Two mono iron complexes Fe（CO）2PR3（NN） （R = Cy （3）, Ph （4）, NN = o-phenylenediamine dianion ligand, N2H2Ph2-） derived from the ligand substitution of Fe（CO）3hPR3 by the NN ligand were isolated and structur...Two mono iron complexes Fe（CO）2PR3（NN） （R = Cy （3）, Ph （4）, NN = o-phenylenediamine dianion ligand, N2H2Ph2-） derived from the ligand substitution of Fe（CO）3hPR3 by the NN ligand were isolated and structurally characterized by single crystal X-ray diffraction. They have a similar first coordination sphere and oxidation state of the iron center as the [Fe]-hydrogenase active site, and can be a model of it IR demonstrated that the effect of the NN ligand on the coordinated CO stretch- ing frequencies was due to its excellent electron donating ability. The reversible protonation/deprotonation of the NN ligand was identified by infrared spectroscopy and density functional theory computation. The NN ligand is an effective proton acceptor as the internal base of the cysteine thiolate ligand in [Fe]-hydrogenase. The electrochemical properties of complexes 3, 4 were investigated by cyclic voltammograms. Complex 3 catalyzed the transfer hydrogenation of benzoquinone to hydroquinone effectively under mild conditions.展开更多
The kinetic of the direct COhydrogenation to higher hydrocarbons via Fischer–Tropsch synthesis（FTS）and reverse water-gas shift reaction（RWGS） mechanisms over a series of precipitated Fe/Cu/K catalysts with variou...The kinetic of the direct COhydrogenation to higher hydrocarbons via Fischer–Tropsch synthesis（FTS）and reverse water-gas shift reaction（RWGS） mechanisms over a series of precipitated Fe/Cu/K catalysts with various particle sizes was studied in a well mixed, continuous spinning basket reactor. The iron catalysts promoted with copper and potassium were prepared via precipitation technique in various alcohol/water mixtures to achieve a series of catalyst particle sizes between 38 and 14 nm. A new kinetic model for direct COhydrogenation was developed with combination of kinetic model for FTS reaction and RWGS equilibrium condition. For estimate of structure sensitivity of indirect COhydrogenation to higher hydrocarbons, the kinetic parameters of developed model are evaluated for a series of iron catalysts with various particle sizes. For kinetic study a wide range of syngas conversions have been obtained by varying experimental conditions. The results show that the new developed model fits favorably with experimental data. The values of activation energies for indirect COhydrogenation reaction are fall within the narrow range of 23–16 kJ/mol.展开更多
A cobalt-iron alloy thin-film electrode-based electrochemical hydrogen-phosphate-ion sensor was prepared by electrodepositing on an Au-coated Al2O3 substrate from an aqueous solution of metal-salts. The use of a cobal...A cobalt-iron alloy thin-film electrode-based electrochemical hydrogen-phosphate-ion sensor was prepared by electrodepositing on an Au-coated Al2O3 substrate from an aqueous solution of metal-salts. The use of a cobalt-iron alloy electrode greatly improved the hydrogen-ion sensor response performance, i.e., the sensor worked stably for more than 7 weeks and showed a quick response time of several seconds. Among the cobalt and iron alloy systems tested, the electrodeposited Co58Fe42 thin-film electrode showed the best EMF response characteristics, i.e., the sensor exhibited a linear potentiometric response to hydrogen-phosphate ion at the concentration range between 1.0 × 10–5 and 1.0 × 10–2 M with the slope of –43 mV/decade at pH 5.0 and at 30℃. A sensing mechanism of the Co-based potentiometric hydrogen-phosphate ion sensor was proposed on the basis of results of instrumental analysis.展开更多
Raman peaks at 1951 and 2165 cm^(-1) can be confirmed further by H_2/D_2 isotope exchange as H-adspecies on the doubly promoted iron catalyst for ammonia synthesis and are probably ascribed to two terminally adsorbed ...Raman peaks at 1951 and 2165 cm^(-1) can be confirmed further by H_2/D_2 isotope exchange as H-adspecies on the doubly promoted iron catalyst for ammonia synthesis and are probably ascribed to two terminally adsorbed H-species.展开更多
The zero valent iron/granular active carbon(ZVI/GAC) micro-electrolysis enhanced by ultrasound(US) coupled with hydrogen peroxide(H_2O_2) was investigated for the deep degradation of nitrobenzene-containing wastewater...The zero valent iron/granular active carbon(ZVI/GAC) micro-electrolysis enhanced by ultrasound(US) coupled with hydrogen peroxide(H_2O_2) was investigated for the deep degradation of nitrobenzene-containing wastewater. The results of scanning electron microscopy-energy dispersive X-rays analysis(SEM-EDS) demonstrated that continuously accelerated regeneration of ZVI and GAC in situ by US could improve the process for converting nitrobenzene(NB) to aniline(AN). H_2O_2 was decomposed catalytically by the byproduct Fe^(2+) ions generated in the micro-electrolysis process to hydroxyl radicals and the organic pollutants in the wastewater were finally mineralized to CO2 and H2O. Effects of the ZVI dosage, the ZVI/GAC mass ratio, the initial pH value and the H_2O_2 dosage on the efficiency for degradation of NB were studied in these experiments. The optimal operating conditions covered a ZVI dosage of 15 g/L, a ZVI/GAC mass ratio of 1:2,an initial pH value of 3 and a H_2O_2 dosage of 4 mL. In this case, the NB removal efficiency reached 97.72% and the total organic carbon(TOC) removal efficiency reached 73.42% at a NB concentration of 300 mg/L. The reduction of NB by USZVI/GAC followed the pseudo-first-order kinetics model, and the pseudo-first-order rate constants were given at different initial pH values. The reaction intermediates such as AN, benzoquinonimine, p-benzoquinone, p-nitrophenol and other organic acids were detected and a probable pathway for NB degradation has been proposed.展开更多
Hydrogen peroxide bleaching has been extensivelyused in high-yield pulp bleaching. Unfortunately,hydrogen peroxide can be decomposed underalkaline condition, especially when transition metalions exit. Experiments show...Hydrogen peroxide bleaching has been extensivelyused in high-yield pulp bleaching. Unfortunately,hydrogen peroxide can be decomposed underalkaline condition, especially when transition metalions exit. Experiments show that the valence oftransition metal ion is also responsible for thedecomposition of hydrogen peroxide.Iron ions are present in two oxidation states, Fe2+ andFe3+. They are both catalytically active to hydrogenperoxide decomposition. Because Fe3+ is brown, itcan affect the brightness of pulp directly, it can alsocombine with phenol, forming complexes which notonly are stable structures and are difficult to beremoved from pulp, but also significantly affect thebrightness of pulp because of their color.Sodium silicate and magnesium sulfate, when usedtogether, can greatly decrease hydrogen peroxidedecomposition. The optimum dosage of sodiumsilicate is about 0.1% (on solution) for Fe2~ and0.25% (on solution) for Fe3~. Adding chelants such asDTPA or EDTA with stabilizers simultaneously canobviously improve pulp brightness. For iron ions, thechelate effect of DTPA is better than that of EDTA.Under acidic conditions, sodium hyposulfite andcellulose can reduce Fe3+ to Fez+ effectively, and pulpbrightness is improved greatly. Adding sodiumthiosulfate simultaneously with magnesium sulfate,sodium silicate, and DTPA to alkaline peroxidesolution can result in higher brightness of pulp.pH is a key parameter during hydrogen peroxidebleaching, the optimum pH value should be 10.5-12.展开更多
The hydrogen content in liquid binary aluminum alloys with 1,3,5 and 8 wt% iron has been determined in the temperature range from 973K to 1103K.The hydrogen content in molten Al-Fe alloys increases remarkably when the...The hydrogen content in liquid binary aluminum alloys with 1,3,5 and 8 wt% iron has been determined in the temperature range from 973K to 1103K.The hydrogen content in molten Al-Fe alloys increases remarkably when the temperature of the melt rises to about 1053K.This work indicates that the alloying element iron plays an important role in hydrogen content in superheated Al-Fe alloy melts below about 1053K.The results make it clear that the hydrogen content in the melt aluminum reduces with the increasing element levels.A conclusion is drawn that the degree of gassing in molten Al-Fe alloys is bound up with the properties of oxide film of aluminum alloy melts.The element iron has no effect on the compact structure of oxide film in aluminum melts.The effects of alloying element are theoretically analyzed in terms of Wagner interaction parameter.According to the values of the first order interaction parameter,it is concluded that the interaction between iron atom and aluminum is much stronger than that between hydrogen atom and aluminum,and the addition of the alloying element decreases the affinity of liquid aluminum for hydrogen.展开更多
CO2 hydrogenation reaction was performed on precipitated iron catalysts which were promoted by Si, Zn, K and Cu. The optimum SiO2 content in the catalysts is about 15 wt% relative to Fe2O3 mass. With reaction temperat...CO2 hydrogenation reaction was performed on precipitated iron catalysts which were promoted by Si, Zn, K and Cu. The optimum SiO2 content in the catalysts is about 15 wt% relative to Fe2O3 mass. With reaction temperature raised, CO2 conversion is increased continually, but CO and CH4 selectivity only fluctuate in a narrow range which is beneficial to the synthesis of C2+ hydrocarbons. Two kinds of catalyst filling constitution were experimentally compared in order to increase the yield of C5+ hydrocarbons.展开更多
The discrete variational method (DVM)and cluster model are used to study the electronic structure and atomic configuration of the hydrogen-vacancy complex in iron.The optimum location of hydrogen atom in the monovacan...The discrete variational method (DVM)and cluster model are used to study the electronic structure and atomic configuration of the hydrogen-vacancy complex in iron.The optimum location of hydrogen atom in the monovacancy in iron is determined by minimizing the total energy and the bond characteristic between hydrogen and iron atoms is analyzed Meanwhile, the positron annihilation characteristics of the hydrogen -vacancy complex is also calculated.展开更多
基金supported by the National Natural Science Foundation of China(21103121,21276187)Tianjin Municipal Natural Science Foundation(13JCQNJC05800)the Specialized Research Fund for the Doctoral Program of Higher Education(20121317110009)~~
文摘Two mono iron complexes Fe（CO）2PR3（NN） （R = Cy （3）, Ph （4）, NN = o-phenylenediamine dianion ligand, N2H2Ph2-） derived from the ligand substitution of Fe（CO）3hPR3 by the NN ligand were isolated and structurally characterized by single crystal X-ray diffraction. They have a similar first coordination sphere and oxidation state of the iron center as the [Fe]-hydrogenase active site, and can be a model of it IR demonstrated that the effect of the NN ligand on the coordinated CO stretch- ing frequencies was due to its excellent electron donating ability. The reversible protonation/deprotonation of the NN ligand was identified by infrared spectroscopy and density functional theory computation. The NN ligand is an effective proton acceptor as the internal base of the cysteine thiolate ligand in [Fe]-hydrogenase. The electrochemical properties of complexes 3, 4 were investigated by cyclic voltammograms. Complex 3 catalyzed the transfer hydrogenation of benzoquinone to hydroquinone effectively under mild conditions.
基金Financial support of the Ferdowsi University of Mashhad,Iran(2/38699-21/7/94)
文摘The kinetic of the direct COhydrogenation to higher hydrocarbons via Fischer–Tropsch synthesis（FTS）and reverse water-gas shift reaction（RWGS） mechanisms over a series of precipitated Fe/Cu/K catalysts with various particle sizes was studied in a well mixed, continuous spinning basket reactor. The iron catalysts promoted with copper and potassium were prepared via precipitation technique in various alcohol/water mixtures to achieve a series of catalyst particle sizes between 38 and 14 nm. A new kinetic model for direct COhydrogenation was developed with combination of kinetic model for FTS reaction and RWGS equilibrium condition. For estimate of structure sensitivity of indirect COhydrogenation to higher hydrocarbons, the kinetic parameters of developed model are evaluated for a series of iron catalysts with various particle sizes. For kinetic study a wide range of syngas conversions have been obtained by varying experimental conditions. The results show that the new developed model fits favorably with experimental data. The values of activation energies for indirect COhydrogenation reaction are fall within the narrow range of 23–16 kJ/mol.
文摘A cobalt-iron alloy thin-film electrode-based electrochemical hydrogen-phosphate-ion sensor was prepared by electrodepositing on an Au-coated Al2O3 substrate from an aqueous solution of metal-salts. The use of a cobalt-iron alloy electrode greatly improved the hydrogen-ion sensor response performance, i.e., the sensor worked stably for more than 7 weeks and showed a quick response time of several seconds. Among the cobalt and iron alloy systems tested, the electrodeposited Co58Fe42 thin-film electrode showed the best EMF response characteristics, i.e., the sensor exhibited a linear potentiometric response to hydrogen-phosphate ion at the concentration range between 1.0 × 10–5 and 1.0 × 10–2 M with the slope of –43 mV/decade at pH 5.0 and at 30℃. A sensing mechanism of the Co-based potentiometric hydrogen-phosphate ion sensor was proposed on the basis of results of instrumental analysis.
基金Supported from the State Key Laboratory for Physical Chemistry of the Solid Surface of Xiamen University.
文摘Raman peaks at 1951 and 2165 cm^(-1) can be confirmed further by H_2/D_2 isotope exchange as H-adspecies on the doubly promoted iron catalyst for ammonia synthesis and are probably ascribed to two terminally adsorbed H-species.
基金supported by the Natural Science Foundation of China (U1610106)the Excellent Youth Science and Technology Foundation of Province Shanxi of China (2014021007)+1 种基金the Specialized Research Fund for Sanjin Scholars Pragram of Shanxi Prouince (201707)the North University of China Fund for Distinguished Young Scholars (201701)
文摘The zero valent iron/granular active carbon(ZVI/GAC) micro-electrolysis enhanced by ultrasound(US) coupled with hydrogen peroxide(H_2O_2) was investigated for the deep degradation of nitrobenzene-containing wastewater. The results of scanning electron microscopy-energy dispersive X-rays analysis(SEM-EDS) demonstrated that continuously accelerated regeneration of ZVI and GAC in situ by US could improve the process for converting nitrobenzene(NB) to aniline(AN). H_2O_2 was decomposed catalytically by the byproduct Fe^(2+) ions generated in the micro-electrolysis process to hydroxyl radicals and the organic pollutants in the wastewater were finally mineralized to CO2 and H2O. Effects of the ZVI dosage, the ZVI/GAC mass ratio, the initial pH value and the H_2O_2 dosage on the efficiency for degradation of NB were studied in these experiments. The optimal operating conditions covered a ZVI dosage of 15 g/L, a ZVI/GAC mass ratio of 1:2,an initial pH value of 3 and a H_2O_2 dosage of 4 mL. In this case, the NB removal efficiency reached 97.72% and the total organic carbon(TOC) removal efficiency reached 73.42% at a NB concentration of 300 mg/L. The reduction of NB by USZVI/GAC followed the pseudo-first-order kinetics model, and the pseudo-first-order rate constants were given at different initial pH values. The reaction intermediates such as AN, benzoquinonimine, p-benzoquinone, p-nitrophenol and other organic acids were detected and a probable pathway for NB degradation has been proposed.
文摘Hydrogen peroxide bleaching has been extensivelyused in high-yield pulp bleaching. Unfortunately,hydrogen peroxide can be decomposed underalkaline condition, especially when transition metalions exit. Experiments show that the valence oftransition metal ion is also responsible for thedecomposition of hydrogen peroxide.Iron ions are present in two oxidation states, Fe2+ andFe3+. They are both catalytically active to hydrogenperoxide decomposition. Because Fe3+ is brown, itcan affect the brightness of pulp directly, it can alsocombine with phenol, forming complexes which notonly are stable structures and are difficult to beremoved from pulp, but also significantly affect thebrightness of pulp because of their color.Sodium silicate and magnesium sulfate, when usedtogether, can greatly decrease hydrogen peroxidedecomposition. The optimum dosage of sodiumsilicate is about 0.1% (on solution) for Fe2~ and0.25% (on solution) for Fe3~. Adding chelants such asDTPA or EDTA with stabilizers simultaneously canobviously improve pulp brightness. For iron ions, thechelate effect of DTPA is better than that of EDTA.Under acidic conditions, sodium hyposulfite andcellulose can reduce Fe3+ to Fez+ effectively, and pulpbrightness is improved greatly. Adding sodiumthiosulfate simultaneously with magnesium sulfate,sodium silicate, and DTPA to alkaline peroxidesolution can result in higher brightness of pulp.pH is a key parameter during hydrogen peroxidebleaching, the optimum pH value should be 10.5-12.
文摘The hydrogen content in liquid binary aluminum alloys with 1,3,5 and 8 wt% iron has been determined in the temperature range from 973K to 1103K.The hydrogen content in molten Al-Fe alloys increases remarkably when the temperature of the melt rises to about 1053K.This work indicates that the alloying element iron plays an important role in hydrogen content in superheated Al-Fe alloy melts below about 1053K.The results make it clear that the hydrogen content in the melt aluminum reduces with the increasing element levels.A conclusion is drawn that the degree of gassing in molten Al-Fe alloys is bound up with the properties of oxide film of aluminum alloy melts.The element iron has no effect on the compact structure of oxide film in aluminum melts.The effects of alloying element are theoretically analyzed in terms of Wagner interaction parameter.According to the values of the first order interaction parameter,it is concluded that the interaction between iron atom and aluminum is much stronger than that between hydrogen atom and aluminum,and the addition of the alloying element decreases the affinity of liquid aluminum for hydrogen.
文摘CO2 hydrogenation reaction was performed on precipitated iron catalysts which were promoted by Si, Zn, K and Cu. The optimum SiO2 content in the catalysts is about 15 wt% relative to Fe2O3 mass. With reaction temperature raised, CO2 conversion is increased continually, but CO and CH4 selectivity only fluctuate in a narrow range which is beneficial to the synthesis of C2+ hydrocarbons. Two kinds of catalyst filling constitution were experimentally compared in order to increase the yield of C5+ hydrocarbons.
文摘The discrete variational method (DVM)and cluster model are used to study the electronic structure and atomic configuration of the hydrogen-vacancy complex in iron.The optimum location of hydrogen atom in the monovacancy in iron is determined by minimizing the total energy and the bond characteristic between hydrogen and iron atoms is analyzed Meanwhile, the positron annihilation characteristics of the hydrogen -vacancy complex is also calculated.
