into the synthesis of highly visible-light sensitized biocharsupported photocatalyst through NH_3-ambiance pyrolysis of NPs-laden biomass.展开更多
基金the National Key Research and Development Program of China (No.2017YFA0206500)the National Natural Science Foundation of China (Nos.21802161,21673275,and 21533005).
文摘Replacing Pt-based electrocatalysts for the oxygen reduction reaction (ORR) with high performance and low-cost non-precious metal catalysts is crucial for the commercialization of fuel cells.Herein,we present a highly efficient Fe-N-C porous ORR electrocatalyst with FeNx moieties promoted by Fe2N nanoparticles derived from Fe-doped zeolitic imidazolate framework.The best-performing Fe-N-C/HPC-NH3 catalyst exhibits a superior ORR activity with an onset (E0) and half-wave (E1/2) potential of 0.945 and 0.803 V (RHE),respectively,which is comparable to those of the commercial Pt/C in acidic media.Probing and acid-leaching experiments prove that FeNx moieties play an important role in the ORR and the Fe2N can further improve the ORR activity.Density functional theory calculation reveals a synergistic effect that the existence of Fe2N weakens the adsorption of ORR intermediates on active sites and lowers the reaction free energy of the potential limiting step,thus facilitating the ORR.Both experimental evidence and theoretical analysis for the enhancement of ORR activity by Fe2N decoration in Fe-N-C catalyst might inspire a new strategy for rational design of high performance non-precious metal catalysts.
文摘A novel coordination polymer, [Fe(C 5H 4NCOO) 2] n, was synthesized by hydrothermal reaction and characterized by elemental analysis as well as IR spectroscopy. The crystal structure (with a novel 3-D network) of this compound belongs to monoclinic, space group P2 1/n, a=0.49544(1) nm, b=1.32443(2) nm, c=1.04983(1) nm, β=101.586(1)°. The diffuse reflectance spectra (200～2500 nm) showed that the polymer had strong absorbance in 375～563 nm (E g≈2.5 eV) region and weak absorbance from 720 to 2500 nm (near infrared spectra).
基金supported by the National Basic Research Program of China (973 Program, 2014CB238903)the National Natural Science Foundation of China (Nos. 41672144, 41173032, and 41373110)
文摘A series of new biochar-supported composite based on the combination of biochar and metallic nanoparticles(NPs)were produced through single-step pyrolysis of FeCl_3–Ti(OBu)_4 laden agar biomass under NH_3 environment.The physiochemical properties of composites were characterized thoroughly.It has found that heating temperature and N-doping through NH_3-ambiance pyrolysis significantly influence the visible-light sensitivity and bandgap energy of composites.The catalytic activities of composites were measured by degradation of Methylene Blue(MB)in the presence or absence of H_2O_2 and visible-light irradiation.Our best catalyst(N–TiO_2–Fe_3O_4-biochar)exhibits rapid and high MB removal competency(99.99%)via synergism of adsorption,photodegradation,and Fenton-like reaction.Continuous production of O_2U^-and UOH radicles performs MB degradation and mineralization,confirmed by scavenging experiments and degradation product analysis.The local trap state Ti^(3+),Fe_3O_4,and N-carbon of the catalyst acted as active sites.It has suggested that the Ti^(3+)and N-doped dense carbon layer improve charge separation and shuttle that prolonged photo-Fenton like reaction.Moreover,the catalyst is highly stable,collectible,and recyclable up to 5 cycles with high MB degradation efficiency.This work provides a new insight into the synthesis of highly visible-light sensitized biocharsupported photocatalyst through NH_3-ambiance pyrolysis of NPs-laden biomass.
