Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multicarbon products is an efficient approach for ad-dressing the energy crisis and achieving carbon neutrality.In H-cells,achieving high-current C_(2)products is chall...Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multicarbon products is an efficient approach for ad-dressing the energy crisis and achieving carbon neutrality.In H-cells,achieving high-current C_(2)products is challenging because of the inefficient mass transfer of the catalyst and the presence of the hydrogen evolution reaction(HER).In this study,dendritic Cu/Cu_(2)O with abundant Cu^(0)/Cu^(+)interfaces and numerous dendritic curves was synthesized in a CO_(2)atmosphere,resulting in the high selectivity and current density of the C_(2)products.Dendritic Cu/Cu_(2)O achieved a C_(2)Faradaic efficiency of 69.8%and a C_(2)partial current density of 129.5 mA cm^(-2)in an H-cell.Finite element simulations showed that a dendritic structure with a high curvature generates a strong electric field,leading to a localized CO_(2)concentration.Additionally,DRT analysis showed that a dendritic struc-ture with a high curvature actively adsorbed the surrounding high concentration of CO_(2),enhancing the mass transfer rate and achieving a high current density.During the experiment,the impact of the electronic structure on the performance of the catalyst was investigated by varying the atomic ratio of Cu^(0)/Cu^(+) on the catalyst surface,which resulted in improved ethylene selectivity.Under the optimal atomic ratio of Cu^(0)/Cu^(+),the charge transfer resistance was minimized,and the desorption rate of the intermediates was low,favoring C_(2) generation.Density functional theory calculations indicated that the Cu^(0)/Cu^(+) interfaces exhibited a lower Gibbs free energy for the rate-determining step,enhancing C_(2)H_(4) formation.The Cu/Cu_(2)O catalyst also exhibited a low Cu d-band center,which enhanced the adsorption stability of *CO on the surface and facilitated C_(2)formation.This observa-tion explained the higher yield of C_(2) products at the Cu^(0)/Cu^(+) interface than that of H_(2) under rapid mass transfer.The results of the net present value model showed that the H-cell holds promising industrial prospects,contingent upon it being a catalyst with both high selectivity and high current density.This approach of integrating the structure and composition provides new insights for ad-vancing the CO_(2)RR towards high-current C_(2) products.展开更多
Electrochemical CO_(2)reduction to C_(2)H_(4)can provide a sustainable route to reduce globally accelerating CO_(2)emissions and produce energy-rich chemical feedstocks.However,the poor selectivity in C_(2)H_(4)electr...Electrochemical CO_(2)reduction to C_(2)H_(4)can provide a sustainable route to reduce globally accelerating CO_(2)emissions and produce energy-rich chemical feedstocks.However,the poor selectivity in C_(2)H_(4)electrosynthesis limits its implementation in industrially interesting processes.Herein,we report a composite structured catalyst composed of Ag and Cu_(2)O with different crystal faces to achieve highly efficient reduction of CO_(2)to C_(2)H_(4).The catalyst composed of Ag and octahedral Cu_(2)O enclosed with(111)facet exhibits the best CO_(2)electroreduction performance,with the Faradaic efficiency(FE)and partial current density reaching 66.8%and 17.8 mA cm2 for C_(2)H_(4)product at-1.2 VRHE in 0.5 M KHCO_(3),respectively.Physical characterization and electrochemical test analysis indicate that the high selectivity for C_(2)H_(4)product stems from the synergistic effect of crystal faces control engineering and tandem catalysis.Specifically,Ag can provide optimal availability of CO intermediate by suppressing hydrogen evolution;subsequently,C-C coupling is promoted on the intimate surface of Cu_(2)O with facetdependent selectivity.The insights gained from this work may be beneficial for designing efficient multicomponent catalysts for improving the selectivity of electrochemical CO_(2)reduction reaction to generate C2þproducts.展开更多
The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases ...The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases rapidly with increasing the content of NiO, and the presence of NiO also improves the reduction rate of iron oxides. It is found that NiO is preferentially reduced at the beginning of the reactions, and then the metallic Ni acts as a catalyst promoting the reduction rate of iron oxides. It is also observed that the increase of the Ni O content enhances the formation of awaruite(FeNi3) but decreases the percentage of kamacite(Fe,Ni) and taenite(Fe,Ni). The particle size of the materials tends to be uniform during the reduction process due to the presence of metallic nickel, metallic iron and the formation of Fe-Ni alloy. The concentration of CO in the product gas is greater than that of CO2 at the beginning of the reaction and then slows down. The fastest reduction rate of Fe2O3-NiO composites with CO appears at 400-500 °C, and nucleation growth model can be used to elucidate the reduction mechanism. Nucleation growth process is found to be the rate controlling step when the temperature is lower than 1000 °C.展开更多
The development of highly efficient catalysts for cathodes remains an important objective of fuel cell research. Here, we report Co3O4 nanoparticles assembled on a polypyrrole/graphene oxide electrocatalyst (C...The development of highly efficient catalysts for cathodes remains an important objective of fuel cell research. Here, we report Co3O4 nanoparticles assembled on a polypyrrole/graphene oxide electrocatalyst (Co3O4/Ppy/GO) as an efficient catalyst for the oxygen reduction reaction (ORR) in alkaline media. The catalyst was prepared via the hydrothermal reaction of Co2+ ions with Ppy-modified GO. The GO, Ppy/GO, and Co3O4/Ppy/GO were characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The incorporation of Ppy into GO nanosheets resulted in the formation of a nitrogen-modified GO po-rous structure, which acted as an efficient electron-transport network for the ORR. With further anchoring of Co3O4 on Ppy/GO, the as-prepared Co3O4/Ppy/GO exhibited excellent ORR activity and followed a four-electron route mechanism for the ORR in alkaline solution. An onset potential of -0.10 V vs. a saturated calomel electrode and a diffusion limiting current density of 2.30 mA/cm^2 were achieved for the Co3O4/Ppy/GO catalyst heated at 800 ℃; these values are comparable to those for noble-metal-based Pt/C catalysts. Our work demonstrates that Co3O4/Ppy/GO is highly active for the ORR. Notably, the Ppy coupling effects between Co3O4 and GO provide a new route for the preparation of efficient non-precious electrocatalysts with hierarchical porous structures for fuel cell applications.展开更多
Edmund Husserl's first important move about phenomenology is the"phenomenological reduction"which means that we should reduce the external world to the contents of our consciousness alone. However, Hans-...Edmund Husserl's first important move about phenomenology is the"phenomenological reduction"which means that we should reduce the external world to the contents of our consciousness alone. However, Hans-Georg Gadamer holds the opinion that all interpretation of a past work consists in a dialogue between past and present(Eagleton, T. 2009:62). Gadamer's famous theory is fusion of horizons which means that the event of understanding comes about when our own"horizon"of historical meanings and assumptions"fuses"with the"horizon"within which the work itself is placed. The present thesis takes Hawthorne's YoungGoodmanBrown as an example to illustrate different understandings when readers apply the two different theories.展开更多
Advanced integrated gasification combined cycle (IGCC) power generation systems require the development of high-temperature, regenerable, desulfurization sorbents capable of removing hydrogen sulfide from coal gasif...Advanced integrated gasification combined cycle (IGCC) power generation systems require the development of high-temperature, regenerable, desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels. As a sort of effective desufurizer, such as Fe2O3, ZnO and ZnFe2O4, it will endure strong reducing atmosphere in desulfurization process. The reduced degree of desufurizer can have an effect on its desulfurization reactivity. In this paper, Fe2O3, ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH. After aging, washing and drying, the solids were calcined at 800℃. The reduction behaviors of sample were characterized by temperature-programmed reduction (TPR). It is found that there are two reduction peaks for Fe2O3 in TPR, and whereas no reduction peaks for ZnO are found. The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3. ZnFe2O4 is easier to be reduced than Fe2O3. The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.展开更多
Objective This study was conducted to optimize the operational parameters of anaerobic-anoxic-oxic (A^2/O) processes to reduce the toxicity of municipal wastewater and evaluate its ability to reduce toxicity. Method...Objective This study was conducted to optimize the operational parameters of anaerobic-anoxic-oxic (A^2/O) processes to reduce the toxicity of municipal wastewater and evaluate its ability to reduce toxicity. Methods A luminescent bacterium toxicity bioassay was employed to assess the toxicity of influent and effluent of each reactor in the A2/O system. Results The optimum operational parameters for toxicity reduction were as follows: anaerobic hydraulic retention time (HRT) = 2.8 h, anoxic HRT = 2.8 h, aerobic HRT = 6.9 h, sludge retention time (SRT) = 15 days and internal recycle ratio (IRR) = 100%. An important toxicity reduction (%) was observed in the optimized A2/O process, even when the toluene concentration of the influent was 120.7 mg·L^-1. Conclusions The toxicity of municipal wastewater was reduced significantly during the A^2/O process. A^2/O process can be used for toxicity reduction of municipal wastewater under toxic-shock loading.展开更多
The pre-separation of silica and alumina in aluminosilicates is of great significance for efficiently treating alumina-/ silica-bearing minerals for alumina production. In this work, the reaction behavior of kaolinite...The pre-separation of silica and alumina in aluminosilicates is of great significance for efficiently treating alumina-/ silica-bearing minerals for alumina production. In this work, the reaction behavior of kaolinite with ferric oxide during reduction roasting was investigated. The results of thermodynamic analyses and reduction roasting experiments show that ferrous oxide obtained from ferric oxide reduction preferentially reacts with alumina in kaolinite to form hercynite, meanwhile the silica in kaolinite is transformed into quartz solid solution and/or cristobalite solid solution. With increasing roasting temperature, fayalite formed by reaction of surplus ferrous oxide with silica at low temperature is reduced to silica and metallic iron in the presence of sufficient carbon dosage. However, increasing roasting temperature and decreasing Fe2O3/Al2O3 molar ratio favor mullite formation. The complete conversion of kaolinte into free silica and hercynite can be obtained by roasting raw meal of kaolin, ferric oxide and coal powder with Fe2O3/Al2O3/C molar ratio of 1.2:2.0:1.2 at 1373 K for 60 min. This work may facilitate the development of a technique for comprehensively utilizing silica and alumina in aluminosilicates.展开更多
The Cu2O/SiC photocatalyst was obtained from SiC nanoparticles (NPs) modified by Cu2O. Their photocatalytic activities for reducing CO2 to CH3OH under visible light irradiation have been investigated. The results in...The Cu2O/SiC photocatalyst was obtained from SiC nanoparticles (NPs) modified by Cu2O. Their photocatalytic activities for reducing CO2 to CH3OH under visible light irradiation have been investigated. The results indicated that besides a small quantity of 6H-SiC, SiC NPs mainly consisted of 3C-SiC. The band gaps of SiC and Cu2O were estimated to be about 1.95 and 2.23 eV from UV-Vis spectra, respectively. The Cu2O modification can enhance the photocatalytic performance of SiC NPs, and the largest yields of methanol on SiC, Cu2O and Cu2O/SiC photocatalysts under visible light irradiation were 153, 104 and 191μmol/g, respectively.展开更多
The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. Th...The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. The results demonstrate that AlCl3(g) reacts with Al2O(g) or Al(g) generated from the carbothermal reduction of alumina to form AlCl(g), and the AlCl(g) disproportionates to aluminum and AlCl3(g) at a lower temperature and the reaction rate of AlCl(g) reaches 90% at 980 K and 100 Pa. The aluminum can absorb CO to catalyze its disproportionation to C and CO2, and react backward with CO to form Al4C3, Al2O3, C and CO2, resulting in the aluminum product containing C, Al4C3 and Al2O3. The impurities in the aluminum product decrease as the AlCl(g) disproportionation temperature decreases. AlCl3 condenses at a temperature approximated to the room temperature.展开更多
Monolithic catalysts of Pt/La-Al2O3 and Pt/Ce0.67Zr0.3302 were prepared to investigate methane selective catalytic reduction (SCR) of NO. The results indicate that Pt/Ce0.67Zr0.33O2 shows high activity and both NO a...Monolithic catalysts of Pt/La-Al2O3 and Pt/Ce0.67Zr0.3302 were prepared to investigate methane selective catalytic reduction (SCR) of NO. The results indicate that Pt/Ce0.67Zr0.33O2 shows high activity and both NO and CH4 can be converted completely at 450℃. Meanwhile, NO and CH4 can be converted completely when there exists excess oxygen. The Pt/Ce0.67Zr0.33O2 catalyst were further investigated by using methane as reducing agent to SCR NO in a novel equipment which combined the CH4 selective catalytic reduction of NO with methane combustion. The result shows that the catalyst is high active and the novel equipment is very effective. The conversion of NO is above 92% under the conditions used in this work. The prepared burner and catalysts have great potential for application.展开更多
K2Ti6O13 whiskers were synthesized by conventional sol-gel method, sono-chemical assisted and microwave assisted sol-gel method in order to obtain catalysts with different particle sizes and to modify their optical, t...K2Ti6O13 whiskers were synthesized by conventional sol-gel method, sono-chemical assisted and microwave assisted sol-gel method in order to obtain catalysts with different particle sizes and to modify their optical, textural and electrochemical properties. These modifications improved their photocatalytic activity for H2 evolution and CO2 photo-reduction. Long K2Ti6O13 whiskers prepared by ultrasound assisted sol-gel method are the most active photocatalysts for the hydrogen evolution reaction using pure water as reactant (U-SG, 10,065 μmol g^-1). In contrast, an opposite behavior was observed using a mixture of ethanol-water, where the highest activity was achieved by the shortest and less crystalline K2Ti6O13 whiskers (C-SG, 3,2871 μmol g^-1). In case of CO2 photo-reduction, long whiskers that were also prepared by the sono-chemical assisted sol-gel method were the most active to transform CO2 to formaldehyde, methane, methanol and hydrogen. The EFB value of this catalyst is located very close to the potential for formaldehyde production and favors the selectivity to this organic product.展开更多
N2O is a major by-product emitted during low-temperature selective catalytic reduction of NO with NH3(NH3-SCR), which causes a series of serious environmental problems. A full understanding of the N2O formation mechan...N2O is a major by-product emitted during low-temperature selective catalytic reduction of NO with NH3(NH3-SCR), which causes a series of serious environmental problems. A full understanding of the N2O formation mechanism is essential to suppress the N2O emission during the low-temperature NH3-SCR, and requires an intensive study of this heterogeneous catalysis process. In this study, we investigated the reaction between NH3 and NO over a Pd/CeO2 catalyst in the absence of O2, using X-ray photoelectron spectroscopy, NH3-temperature-programmed desorption, NO-temperature-programmed desorption, and in-situ Fourier-transform infrared spectroscopy. Our results indicate that the N2O formation mechanism is reaction-temperature-dependent. At temperatures below 250 ℃, the dissociation of HON, which is produced from the reaction between surface H· adatoms and adsorbed NO, is the key process for N2O formation. At temperatures above 250 ℃,the reaction between NO and surface N·, which is produced by NO dissociation, is the only route for N2O formation, and the dissociation of NO is the rate-determining step. Under optimal reaction conditions, a high performance with nearly 100% NO conversion and 100% N2 selectivity could be achieved. These results provide important information to clarify the mechanism of N2O formation and possible suppression of N2 O emission during low-temperature NH3-SCR.展开更多
In this investigation, Pt–Ba–Ce/c-Al2O3 catalysts were prepared by incipient wetness impregnation and experiments were performed to evaluate the influence of H2 on the evolution mechanism of nitrogen oxides (NOx) st...In this investigation, Pt–Ba–Ce/c-Al2O3 catalysts were prepared by incipient wetness impregnation and experiments were performed to evaluate the influence of H2 on the evolution mechanism of nitrogen oxides (NOx) storage and reduction (NSR). The physical and chemical properties of the Pt–Ba–Ce/c- Al2O3 catalysts were studied using a combination of characterization techniques, which showed that PtOx, CeO2, and BaCO3, whose peaks were observed in X-ray diffraction (XRD) spectra, dispersed well on the c-Al2O3, as shown by transmission electron microscope (TEM), and that the difference between Ce3+ and Ce4+, as detected by X-ray photoelectron spectroscopy (XPS), facilitated the migration of active oxygen over the catalyst. In the process of a complete NSR experiment, the NOx storage capability was greatly enhanced in the temperature range of 250–350℃, and reached a maximum value of 315.3μmol·gcat^-1 at 350℃, which was ascribed to the increase in NO2 yield. In a lean and rich cycling experiment, the results showed that NOx storage efficiency and conversion were increased when the time of H2 exposure (i.e., 30, 45, and 60 s) was extended. The maximum NOx conversion of the catalyst reached 83.5% when the duration of the lean and rich phases was 240 and 60 s, respectively. The results revealed that increasing the content of H2 by an appropriate amount was favorable to the NSR mechanism due to increased decomposition of nitrate or nitrite, and the refreshing of trapping sites for the next cycle of NSR.展开更多
The V/O5-WO3-MoOy'TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction (XRD), scanning electron micrograph (SEM...The V/O5-WO3-MoOy'TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction (XRD), scanning electron micrograph (SEM) and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass per- centage of V : W : Mo : TiO2 : fiber glass = 1 : 4.5 : 4.5 : 72 : 18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to ruffle by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3. The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615 1640 mg.m-3. Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.展开更多
The CuO/γ-Al2O3/cordierite catalyst, after being sulfated by sulfur dioxide (SO2) at 673 K, exhibits high activities for selective catalytic reduction (SCR) of nitrogen oxide (NO) with ammonia (NH3) at 573-723 K. The...The CuO/γ-Al2O3/cordierite catalyst, after being sulfated by sulfur dioxide (SO2) at 673 K, exhibits high activities for selective catalytic reduction (SCR) of nitrogen oxide (NO) with ammonia (NH3) at 573-723 K. The intrinsic kinetics of SCR of NO with NH3 over CuO/γ-Al2O3/cordierite catalyst has been measured in a fixed-bed reactor in the absence of internal and external diffusions. The experimental results show that the reaction rate can be quantified by a first-order expression with activation energy Eá of 94.01 kJ·mol-1 and the corresponding p re-exponential factor A′ of 3.39×108 cm3·g-1·s-1 when NH3 is excessive. However, when NH3 is not enough, an E ley-Rideal kinetic model based on experimental data is derived with Ea of 105.79 kJ·mol-1, the corresponding A of 2 .94×109 cm3·g-1·s-1, heat of adsorption-Hads of 87.90 kJ·mol-1 and the corresponding Aads of 9.24 cm3·mol-1. The intrinsic kinetic model obtained was incorporated in a 3D mathematical model of monolithic reactor, and the agreement of the prediction with experimental data indicates that the present kinetic model is adequate for the reac-tor design and engineering scale-up.展开更多
The oxidation induration and reduction swelling behavior of the chromium-bearing vanadium titanomagnetite pellets (CVTP) with B2O3 addition were investigated. Besides, the reduction swelling index (RSI) and compressiv...The oxidation induration and reduction swelling behavior of the chromium-bearing vanadium titanomagnetite pellets (CVTP) with B2O3 addition were investigated. Besides, the reduction swelling index (RSI) and compressive strength (CS) of the reduced CVTP were also examined using the simulated coke oven gas (COG). The results suggested that the CS of CVTP was increased from 2448 to 3819.2 N, while the porosity of CVTP was decreased from 14.86% to 10.03% with the increase in B2O3 addition amounts. Moreover, the B2O3 mainly existed in the forms of TiB0.024O2 and Fe3BO5 in both CVTP and the reduced CVTP. Specifically, the CS of the reduced CVTP was elevated from 901 to 956.2 N, while the RSI was reduced from 5.87% to 3.81% as the B2O3 addition amounts were increased. Taken together, B2O3 addition would facilitate the aggregation and diffusion of metallic iron particles, which contributed to reducing the formation of metal iron whiskers and weakening the reduction swelling behavior.展开更多
This work tries to identify the relationship between geometric configuration of monolith catalysts, and transfer and reaction performances for selective catalytic reduction of N2O with CO. Monolith catalysts with five...This work tries to identify the relationship between geometric configuration of monolith catalysts, and transfer and reaction performances for selective catalytic reduction of N2O with CO. Monolith catalysts with five different channel shapes (circle, regular triangle, rectangle, square and hexagon), was investigated to make a comprehensive comparison of their pressure drop, heat transfer Nu number, mass transfer Sh number and N2O conversion. It was found that monolith catalysts have a much lower pressure drop than that of traditional packed bed, and for monolith catalysts with different channel shapes, pressure drop decreases in the order of regular triangle > rectangle > square > hexagon > circle. The order of Nu is in regular triangle > rectangle ≈ square > hexagon > circle, similar to that of Sh. N2O conversion follows the order of regular triangle > rectangular ≈ square ≈ circle > hexagon. The results indicate that chemical reaction including internal diffusion is the controlling step in the selective catalytic reduction of N2O removal with CO. In addition, channel size and gas velocity also have influence on N2O conversion and pressure drop.展开更多
Numerous studies have focused on the reduction thermodynamics of ordinary iron ore;by contrast, the literature contains few thermodynamic studies on the gas-based reduction of vanadium titano-magnetite (VTM) in mixed ...Numerous studies have focused on the reduction thermodynamics of ordinary iron ore;by contrast, the literature contains few thermodynamic studies on the gas-based reduction of vanadium titano-magnetite (VTM) in mixed atmospheres of H2, CO, H2O, CO2, and N2. In this paper, thermodynamic studies on the reduction of oxidized VTM pellets were systematically conducted in an atmosphere of a C–H–O system as a reducing agent. The results indicate that VTM of an equivalent valence state is more difficult to reduce than ordinary iron ore. A reduction equilibrium diagram using the C–H–O system as a reducing agent was obtained;it clearly describes the reduction process. Experiments were performed to investigate the effects of the reduction temperature, the gas composition, and two types of iron ores on the reduction of oxidized VTM pellets. The results show that the final reduction degree increases with increasing reduction temperature, increasing molar ratio of H2/(H2 + CO), and decreasing H2O, CO2, and N2 contents. In addition, the reduction processes under various conditions are discussed. All of the results of the reduction experiments are consistent with those of theoretical thermodynamic analysis. This study is expected to provide valuable thermodynamic theory on the industrial applications of VTM.展开更多
文摘Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multicarbon products is an efficient approach for ad-dressing the energy crisis and achieving carbon neutrality.In H-cells,achieving high-current C_(2)products is challenging because of the inefficient mass transfer of the catalyst and the presence of the hydrogen evolution reaction(HER).In this study,dendritic Cu/Cu_(2)O with abundant Cu^(0)/Cu^(+)interfaces and numerous dendritic curves was synthesized in a CO_(2)atmosphere,resulting in the high selectivity and current density of the C_(2)products.Dendritic Cu/Cu_(2)O achieved a C_(2)Faradaic efficiency of 69.8%and a C_(2)partial current density of 129.5 mA cm^(-2)in an H-cell.Finite element simulations showed that a dendritic structure with a high curvature generates a strong electric field,leading to a localized CO_(2)concentration.Additionally,DRT analysis showed that a dendritic struc-ture with a high curvature actively adsorbed the surrounding high concentration of CO_(2),enhancing the mass transfer rate and achieving a high current density.During the experiment,the impact of the electronic structure on the performance of the catalyst was investigated by varying the atomic ratio of Cu^(0)/Cu^(+) on the catalyst surface,which resulted in improved ethylene selectivity.Under the optimal atomic ratio of Cu^(0)/Cu^(+),the charge transfer resistance was minimized,and the desorption rate of the intermediates was low,favoring C_(2) generation.Density functional theory calculations indicated that the Cu^(0)/Cu^(+) interfaces exhibited a lower Gibbs free energy for the rate-determining step,enhancing C_(2)H_(4) formation.The Cu/Cu_(2)O catalyst also exhibited a low Cu d-band center,which enhanced the adsorption stability of *CO on the surface and facilitated C_(2)formation.This observa-tion explained the higher yield of C_(2) products at the Cu^(0)/Cu^(+) interface than that of H_(2) under rapid mass transfer.The results of the net present value model showed that the H-cell holds promising industrial prospects,contingent upon it being a catalyst with both high selectivity and high current density.This approach of integrating the structure and composition provides new insights for ad-vancing the CO_(2)RR towards high-current C_(2) products.
基金This work was supported by the University of Science and Technology Beijing.DG acknowledges the financial support from 111 Project(no.B170003)Foshan Science and Technology Innovation Project(no.2018IT100363).
文摘Electrochemical CO_(2)reduction to C_(2)H_(4)can provide a sustainable route to reduce globally accelerating CO_(2)emissions and produce energy-rich chemical feedstocks.However,the poor selectivity in C_(2)H_(4)electrosynthesis limits its implementation in industrially interesting processes.Herein,we report a composite structured catalyst composed of Ag and Cu_(2)O with different crystal faces to achieve highly efficient reduction of CO_(2)to C_(2)H_(4).The catalyst composed of Ag and octahedral Cu_(2)O enclosed with(111)facet exhibits the best CO_(2)electroreduction performance,with the Faradaic efficiency(FE)and partial current density reaching 66.8%and 17.8 mA cm2 for C_(2)H_(4)product at-1.2 VRHE in 0.5 M KHCO_(3),respectively.Physical characterization and electrochemical test analysis indicate that the high selectivity for C_(2)H_(4)product stems from the synergistic effect of crystal faces control engineering and tandem catalysis.Specifically,Ag can provide optimal availability of CO intermediate by suppressing hydrogen evolution;subsequently,C-C coupling is promoted on the intimate surface of Cu_(2)O with facetdependent selectivity.The insights gained from this work may be beneficial for designing efficient multicomponent catalysts for improving the selectivity of electrochemical CO_(2)reduction reaction to generate C2þproducts.
基金Projects(51304091,U1302274)supported by the National Natural Science Foundation of ChinaProjects(2013FD009,2013FZ007)supported by Applied Basic Research Program of Yunnan Province,ChinaProject(2012HB009)supported by the Candidate Talents Training Fund of Yunnan Province,China
文摘The non-isothermal reduction kinetics and mechanism of Fe2O3-NiO composites with different Fe2O3-NiO compacts using carbon monoxide as reductant were investigated. The results show that the reduction degree increases rapidly with increasing the content of NiO, and the presence of NiO also improves the reduction rate of iron oxides. It is found that NiO is preferentially reduced at the beginning of the reactions, and then the metallic Ni acts as a catalyst promoting the reduction rate of iron oxides. It is also observed that the increase of the Ni O content enhances the formation of awaruite(FeNi3) but decreases the percentage of kamacite(Fe,Ni) and taenite(Fe,Ni). The particle size of the materials tends to be uniform during the reduction process due to the presence of metallic nickel, metallic iron and the formation of Fe-Ni alloy. The concentration of CO in the product gas is greater than that of CO2 at the beginning of the reaction and then slows down. The fastest reduction rate of Fe2O3-NiO composites with CO appears at 400-500 °C, and nucleation growth model can be used to elucidate the reduction mechanism. Nucleation growth process is found to be the rate controlling step when the temperature is lower than 1000 °C.
基金supported by the National Natural Science Foundation of China(21373042)~~
文摘The development of highly efficient catalysts for cathodes remains an important objective of fuel cell research. Here, we report Co3O4 nanoparticles assembled on a polypyrrole/graphene oxide electrocatalyst (Co3O4/Ppy/GO) as an efficient catalyst for the oxygen reduction reaction (ORR) in alkaline media. The catalyst was prepared via the hydrothermal reaction of Co2+ ions with Ppy-modified GO. The GO, Ppy/GO, and Co3O4/Ppy/GO were characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The incorporation of Ppy into GO nanosheets resulted in the formation of a nitrogen-modified GO po-rous structure, which acted as an efficient electron-transport network for the ORR. With further anchoring of Co3O4 on Ppy/GO, the as-prepared Co3O4/Ppy/GO exhibited excellent ORR activity and followed a four-electron route mechanism for the ORR in alkaline solution. An onset potential of -0.10 V vs. a saturated calomel electrode and a diffusion limiting current density of 2.30 mA/cm^2 were achieved for the Co3O4/Ppy/GO catalyst heated at 800 ℃; these values are comparable to those for noble-metal-based Pt/C catalysts. Our work demonstrates that Co3O4/Ppy/GO is highly active for the ORR. Notably, the Ppy coupling effects between Co3O4 and GO provide a new route for the preparation of efficient non-precious electrocatalysts with hierarchical porous structures for fuel cell applications.
文摘Edmund Husserl's first important move about phenomenology is the"phenomenological reduction"which means that we should reduce the external world to the contents of our consciousness alone. However, Hans-Georg Gadamer holds the opinion that all interpretation of a past work consists in a dialogue between past and present(Eagleton, T. 2009:62). Gadamer's famous theory is fusion of horizons which means that the event of understanding comes about when our own"horizon"of historical meanings and assumptions"fuses"with the"horizon"within which the work itself is placed. The present thesis takes Hawthorne's YoungGoodmanBrown as an example to illustrate different understandings when readers apply the two different theories.
基金the Ministry of Science and Technology of China under the Grant No. G2005CB221203the Natural Science Foundation of China(20776092)
文摘Advanced integrated gasification combined cycle (IGCC) power generation systems require the development of high-temperature, regenerable, desulfurization sorbents capable of removing hydrogen sulfide from coal gasifier gas to very low levels. As a sort of effective desufurizer, such as Fe2O3, ZnO and ZnFe2O4, it will endure strong reducing atmosphere in desulfurization process. The reduced degree of desufurizer can have an effect on its desulfurization reactivity. In this paper, Fe2O3, ZnO and ZnFe2O4 were synthesized by precipitation or co-precipitation at constant pH. After aging, washing and drying, the solids were calcined at 800℃. The reduction behaviors of sample were characterized by temperature-programmed reduction (TPR). It is found that there are two reduction peaks for Fe2O3 in TPR, and whereas no reduction peaks for ZnO are found. The reduction process of ZnFe2O4 prepared by co-precipitation is different from that of Fe2O3. ZnFe2O4 is easier to be reduced than Fe2O3. The activation energy of reduction process for Fe2O3 and ZnFe2O4 is obtained at different reduction periods.
基金supported by the National Science Foundation Project grants of China(No.50878165,No.21007010)the Program for New Century Excellent Talents in University(NCET-08-0403)+4 种基金the Research Fund for the Doctoral Program of Higher Education of China(No.20090075120007)the Shanghai Committee of Science and Technology,China(No.09230500200)the Fundamental Research Funds for the Central Universities of China(No.10D11308)the Key Special Program on the S&T for the Pollution Control and Treatment of Water Bodies(No. 2008ZX07316-003)the Shanghai Leading Academic Discipline Project (No.B604)
文摘Objective This study was conducted to optimize the operational parameters of anaerobic-anoxic-oxic (A^2/O) processes to reduce the toxicity of municipal wastewater and evaluate its ability to reduce toxicity. Methods A luminescent bacterium toxicity bioassay was employed to assess the toxicity of influent and effluent of each reactor in the A2/O system. Results The optimum operational parameters for toxicity reduction were as follows: anaerobic hydraulic retention time (HRT) = 2.8 h, anoxic HRT = 2.8 h, aerobic HRT = 6.9 h, sludge retention time (SRT) = 15 days and internal recycle ratio (IRR) = 100%. An important toxicity reduction (%) was observed in the optimized A2/O process, even when the toluene concentration of the influent was 120.7 mg·L^-1. Conclusions The toxicity of municipal wastewater was reduced significantly during the A^2/O process. A^2/O process can be used for toxicity reduction of municipal wastewater under toxic-shock loading.
基金Project(51604309)supported by the National Natural Science Foundation of China
文摘The pre-separation of silica and alumina in aluminosilicates is of great significance for efficiently treating alumina-/ silica-bearing minerals for alumina production. In this work, the reaction behavior of kaolinite with ferric oxide during reduction roasting was investigated. The results of thermodynamic analyses and reduction roasting experiments show that ferrous oxide obtained from ferric oxide reduction preferentially reacts with alumina in kaolinite to form hercynite, meanwhile the silica in kaolinite is transformed into quartz solid solution and/or cristobalite solid solution. With increasing roasting temperature, fayalite formed by reaction of surplus ferrous oxide with silica at low temperature is reduced to silica and metallic iron in the presence of sufficient carbon dosage. However, increasing roasting temperature and decreasing Fe2O3/Al2O3 molar ratio favor mullite formation. The complete conversion of kaolinte into free silica and hercynite can be obtained by roasting raw meal of kaolin, ferric oxide and coal powder with Fe2O3/Al2O3/C molar ratio of 1.2:2.0:1.2 at 1373 K for 60 min. This work may facilitate the development of a technique for comprehensively utilizing silica and alumina in aluminosilicates.
基金supported by the National Natural Science Foundation of China (Grant No. 20906034)the Key Academic Program of the 3rd Phase "211 Project" of South China Agricultural University (Grant No. 2009B010100001)China Postdoctoral Science Foundation (Grant No. 20080430820)
文摘The Cu2O/SiC photocatalyst was obtained from SiC nanoparticles (NPs) modified by Cu2O. Their photocatalytic activities for reducing CO2 to CH3OH under visible light irradiation have been investigated. The results indicated that besides a small quantity of 6H-SiC, SiC NPs mainly consisted of 3C-SiC. The band gaps of SiC and Cu2O were estimated to be about 1.95 and 2.23 eV from UV-Vis spectra, respectively. The Cu2O modification can enhance the photocatalytic performance of SiC NPs, and the largest yields of methanol on SiC, Cu2O and Cu2O/SiC photocatalysts under visible light irradiation were 153, 104 and 191μmol/g, respectively.
基金Project (u0837604) supported by the Joint Funds of the National Natural Science Foundation of China and Yunnan Province
文摘The carbothermal reduction-chlorination-disproportionation of alumina in vacuum was investigated by XRD and thermodynamic analysis. The experiments on alumina and graphite at 1643-1843 K in vacuum were carried out. The results demonstrate that AlCl3(g) reacts with Al2O(g) or Al(g) generated from the carbothermal reduction of alumina to form AlCl(g), and the AlCl(g) disproportionates to aluminum and AlCl3(g) at a lower temperature and the reaction rate of AlCl(g) reaches 90% at 980 K and 100 Pa. The aluminum can absorb CO to catalyze its disproportionation to C and CO2, and react backward with CO to form Al4C3, Al2O3, C and CO2, resulting in the aluminum product containing C, Al4C3 and Al2O3. The impurities in the aluminum product decrease as the AlCl(g) disproportionation temperature decreases. AlCl3 condenses at a temperature approximated to the room temperature.
基金Supported by the National High Technology Research and Development Program of China (863 Program, 2006AA06Z347)the NationalNatural Science Foundation of China (20773090).
文摘Monolithic catalysts of Pt/La-Al2O3 and Pt/Ce0.67Zr0.3302 were prepared to investigate methane selective catalytic reduction (SCR) of NO. The results indicate that Pt/Ce0.67Zr0.33O2 shows high activity and both NO and CH4 can be converted completely at 450℃. Meanwhile, NO and CH4 can be converted completely when there exists excess oxygen. The Pt/Ce0.67Zr0.33O2 catalyst were further investigated by using methane as reducing agent to SCR NO in a novel equipment which combined the CH4 selective catalytic reduction of NO with methane combustion. The result shows that the catalyst is high active and the novel equipment is very effective. The conversion of NO is above 92% under the conditions used in this work. The prepared burner and catalysts have great potential for application.
基金CONACYT (CB-2014-237049, PDCPN-2015-487 and Ph. D. scholarship 635249) for the financial support
文摘K2Ti6O13 whiskers were synthesized by conventional sol-gel method, sono-chemical assisted and microwave assisted sol-gel method in order to obtain catalysts with different particle sizes and to modify their optical, textural and electrochemical properties. These modifications improved their photocatalytic activity for H2 evolution and CO2 photo-reduction. Long K2Ti6O13 whiskers prepared by ultrasound assisted sol-gel method are the most active photocatalysts for the hydrogen evolution reaction using pure water as reactant (U-SG, 10,065 μmol g^-1). In contrast, an opposite behavior was observed using a mixture of ethanol-water, where the highest activity was achieved by the shortest and less crystalline K2Ti6O13 whiskers (C-SG, 3,2871 μmol g^-1). In case of CO2 photo-reduction, long whiskers that were also prepared by the sono-chemical assisted sol-gel method were the most active to transform CO2 to formaldehyde, methane, methanol and hydrogen. The EFB value of this catalyst is located very close to the potential for formaldehyde production and favors the selectivity to this organic product.
基金support of the National Key Research and Development Program of China(2017YFB0310403)the National Natural Science Foundation of China(51872260,51390474,91645103)+2 种基金the Ministry of Science and Technology of China(2016YFE0105700)the Environmentally Sustainable Management of Medical Wastes in China(C/V/S/10/251)the Zhejiang Provincial Natural Science Foundation of China(Z4080070,LD19B030001)~~
文摘N2O is a major by-product emitted during low-temperature selective catalytic reduction of NO with NH3(NH3-SCR), which causes a series of serious environmental problems. A full understanding of the N2O formation mechanism is essential to suppress the N2O emission during the low-temperature NH3-SCR, and requires an intensive study of this heterogeneous catalysis process. In this study, we investigated the reaction between NH3 and NO over a Pd/CeO2 catalyst in the absence of O2, using X-ray photoelectron spectroscopy, NH3-temperature-programmed desorption, NO-temperature-programmed desorption, and in-situ Fourier-transform infrared spectroscopy. Our results indicate that the N2O formation mechanism is reaction-temperature-dependent. At temperatures below 250 ℃, the dissociation of HON, which is produced from the reaction between surface H· adatoms and adsorbed NO, is the key process for N2O formation. At temperatures above 250 ℃,the reaction between NO and surface N·, which is produced by NO dissociation, is the only route for N2O formation, and the dissociation of NO is the rate-determining step. Under optimal reaction conditions, a high performance with nearly 100% NO conversion and 100% N2 selectivity could be achieved. These results provide important information to clarify the mechanism of N2O formation and possible suppression of N2 O emission during low-temperature NH3-SCR.
基金the National Natural Science Foundation of China (51676090)the Natural Science Foundation of Jiangsu Province (BK20150513), and the Six Talent Peaks Project in Jiangsu Province.
文摘In this investigation, Pt–Ba–Ce/c-Al2O3 catalysts were prepared by incipient wetness impregnation and experiments were performed to evaluate the influence of H2 on the evolution mechanism of nitrogen oxides (NOx) storage and reduction (NSR). The physical and chemical properties of the Pt–Ba–Ce/c- Al2O3 catalysts were studied using a combination of characterization techniques, which showed that PtOx, CeO2, and BaCO3, whose peaks were observed in X-ray diffraction (XRD) spectra, dispersed well on the c-Al2O3, as shown by transmission electron microscope (TEM), and that the difference between Ce3+ and Ce4+, as detected by X-ray photoelectron spectroscopy (XPS), facilitated the migration of active oxygen over the catalyst. In the process of a complete NSR experiment, the NOx storage capability was greatly enhanced in the temperature range of 250–350℃, and reached a maximum value of 315.3μmol·gcat^-1 at 350℃, which was ascribed to the increase in NO2 yield. In a lean and rich cycling experiment, the results showed that NOx storage efficiency and conversion were increased when the time of H2 exposure (i.e., 30, 45, and 60 s) was extended. The maximum NOx conversion of the catalyst reached 83.5% when the duration of the lean and rich phases was 240 and 60 s, respectively. The results revealed that increasing the content of H2 by an appropriate amount was favorable to the NSR mechanism due to increased decomposition of nitrate or nitrite, and the refreshing of trapping sites for the next cycle of NSR.
基金Supported by the Science and Technology Development Planning of Shandong Province(2011GSF11716)China Scholarship Council for Researching in University of Birmingham
文摘The V/O5-WO3-MoOy'TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction (XRD), scanning electron micrograph (SEM) and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass per- centage of V : W : Mo : TiO2 : fiber glass = 1 : 4.5 : 4.5 : 72 : 18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to ruffle by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3. The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615 1640 mg.m-3. Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.
基金Supported by the National Natural Science Foundation of China (20821004 20736001 21076008) the Research Fund for the Doctoral Program of Higher Education of China (2090010110002)
文摘The CuO/γ-Al2O3/cordierite catalyst, after being sulfated by sulfur dioxide (SO2) at 673 K, exhibits high activities for selective catalytic reduction (SCR) of nitrogen oxide (NO) with ammonia (NH3) at 573-723 K. The intrinsic kinetics of SCR of NO with NH3 over CuO/γ-Al2O3/cordierite catalyst has been measured in a fixed-bed reactor in the absence of internal and external diffusions. The experimental results show that the reaction rate can be quantified by a first-order expression with activation energy Eá of 94.01 kJ·mol-1 and the corresponding p re-exponential factor A′ of 3.39×108 cm3·g-1·s-1 when NH3 is excessive. However, when NH3 is not enough, an E ley-Rideal kinetic model based on experimental data is derived with Ea of 105.79 kJ·mol-1, the corresponding A of 2 .94×109 cm3·g-1·s-1, heat of adsorption-Hads of 87.90 kJ·mol-1 and the corresponding Aads of 9.24 cm3·mol-1. The intrinsic kinetic model obtained was incorporated in a 3D mathematical model of monolithic reactor, and the agreement of the prediction with experimental data indicates that the present kinetic model is adequate for the reac-tor design and engineering scale-up.
基金Projects(51674084,51174051,51574082)supported by the National Natural Science Foundation of China
文摘The oxidation induration and reduction swelling behavior of the chromium-bearing vanadium titanomagnetite pellets (CVTP) with B2O3 addition were investigated. Besides, the reduction swelling index (RSI) and compressive strength (CS) of the reduced CVTP were also examined using the simulated coke oven gas (COG). The results suggested that the CS of CVTP was increased from 2448 to 3819.2 N, while the porosity of CVTP was decreased from 14.86% to 10.03% with the increase in B2O3 addition amounts. Moreover, the B2O3 mainly existed in the forms of TiB0.024O2 and Fe3BO5 in both CVTP and the reduced CVTP. Specifically, the CS of the reduced CVTP was elevated from 901 to 956.2 N, while the RSI was reduced from 5.87% to 3.81% as the B2O3 addition amounts were increased. Taken together, B2O3 addition would facilitate the aggregation and diffusion of metallic iron particles, which contributed to reducing the formation of metal iron whiskers and weakening the reduction swelling behavior.
基金Supported by the National Natural Science Foundation of China (21121064, 21076008) the Projects in the National Science & Technology Pillar Program During the 12th Five-Year Plan Period (2011BAC06B04)
文摘This work tries to identify the relationship between geometric configuration of monolith catalysts, and transfer and reaction performances for selective catalytic reduction of N2O with CO. Monolith catalysts with five different channel shapes (circle, regular triangle, rectangle, square and hexagon), was investigated to make a comprehensive comparison of their pressure drop, heat transfer Nu number, mass transfer Sh number and N2O conversion. It was found that monolith catalysts have a much lower pressure drop than that of traditional packed bed, and for monolith catalysts with different channel shapes, pressure drop decreases in the order of regular triangle > rectangle > square > hexagon > circle. The order of Nu is in regular triangle > rectangle ≈ square > hexagon > circle, similar to that of Sh. N2O conversion follows the order of regular triangle > rectangular ≈ square ≈ circle > hexagon. The results indicate that chemical reaction including internal diffusion is the controlling step in the selective catalytic reduction of N2O removal with CO. In addition, channel size and gas velocity also have influence on N2O conversion and pressure drop.
基金financially supported by the Ministry of Land and Resources Public Welfare Industry Research Project, China (No. 201511062-02)
文摘Numerous studies have focused on the reduction thermodynamics of ordinary iron ore;by contrast, the literature contains few thermodynamic studies on the gas-based reduction of vanadium titano-magnetite (VTM) in mixed atmospheres of H2, CO, H2O, CO2, and N2. In this paper, thermodynamic studies on the reduction of oxidized VTM pellets were systematically conducted in an atmosphere of a C–H–O system as a reducing agent. The results indicate that VTM of an equivalent valence state is more difficult to reduce than ordinary iron ore. A reduction equilibrium diagram using the C–H–O system as a reducing agent was obtained;it clearly describes the reduction process. Experiments were performed to investigate the effects of the reduction temperature, the gas composition, and two types of iron ores on the reduction of oxidized VTM pellets. The results show that the final reduction degree increases with increasing reduction temperature, increasing molar ratio of H2/(H2 + CO), and decreasing H2O, CO2, and N2 contents. In addition, the reduction processes under various conditions are discussed. All of the results of the reduction experiments are consistent with those of theoretical thermodynamic analysis. This study is expected to provide valuable thermodynamic theory on the industrial applications of VTM.