Conversion of CO2 into CO using plasma processing powered by renewable energy is a promising method to convert intermittent sustainable electricity into storable chemical energy.Despite extensive research efforts worl...Conversion of CO2 into CO using plasma processing powered by renewable energy is a promising method to convert intermittent sustainable electricity into storable chemical energy.Despite extensive research efforts worldwide,there is currently no process that achieves economically viable values for both CO2 conversion fraction and energy recovery efficiency simultaneously.Here we demonstrate that a process that utilizes the Boudouard reaction,CO^2++C→2 CO,driven by a thermal plasma allows both 95%CO2 conversion to CO and energy recovery efficiency of 70%,values far higher than seen so far.By comparing the conversion process with and without CO2 excitation by a plasma and by using optical emission spectroscopy we show that the improved performance is due to a novel mode of operation where CO2 is pyrolyzed into an active mixture of CO,O and O2 by an arc discharge which is then introduced into a fixed bed to interact with carbon material.In this way,the free oxygen in the mixture combusts with carbon to form CO,and residual plasma excited CO2 is reduced by carbon.In the overall process,the endothermic Boudouard reaction is partially replaced by an exothermic reaction,and the excess electric energy to produce CO2 plasma is reused in the carbon bed.展开更多
Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impac...Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m^(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.展开更多
The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C_4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid c...The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C_4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid(i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22(i.e., MCM-22-IL)was characterized by FTIR, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to 1-butene(I/O) were investigated to correlate with surface features of MCM-22-IL. Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene(I/O) was significantly improved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length of ILs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.展开更多
Superhydrophobic coating has been widely studied for its great applicational potential, such as for corrosion protection of magnesium alloys while it has been restrained by expensive materials, sophisticated preparati...Superhydrophobic coating has been widely studied for its great applicational potential, such as for corrosion protection of magnesium alloys while it has been restrained by expensive materials, sophisticated preparation process and infirm rough structures. In this study, the electrochemical method was adopted by using a two-electrode system for rapid hydrophobic modification to obtain superhydrophobic kaolin.By mixing the modified superhydrophobic kaolin with commercial epoxy resin and polydimethylsiloxane glue, a paint can be formed and easily used on various substrates for preparation of superhydrophobic coating via spraying method. The influence factors on wettability of the modified kaolin and the mixing ratio of each component of the coating were explored. Also, the wettability, durability and anticorrosion of the prepared coating were evaluated comprehensively. The coating was able to maintain superhydrophobic after immersed in HCl solution at pH 1, the NaOH solution at pH 14, and 3.5 wt.% NaCl solution for 16, 21, 30 days, respectively. In addition, the coating exhibited 4A grade adhesion, high hydrophobicity after abraded for 200 cycles on a 600-mesh sandpaper with 100 g weight, and 99.86% anticorrosion efficiency after soaked in 3.5 wt.% NaCl solution for 20 days, demonstrating a good robustness and anti-corrosion property. Furthermore, the coating showed good transparency, flexibility and was easy to make in a large scale by the spraying method, which is of great significance to promote the practical application of superhydrophobic coatings and the anticorrosion Mg alloys.展开更多
The commercial sulfate process for pigment production uses concentrated sulfuric acid(N 85 wt% H_2SO_4) as feeding material and discharges 8–10 tons of spend dilute acid(20 wt% H_2SO_4) per ton of product. Re-using s...The commercial sulfate process for pigment production uses concentrated sulfuric acid(N 85 wt% H_2SO_4) as feeding material and discharges 8–10 tons of spend dilute acid(20 wt% H_2SO_4) per ton of product. Re-using spend acid to leach ilmenite can cut the waste emission and save fresh feeding acid. However, the leaching reaction with dilute acid is very slow and the digestion efficiency is fairly low. This paper describes a wet-milling process to enhance the dilute-acid leaching of ilmenite that makes it possible to produce TiO_2 pigment in a more environmentally benign routine. The leaching kinetic study of unmilled ilmenite, dry milled 60 min ilmenite and wet milled 60 min ilmenite was conducted by revision of the shrinking core model(SCM), incorporation of particle size distribution(PSD) into SCM. The results revealed that mechano-chemical activation method significantly increased the leaching efficiency of titanium from 36% to 76% by reducing the particle size and increasing the reaction contact area. On the other hand, the milling process increased the lattice deformation and amorphization of crystalline, which lowered the activation energies in the leaching process. Compared with dry milling operation, wet milling is more effective, the particle size distribution of wet-milled ilmenite was much narrower, smaller, and more uniform. Wet milling of ilmenite makes the leaching reaction with dilute acid(60 wt% H_2 SO_4) practicable and the re-use of spend acid becomes possible and economical.展开更多
Doping is a reasonable solution to improve the electronic structure and surface properties of nanomaterials.Herein,we propose a rapid and simple methodology,flame synthesis,as an effective preparation strategy for inc...Doping is a reasonable solution to improve the electronic structure and surface properties of nanomaterials.Herein,we propose a rapid and simple methodology,flame synthesis,as an effective preparation strategy for incorporating high-valence metal ions(Ti^(4+),Sn^(4+),and Zr^(4+))into ultrasmall Fe_(2)O_(3)on carbon nanotube support(i.e.,M-FeO-CNT).The resulting materials exhibit not only a boosted Na+adsorption as shown by density functional theory(DFT)calculations,but also display an increased oxygen deficiency.The electrochemical activity and charge transfer efficiency of Fe 2 O 3 can be improved by reasonably sub-stituting Fe 3+with Ti^(4+),Sn^(4+),and Zr^(4+).The electrochemical investigation of Ti-doped Fe 2 O 3(Ti-FeO-CNT)electrode demonstrates a splendid specific capacitance of 1.25 F cm^(−2)at 1 mA cm^(−2)in 1 M Na_(2)SO_(4).This is significantly higher as compared to the capacitance of 0.48 F cm^(−2).Flexible solid-state asymmetric su-percapacitor Ti-FeO-CNT//MnO_(2)is verified with operating voltage of 2.0 V and stability over 3000 cycles,and delivers a high energy density of 2.14 mWh cm^(−3)at power density of 25 mW cm−3.The flame synthesis is expected to be widely applicable for the preparation of high-valence metal ions doped nanosized Fe_(2)O_(3)functionalized materials,thus opening up new avenues for energy and catalysis research.展开更多
Designing of hetero-atomic doped carbon-based systems through pyrolysis of abundant element organic precursors is a novel approach to construct rational porous carbon materials.Herein,a highly-cross-linked triazine po...Designing of hetero-atomic doped carbon-based systems through pyrolysis of abundant element organic precursors is a novel approach to construct rational porous carbon materials.Herein,a highly-cross-linked triazine polymer is employed to fabricate N,P co-doped porous carbon(A-TDP-12)with tunable active nitrogen in the carbon framework for simultaneous enhancement of CO_(2) capture capability and Supercapacitance(SC).The synthesized A-TDP-12 possesses a typical hierarchically porous framework(micro-pores and meso-pores)with a large surface area(1332 m^(2) g^(-1))and a rich content of N(7.89 at.%)and P(0.74 at.%).It delivers a CO_(2) adsorption capacity of 1.52 and 5.68 mmol g^(-1) at 1 and 5 bar,respectively,with almost no decay after successive 8 recycles.In 6 M KOH aqueous electrolyte,A-TDP-12 exhibits a superior specific capacitance of 172.7 F g^(-1) at a current density of 1 A g^(-1).Even at a high current density of 10 A g^(-1),80%of its initial capacity still remains.This work not only offers a novel strategy for fabricating promising adsorbents and electrodes for CO_(2) uptake and SCs,but also provides new insights into design of porous carbon material for related applications.展开更多
基金supported by the National Natural Science Foundation of China(Grants nos.11775155,51561135013,21603202)。
文摘Conversion of CO2 into CO using plasma processing powered by renewable energy is a promising method to convert intermittent sustainable electricity into storable chemical energy.Despite extensive research efforts worldwide,there is currently no process that achieves economically viable values for both CO2 conversion fraction and energy recovery efficiency simultaneously.Here we demonstrate that a process that utilizes the Boudouard reaction,CO^2++C→2 CO,driven by a thermal plasma allows both 95%CO2 conversion to CO and energy recovery efficiency of 70%,values far higher than seen so far.By comparing the conversion process with and without CO2 excitation by a plasma and by using optical emission spectroscopy we show that the improved performance is due to a novel mode of operation where CO2 is pyrolyzed into an active mixture of CO,O and O2 by an arc discharge which is then introduced into a fixed bed to interact with carbon material.In this way,the free oxygen in the mixture combusts with carbon to form CO,and residual plasma excited CO2 is reduced by carbon.In the overall process,the endothermic Boudouard reaction is partially replaced by an exothermic reaction,and the excess electric energy to produce CO2 plasma is reused in the carbon bed.
基金Supported by the National Natural Science Foundation of China(No.21276163,and No.21576168)
文摘Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m^(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.
基金Supported by the National Natural Science Foundation of China(21576168,21276163)
文摘The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C_4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid(i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22(i.e., MCM-22-IL)was characterized by FTIR, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to 1-butene(I/O) were investigated to correlate with surface features of MCM-22-IL. Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene(I/O) was significantly improved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length of ILs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.
基金the financial support of the National Natural Science Foundation of China (Grant No. 21978182)。
文摘Superhydrophobic coating has been widely studied for its great applicational potential, such as for corrosion protection of magnesium alloys while it has been restrained by expensive materials, sophisticated preparation process and infirm rough structures. In this study, the electrochemical method was adopted by using a two-electrode system for rapid hydrophobic modification to obtain superhydrophobic kaolin.By mixing the modified superhydrophobic kaolin with commercial epoxy resin and polydimethylsiloxane glue, a paint can be formed and easily used on various substrates for preparation of superhydrophobic coating via spraying method. The influence factors on wettability of the modified kaolin and the mixing ratio of each component of the coating were explored. Also, the wettability, durability and anticorrosion of the prepared coating were evaluated comprehensively. The coating was able to maintain superhydrophobic after immersed in HCl solution at pH 1, the NaOH solution at pH 14, and 3.5 wt.% NaCl solution for 16, 21, 30 days, respectively. In addition, the coating exhibited 4A grade adhesion, high hydrophobicity after abraded for 200 cycles on a 600-mesh sandpaper with 100 g weight, and 99.86% anticorrosion efficiency after soaked in 3.5 wt.% NaCl solution for 20 days, demonstrating a good robustness and anti-corrosion property. Furthermore, the coating showed good transparency, flexibility and was easy to make in a large scale by the spraying method, which is of great significance to promote the practical application of superhydrophobic coatings and the anticorrosion Mg alloys.
基金Supported by the National Natural Science Foundation of China(21236004)
文摘The commercial sulfate process for pigment production uses concentrated sulfuric acid(N 85 wt% H_2SO_4) as feeding material and discharges 8–10 tons of spend dilute acid(20 wt% H_2SO_4) per ton of product. Re-using spend acid to leach ilmenite can cut the waste emission and save fresh feeding acid. However, the leaching reaction with dilute acid is very slow and the digestion efficiency is fairly low. This paper describes a wet-milling process to enhance the dilute-acid leaching of ilmenite that makes it possible to produce TiO_2 pigment in a more environmentally benign routine. The leaching kinetic study of unmilled ilmenite, dry milled 60 min ilmenite and wet milled 60 min ilmenite was conducted by revision of the shrinking core model(SCM), incorporation of particle size distribution(PSD) into SCM. The results revealed that mechano-chemical activation method significantly increased the leaching efficiency of titanium from 36% to 76% by reducing the particle size and increasing the reaction contact area. On the other hand, the milling process increased the lattice deformation and amorphization of crystalline, which lowered the activation energies in the leaching process. Compared with dry milling operation, wet milling is more effective, the particle size distribution of wet-milled ilmenite was much narrower, smaller, and more uniform. Wet milling of ilmenite makes the leaching reaction with dilute acid(60 wt% H_2 SO_4) practicable and the re-use of spend acid becomes possible and economical.
基金supported by the National Natu-ral Science Foundation of China(No.21978182)the Miaozi Project in Science and Technology Innovation Program of Sichuan Province(No.21-YCG021).
文摘Doping is a reasonable solution to improve the electronic structure and surface properties of nanomaterials.Herein,we propose a rapid and simple methodology,flame synthesis,as an effective preparation strategy for incorporating high-valence metal ions(Ti^(4+),Sn^(4+),and Zr^(4+))into ultrasmall Fe_(2)O_(3)on carbon nanotube support(i.e.,M-FeO-CNT).The resulting materials exhibit not only a boosted Na+adsorption as shown by density functional theory(DFT)calculations,but also display an increased oxygen deficiency.The electrochemical activity and charge transfer efficiency of Fe 2 O 3 can be improved by reasonably sub-stituting Fe 3+with Ti^(4+),Sn^(4+),and Zr^(4+).The electrochemical investigation of Ti-doped Fe 2 O 3(Ti-FeO-CNT)electrode demonstrates a splendid specific capacitance of 1.25 F cm^(−2)at 1 mA cm^(−2)in 1 M Na_(2)SO_(4).This is significantly higher as compared to the capacitance of 0.48 F cm^(−2).Flexible solid-state asymmetric su-percapacitor Ti-FeO-CNT//MnO_(2)is verified with operating voltage of 2.0 V and stability over 3000 cycles,and delivers a high energy density of 2.14 mWh cm^(−3)at power density of 25 mW cm−3.The flame synthesis is expected to be widely applicable for the preparation of high-valence metal ions doped nanosized Fe_(2)O_(3)functionalized materials,thus opening up new avenues for energy and catalysis research.
基金supported by the National Natural Science Foundation of China (21978182)
文摘Designing of hetero-atomic doped carbon-based systems through pyrolysis of abundant element organic precursors is a novel approach to construct rational porous carbon materials.Herein,a highly-cross-linked triazine polymer is employed to fabricate N,P co-doped porous carbon(A-TDP-12)with tunable active nitrogen in the carbon framework for simultaneous enhancement of CO_(2) capture capability and Supercapacitance(SC).The synthesized A-TDP-12 possesses a typical hierarchically porous framework(micro-pores and meso-pores)with a large surface area(1332 m^(2) g^(-1))and a rich content of N(7.89 at.%)and P(0.74 at.%).It delivers a CO_(2) adsorption capacity of 1.52 and 5.68 mmol g^(-1) at 1 and 5 bar,respectively,with almost no decay after successive 8 recycles.In 6 M KOH aqueous electrolyte,A-TDP-12 exhibits a superior specific capacitance of 172.7 F g^(-1) at a current density of 1 A g^(-1).Even at a high current density of 10 A g^(-1),80%of its initial capacity still remains.This work not only offers a novel strategy for fabricating promising adsorbents and electrodes for CO_(2) uptake and SCs,but also provides new insights into design of porous carbon material for related applications.