Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxi...Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxidative desulfurization activity. In this study, a new family of caprolactam-based acidic DESs was prepared with different molar ratios of caprolactam and oxalic acid. The prepared DESs were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance, and thermogravimetric analyses. These DESs were employed for oxidative desulfurization reactions and the desulfurization efficiency was found to vary regularly with the DES composition. The factors influencing the removal of dibenzothiophene were systematically investigated and the desulfurization efficiency of the caprolactam-based acidic DESs reached as high as 98% under optimal conditions. The removal of different sulfur compounds followed the order： dibenzothiophene 4,6-dimethyldibenzothiophene benzothiophene. The combined experimental data and characterization results revealed that the oxidative desulfurization efficiency of the system was influenced by the hydrogen bonding interactions with the DES, which can be optimized by adjusting the DES composition. These findings regarding hydrogen bonding in DESs provide new insight for better understanding of the mechanism of diesel deep desulfurization processes.展开更多
In this work,the growth of copper sulfide crystal onto azurite surfaces during sulfurization and its response to flotation are investigated.Filed emission scanning electron microscopy-energy dispersive X-ray spectrosc...In this work,the growth of copper sulfide crystal onto azurite surfaces during sulfurization and its response to flotation are investigated.Filed emission scanning electron microscopy-energy dispersive X-ray spectroscopy(FESEM) and X-ray diffraction(XRD) studies confirmed that the sulfurization of azurite is not limited to the mineral surface,but rather penetrates into the bulk to form covellite crystal(synCuS),creating favorable conditions for the stable adsorption of xanthate and greatly promoting the azurite flotation.Additionally,as demonstrated by X-ray photoelectron spectroscopy(XPS) and time of flight secondary ion mass spectrometry(TOF-SIMS) analyses,a redox reaction occurred during this process,and Cu(Ⅱ) onto the mineral surface was reduced to Cu(Ⅰ).Correspondingly,reduced S^(2-) was oxidized to(S_(2))^(2-),(S_n)^(-2),and even to deeper oxidation state S~0,(S_(x)O_(y))^(n-) and SO_(4)^(2-).Excess sodium sulfide strengthens copper sulfide to form onto the azurite surface,and provides enough raw material for crystal copper sulfide to grow,resulting in the formation of "flake-like" covellite with a better crystallinity.However,the floatability of azurite decreased dramatically under this condition,because the generated massive colloidal copper sulfide in flotation pulp deteriorates the flotation environment,resulting in a decreased effective adsorption of collector onto azurite surfaces.展开更多
The change of iron composition as well as the removal of copper from iron was investigated in the reduction process, and a new way to deal with copper slag was proposed. The iron in copper slag exists mainly in the fo...The change of iron composition as well as the removal of copper from iron was investigated in the reduction process, and a new way to deal with copper slag was proposed. The iron in copper slag exists mainly in the form of fayalite, and the copper sulfide content accounts for just about 50%. Therefore, the magnetic separation as well as grinding floatation method is not suitable, and a pyrogenic treatment on copper slag is necessary. The carhurization and desulfurization process is restricted to a degree within the carbon composite pellets, and copper matte phase pre- cipitates from copper slag in the reduction process, which is immiscible with molten iron and slag. The copper con- tent decreases to 0.4% as the carbon content in molten iron reaches 3.84%, and the removal ratio of copper from molten iron approaches to 80%. The reduction and sulfurization process can be eompleted in one step, and the copper is separated from iron based on the ternary system of iron-matte-slag.展开更多
Surface treatment is an effective method to improve the photoelectrochemical(PEC) performance of photoelectrodes. Herein, we introduced a novel strategy of surface sulfurization to modify hematite(a-Fe2 O3)nanorods gr...Surface treatment is an effective method to improve the photoelectrochemical(PEC) performance of photoelectrodes. Herein, we introduced a novel strategy of surface sulfurization to modify hematite(a-Fe2 O3)nanorods grown in an aqueous solution, which triggered encouraging improvement in PEC performances.In comparison to the solution-grown pristine a-Fe2 O3 nanorod photoanode that is PEC inefficient and always needs high temperature(>600 °C) activation, the surface sulfurized a-Fe2 O3 nanorods show photocurrent density increased by orders of magnitude, reaching 0.46 mA cmà2 at 1.23 V vs. RHE(reversible hydrogen electrode) under simulated solar illumination. This improvement in PEC performances should be attributed to the synergy of the increased carrier density, the reduced surface charge carrier recombination and the accelerated water oxidation kinetics at the a-Fe2 O3/electrolyte interface, as induced by the incorporation of S ions and the formation of multi-state S species(Fe-Sx-Oy) at the surface of a-Fe2 O3 nanorods. This study paves a new and facile approach to activate a-Fe2 O3 and even other metal oxides as photoelectrodes for improved PEC water splitting performances, by engineering the surface structure to relieve the bottlenecks of charge transfer dynamics and redox reaction kinetics at the electrode/electrolyte interface.展开更多
基金supported by the National Natural Science Foundation of China(21676230,21373177)~~
文摘Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxidative desulfurization activity. In this study, a new family of caprolactam-based acidic DESs was prepared with different molar ratios of caprolactam and oxalic acid. The prepared DESs were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance, and thermogravimetric analyses. These DESs were employed for oxidative desulfurization reactions and the desulfurization efficiency was found to vary regularly with the DES composition. The factors influencing the removal of dibenzothiophene were systematically investigated and the desulfurization efficiency of the caprolactam-based acidic DESs reached as high as 98% under optimal conditions. The removal of different sulfur compounds followed the order： dibenzothiophene 4,6-dimethyldibenzothiophene benzothiophene. The combined experimental data and characterization results revealed that the oxidative desulfurization efficiency of the system was influenced by the hydrogen bonding interactions with the DES, which can be optimized by adjusting the DES composition. These findings regarding hydrogen bonding in DESs provide new insight for better understanding of the mechanism of diesel deep desulfurization processes.
基金supported by the National Natural Science Foundation of China (No. 52074138)Basic research project of Yunnan Province (No. 202001AS070030)Open Foundation of State Key Laboratory of Mineral Processing (BGRIMM-KJSKL2020-03)。
文摘In this work,the growth of copper sulfide crystal onto azurite surfaces during sulfurization and its response to flotation are investigated.Filed emission scanning electron microscopy-energy dispersive X-ray spectroscopy(FESEM) and X-ray diffraction(XRD) studies confirmed that the sulfurization of azurite is not limited to the mineral surface,but rather penetrates into the bulk to form covellite crystal(synCuS),creating favorable conditions for the stable adsorption of xanthate and greatly promoting the azurite flotation.Additionally,as demonstrated by X-ray photoelectron spectroscopy(XPS) and time of flight secondary ion mass spectrometry(TOF-SIMS) analyses,a redox reaction occurred during this process,and Cu(Ⅱ) onto the mineral surface was reduced to Cu(Ⅰ).Correspondingly,reduced S^(2-) was oxidized to(S_(2))^(2-),(S_n)^(-2),and even to deeper oxidation state S~0,(S_(x)O_(y))^(n-) and SO_(4)^(2-).Excess sodium sulfide strengthens copper sulfide to form onto the azurite surface,and provides enough raw material for crystal copper sulfide to grow,resulting in the formation of "flake-like" covellite with a better crystallinity.However,the floatability of azurite decreased dramatically under this condition,because the generated massive colloidal copper sulfide in flotation pulp deteriorates the flotation environment,resulting in a decreased effective adsorption of collector onto azurite surfaces.
基金Item Sponsored by National Natural Science Foundation of China(51404075)
文摘The change of iron composition as well as the removal of copper from iron was investigated in the reduction process, and a new way to deal with copper slag was proposed. The iron in copper slag exists mainly in the form of fayalite, and the copper sulfide content accounts for just about 50%. Therefore, the magnetic separation as well as grinding floatation method is not suitable, and a pyrogenic treatment on copper slag is necessary. The carhurization and desulfurization process is restricted to a degree within the carbon composite pellets, and copper matte phase pre- cipitates from copper slag in the reduction process, which is immiscible with molten iron and slag. The copper con- tent decreases to 0.4% as the carbon content in molten iron reaches 3.84%, and the removal ratio of copper from molten iron approaches to 80%. The reduction and sulfurization process can be eompleted in one step, and the copper is separated from iron based on the ternary system of iron-matte-slag.
基金financially supported by the National Natural Science Foundation of China (21875183, 51672210 and 51888103)the National Program for Support of Top-notch Young Professionalsthe ‘‘Fundamental Research Funds for the Central Universities”
文摘Surface treatment is an effective method to improve the photoelectrochemical(PEC) performance of photoelectrodes. Herein, we introduced a novel strategy of surface sulfurization to modify hematite(a-Fe2 O3)nanorods grown in an aqueous solution, which triggered encouraging improvement in PEC performances.In comparison to the solution-grown pristine a-Fe2 O3 nanorod photoanode that is PEC inefficient and always needs high temperature(>600 °C) activation, the surface sulfurized a-Fe2 O3 nanorods show photocurrent density increased by orders of magnitude, reaching 0.46 mA cmà2 at 1.23 V vs. RHE(reversible hydrogen electrode) under simulated solar illumination. This improvement in PEC performances should be attributed to the synergy of the increased carrier density, the reduced surface charge carrier recombination and the accelerated water oxidation kinetics at the a-Fe2 O3/electrolyte interface, as induced by the incorporation of S ions and the formation of multi-state S species(Fe-Sx-Oy) at the surface of a-Fe2 O3 nanorods. This study paves a new and facile approach to activate a-Fe2 O3 and even other metal oxides as photoelectrodes for improved PEC water splitting performances, by engineering the surface structure to relieve the bottlenecks of charge transfer dynamics and redox reaction kinetics at the electrode/electrolyte interface.
