Direct methanol fuel cells(DMFC) are widely considered to be an ideal green energy conversion device but their widespread applications are limited by the high price of the Pt-based catalysts and the instability in ter...Direct methanol fuel cells(DMFC) are widely considered to be an ideal green energy conversion device but their widespread applications are limited by the high price of the Pt-based catalysts and the instability in terms of surface CO toxicity in long-term operation.Herein,the PtFe alloy nanoparticles(NPs) with small particle size(~4.12 nm) supported on carbon black catalysts with different Pt/Fe atomic ratios(Pt_(1)Fe_(2)/C,Pt_(3)Fe_(4)/C,Pt_(1)Fe_(1)/C,and Pt_(2)Fe_(1)/C) are successfully prepared for enhanced anti-CO poisoning during methanol oxidation reaction(MOR).The optimal atomic ratio of Pt/Fe for the MOR is 1:2,and the mass activity of Pt_(1)Fe_(2)/C(5.40 A mg_(Pt)^(-1)) is 13.5 times higher than that of conventional commercial Pt/C(Pt/C-JM)(0.40 A mg_(Pt)^(-1)).The introduction of Fe into the Pt lattice forms the PtFe alloy phase,and the electron density of Pt is reduced after forming the PtFe alloy.In-situ Fourier transform infrared results indicate that the addition of oxyphilic metal Fe has reduced the adsorption of reactant molecules on Pt during the MOR.The doping of Fe atoms helps to desorb toxic intermediates and regenerate Pt active sites,promoting the cleavage of C-O bonds with good selectivity of CO_(2)(58.1%).Moreover,the Pt_(1)Fe_(2)/C catalyst exhibits higher CO tolerance,methanol electrooxidation activity,and long-term stability than other Pt_(x)Fe_(y)/C catalysts.展开更多
A non-noble metal oxygen reduction reaction （ORR） catalyst labeled as Co-C-N（800） was synthesized by heat-treating a mixture of urea, cobalt chloride and acetylene black for 2 h at 800 ℃ in an inert nitrogen atmo...A non-noble metal oxygen reduction reaction （ORR） catalyst labeled as Co-C-N（800） was synthesized by heat-treating a mixture of urea, cobalt chloride and acetylene black for 2 h at 800 ℃ in an inert nitrogen atmosphere. X-ray diffraction pattern indicates that a metallic β-Co is generated after the heat-treating process. The results from cyclic voltammograms show that the obtained Co-C-N（800） catalyst has good ORR catalytic activity in 0.5 mol/L H2SO4 solution. The catalyst is also good at methanol tolerance and stability in the acidic solution.展开更多
Electrochemical impedance spectroscopy (EIS) is widely used in fuel cell impedance analysis. However, for ohmic resistance (R Ω), EIS has some disadvantages such as long test period and complex data analysis with equ...Electrochemical impedance spectroscopy (EIS) is widely used in fuel cell impedance analysis. However, for ohmic resistance (R Ω), EIS has some disadvantages such as long test period and complex data analysis with equivalent circuits. Therefore, the current interruption method is explored to measure the value of RΩ in direct methanol fuel cells (DMFC) at different temperatures and current densities. It is found that RΩ decreases as temperature increase, and decreases initially and then increases as current density increases. These results are consistent with those measured by the EIS technique. In most cases, the ohmic resistances with current interruption (R iR ) are larger than those with EIS (R EIS ), but the difference is small, in the range from –0.848% to 5.337%. The errors of R iR at high current densities are less than those of R EIS . Our results show that the R iR data are reliable and easy to obtain in the measurement of ohmic resistance in DMFC.展开更多
In this study,the two-stage upflow anaerobic sludge blanket(UASB)system and batch experiments were employed to evaluate the performance of anaerobic digestion for the treatment of high concentration methanol wastewate...In this study,the two-stage upflow anaerobic sludge blanket(UASB)system and batch experiments were employed to evaluate the performance of anaerobic digestion for the treatment of high concentration methanol wastewater.The acid resistance of granular sludge and methanogenic bacteria and their metabolizing activity were investigated.The results show that the pH of the first UASB changed from 4.9 to 5.8 and 5.5 to 6.2 for the second reactor.Apparently,these were not the advisable pH levels that common metha-nogenic bacteria could accept.The methanogenic bacteria of the system,viz.Methanosarcina barkeri,had some acid resis-tance and could still degrade methanol at pH 5.0.If the meth-anogenic bacteria were trained further,their acid resistance would be improved somewhat.Granular sludge of the system could protect the methanogenic bacteria within its body against the impact of the acidic environment and make them degrade methanol at pH 4.5.The performance of granular sludge was attributed to its structure,bacteria species,and the distribution of bacterium inside the granule.展开更多
The research investigated the corrosion of the reinjection water system to ensure the safe production of the system.By analyzing the composition of the methanol-containing wastewater,the corrosion status of the inject...The research investigated the corrosion of the reinjection water system to ensure the safe production of the system.By analyzing the composition of the methanol-containing wastewater,the corrosion status of the injection water system was studied by the on-site materials 20#steel,Q235B steel and L316 steel for that the methanol-containing wastewater of a natural gas processing plant in northern Shaanxi had high acidity,Cl-and sulfide contents,salinity and corrosion.Then the grey system theory modeling software 3.0 was used to study the influence degree of various corrosion factors on the corrosion rate and depth of Q235B steel.The most important factors were determined,and countermeasures against corrosion were proposed.The results showed that L316 steel was more resistant to corrosion,and the corrosion rate was 0.0015 mm/a,which was less than the national standard(0.0760 mm/a).The maximum corrosion depth was 47.63μm,which was the lowest among the three materials.The corrosion rate and depth were the parent factors.Among the four factors of sulfide,Cl-,salinity and pH,grey relational degrees of sulfide were 0.75 and 0.80,respectively,which was the most important factor causing corrosion;using sulfur corrosion inhibitor protection method,TS-792C was selected by electrochemical method from three corrosion inhibitors.The impedance data simulation software ZSimpWin was used to simulate the equivalent circuit diagram,and the impedance of Q235B steel was the largest.The corrosion inhibition rate was up to 90.26%when corrosion rate was 0.0130 mm/a under the fitting of Tafel polarization curve,with the best anti-sulfur effect.At 80℃and a sulfide content of 300 mg/L,the corrosion rate of Q235B steel was less than 0.0760 mm/a.When the added amount was 100 mg/L,the corrosion current density and corrosion rate of the reinjection sewage was 0.462 mA/cm 2 and 0.0505 mm/a,both at the lowest values and with good temperature and sulfur resistance.展开更多
基金supported by the National Natural Science Foundation of China(22162012 and 22202089)the Youth Jinggang Scholars Program in Jiangxi Province([2019]57)+6 种基金the Thousand Talents Plan of Jiangxi Province(jxsq2019201083)the Natural Science Foundation of Jiangxi Province for Distinguished Young Scholars(20224ACB213005)the Program of Qingjiang Excellent Young Talents,Jiangxi University of Science and Technology(JXUSTQJBJ2019002)the Research Foundation of Education Bureau of Jiangxi Province of China(GJJ210833)the Foundation of State Key Laboratory of Physical Chemistry of Solid Surfaces(202022)the China Postdoctoral Science Foundation(2021M693893)the Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry(20212BCD42018)。
文摘Direct methanol fuel cells(DMFC) are widely considered to be an ideal green energy conversion device but their widespread applications are limited by the high price of the Pt-based catalysts and the instability in terms of surface CO toxicity in long-term operation.Herein,the PtFe alloy nanoparticles(NPs) with small particle size(~4.12 nm) supported on carbon black catalysts with different Pt/Fe atomic ratios(Pt_(1)Fe_(2)/C,Pt_(3)Fe_(4)/C,Pt_(1)Fe_(1)/C,and Pt_(2)Fe_(1)/C) are successfully prepared for enhanced anti-CO poisoning during methanol oxidation reaction(MOR).The optimal atomic ratio of Pt/Fe for the MOR is 1:2,and the mass activity of Pt_(1)Fe_(2)/C(5.40 A mg_(Pt)^(-1)) is 13.5 times higher than that of conventional commercial Pt/C(Pt/C-JM)(0.40 A mg_(Pt)^(-1)).The introduction of Fe into the Pt lattice forms the PtFe alloy phase,and the electron density of Pt is reduced after forming the PtFe alloy.In-situ Fourier transform infrared results indicate that the addition of oxyphilic metal Fe has reduced the adsorption of reactant molecules on Pt during the MOR.The doping of Fe atoms helps to desorb toxic intermediates and regenerate Pt active sites,promoting the cleavage of C-O bonds with good selectivity of CO_(2)(58.1%).Moreover,the Pt_(1)Fe_(2)/C catalyst exhibits higher CO tolerance,methanol electrooxidation activity,and long-term stability than other Pt_(x)Fe_(y)/C catalysts.
文摘A non-noble metal oxygen reduction reaction （ORR） catalyst labeled as Co-C-N（800） was synthesized by heat-treating a mixture of urea, cobalt chloride and acetylene black for 2 h at 800 ℃ in an inert nitrogen atmosphere. X-ray diffraction pattern indicates that a metallic β-Co is generated after the heat-treating process. The results from cyclic voltammograms show that the obtained Co-C-N（800） catalyst has good ORR catalytic activity in 0.5 mol/L H2SO4 solution. The catalyst is also good at methanol tolerance and stability in the acidic solution.
基金Supported by the National High Technology Research and Development Program of China （2007AA05Z150） the National Natural Science Foundation of China （50911140287 50973055）
文摘Electrochemical impedance spectroscopy (EIS) is widely used in fuel cell impedance analysis. However, for ohmic resistance (R Ω), EIS has some disadvantages such as long test period and complex data analysis with equivalent circuits. Therefore, the current interruption method is explored to measure the value of RΩ in direct methanol fuel cells (DMFC) at different temperatures and current densities. It is found that RΩ decreases as temperature increase, and decreases initially and then increases as current density increases. These results are consistent with those measured by the EIS technique. In most cases, the ohmic resistances with current interruption (R iR ) are larger than those with EIS (R EIS ), but the difference is small, in the range from –0.848% to 5.337%. The errors of R iR at high current densities are less than those of R EIS . Our results show that the R iR data are reliable and easy to obtain in the measurement of ohmic resistance in DMFC.
基金This work was supported by the Ministry of Construction of China,and we would like to thank the good cooperation of Wujin Fine Chemical Factory during the methanol wastewater treatment.
文摘In this study,the two-stage upflow anaerobic sludge blanket(UASB)system and batch experiments were employed to evaluate the performance of anaerobic digestion for the treatment of high concentration methanol wastewater.The acid resistance of granular sludge and methanogenic bacteria and their metabolizing activity were investigated.The results show that the pH of the first UASB changed from 4.9 to 5.8 and 5.5 to 6.2 for the second reactor.Apparently,these were not the advisable pH levels that common metha-nogenic bacteria could accept.The methanogenic bacteria of the system,viz.Methanosarcina barkeri,had some acid resis-tance and could still degrade methanol at pH 5.0.If the meth-anogenic bacteria were trained further,their acid resistance would be improved somewhat.Granular sludge of the system could protect the methanogenic bacteria within its body against the impact of the acidic environment and make them degrade methanol at pH 4.5.The performance of granular sludge was attributed to its structure,bacteria species,and the distribution of bacterium inside the granule.
文摘The research investigated the corrosion of the reinjection water system to ensure the safe production of the system.By analyzing the composition of the methanol-containing wastewater,the corrosion status of the injection water system was studied by the on-site materials 20#steel,Q235B steel and L316 steel for that the methanol-containing wastewater of a natural gas processing plant in northern Shaanxi had high acidity,Cl-and sulfide contents,salinity and corrosion.Then the grey system theory modeling software 3.0 was used to study the influence degree of various corrosion factors on the corrosion rate and depth of Q235B steel.The most important factors were determined,and countermeasures against corrosion were proposed.The results showed that L316 steel was more resistant to corrosion,and the corrosion rate was 0.0015 mm/a,which was less than the national standard(0.0760 mm/a).The maximum corrosion depth was 47.63μm,which was the lowest among the three materials.The corrosion rate and depth were the parent factors.Among the four factors of sulfide,Cl-,salinity and pH,grey relational degrees of sulfide were 0.75 and 0.80,respectively,which was the most important factor causing corrosion;using sulfur corrosion inhibitor protection method,TS-792C was selected by electrochemical method from three corrosion inhibitors.The impedance data simulation software ZSimpWin was used to simulate the equivalent circuit diagram,and the impedance of Q235B steel was the largest.The corrosion inhibition rate was up to 90.26%when corrosion rate was 0.0130 mm/a under the fitting of Tafel polarization curve,with the best anti-sulfur effect.At 80℃and a sulfide content of 300 mg/L,the corrosion rate of Q235B steel was less than 0.0760 mm/a.When the added amount was 100 mg/L,the corrosion current density and corrosion rate of the reinjection sewage was 0.462 mA/cm 2 and 0.0505 mm/a,both at the lowest values and with good temperature and sulfur resistance.
