The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed...The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed bipolar waveforms with various cathodic duty cycles and cathodic current densities.The coatings were characterized by SEM,EDS,and XRD.EIS was applied to investigate the electrochemical properties.It was observed that the increase of cathodic duty cycle and cathodic current density from 20%and 6 A/dm^(2) to 40%and 12 A/dm^(2) enhances the growth rate of the inner layer from 0.22 to 0.75μm/min.Adding PTO into the bath showed a fortifying effect on influence of the cathodic pulse and the mentioned change of cathodic pulse parameters,resulting in an increase of the inner layer growth rate from 0.25 to 1.10μm/min.Based on EDS analysis,Si and Ti were incorporated dominantly in the upper parts of the coatings.XRD technique merely detectedγ-Al_(2)O_(3),and there were no detectable peaks related to Ti and Si compounds.However,the EIS results confirmed that the incorporation of Ti^(4+)into alumina changed the electronic properties of the coating.The coatings obtained from the bath containing PTO using the bipolar waveforms with a cathodic duty cycle of 40%and current density values higher than 6 A/dm^(2) showed highly appropriate electrochemical behavior during 240 d of immersion due to an efficient repairing mechanism.Regarding the effects of studied parameters on the coating properties,the roles of cathodic pulse parameters and PTO in the PEO process were highlighted.展开更多
开发了钠焙烧-还原浸出联合工艺从废Pd/Al_(2)O_(3)催化剂中回收Pd和Al_(2)O_(3)。钠化焙烧热力学分析表明,在最佳的Na_(2)O/Al_(2)O_(3)摩尔比和温度下,NaOH、Na_(2)CO_(3)和Na_(2)C2O4均可以与Al_(2)O_(3)完全反应生成Na Al O2。NaOH...开发了钠焙烧-还原浸出联合工艺从废Pd/Al_(2)O_(3)催化剂中回收Pd和Al_(2)O_(3)。钠化焙烧热力学分析表明,在最佳的Na_(2)O/Al_(2)O_(3)摩尔比和温度下,NaOH、Na_(2)CO_(3)和Na_(2)C2O4均可以与Al_(2)O_(3)完全反应生成Na Al O2。NaOH、Na_(2)CO_(3)和Na_(2)C_(2)O_(4)的焙烧渣经水浸后,Al_(2)O_(3)浸出率分别为99.6%、61.0%和55.3%。机械活化-NaOH无水焙烧工艺避免了焙烧渣的固结且可获得较高的Al_(2)O_(3)浸出率。N_(2)H_(4)·H_(2)O还原浸出避免了水浸过程中Pd的溶解损失且催化剂中99.7%的Al_(2)O_(3)被浸出。最终得到Na Al O2浸出液和富钯渣,其中有价的铝和钯可被进一步回收。展开更多
Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub&...Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> was determined by nano-particle size analyzer, and the effects of nano-α-Al<sub>2</sub>O<sub>3</sub> content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al<sub>2</sub>O<sub>3</sub> dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al<sub>2</sub>O<sub>3</sub> increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al<sub>2</sub>O<sub>3</sub>.展开更多
In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can r...In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can reduce silver ions to generate crystalline silver nanoparticles(Ag NPs)of good dispersion and uniformity on the alumina surface,leading to the formation of Ag/γ-Al_(2)O_(3)catalysts in a green manner without traditional chemical reductants.Ag/γ-Al_(2)O_(3)exhibited good catalytic activity and stability in CO oxidation reactions,and the activity increased with increase in the Ag content.For catalysts with more than 2 wt%Ag,100%CO conversion can be achieved at 300°C.The catalytic activity of the Ag/γ-Al_(2)O_(3)catalysts is also closely related to the size of theγ-alumina,where Ag/nano-γ-Al_(2)O_(3)catalysts demonstrate better performance than Ag/micro-γ-Al_(2)O_(3)catalysts with the same Ag content.In addition,the catalytic properties of plasma-generated Ag/nano-γ-Al_(2)O_(3)(Ag/γ-Al_(2)O_(3)-P)catalysts were compared with those of Ag/nano-γ-Al_(2)O_(3)catalysts prepared by the traditional calcination approach(Ag/γ-Al_(2)O_(3)-C),with the plasma-generated samples demonstrating better overall performance.This simple,rapid and green plasma process is considered to be applicable for the synthesis of diverse noble metal-based catalysts.展开更多
Galvanic deposition method was used to prepare the Pd/Ni-Al2O3-GD catalyst for the combustion of methane under lean conditions. The new catalyst and compared catalysts （Pd/Al2O3-IW, Pd-Ni/Al2O3-IW, Pd/Ni-Al2O3-IW） p...Galvanic deposition method was used to prepare the Pd/Ni-Al2O3-GD catalyst for the combustion of methane under lean conditions. The new catalyst and compared catalysts （Pd/Al2O3-IW, Pd-Ni/Al2O3-IW, Pd/Ni-Al2O3-IW） prepared by incipient wetness impregnation were characterized by N2-physisorption, XRD and TEM to clarify particle size and size distribution of palladium species. Combined O2-TPD and XPS results with the catalytic data, it shows that the surface palladium species with low valence exhibits better combustion performance due to their stronger interaction with support. The results indicate that the galvanic deposition method is an effective route to prepare efficient catalyst for methane combustion, and it also provides useful information for improving the present commercial catalyst.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
Alkali-promoted Pd/Al2O3 catalysts exhibit much higher activities in NO decomposition than Pd/Al2O3. FTIR study shows that on the alkali promoted catalyst.nitric oxide exists on the surface mainly in negatively charge...Alkali-promoted Pd/Al2O3 catalysts exhibit much higher activities in NO decomposition than Pd/Al2O3. FTIR study shows that on the alkali promoted catalyst.nitric oxide exists on the surface mainly in negatively charged form(NO-)at high temperatures.which is consistent with the activity improvement.展开更多
文摘The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed bipolar waveforms with various cathodic duty cycles and cathodic current densities.The coatings were characterized by SEM,EDS,and XRD.EIS was applied to investigate the electrochemical properties.It was observed that the increase of cathodic duty cycle and cathodic current density from 20%and 6 A/dm^(2) to 40%and 12 A/dm^(2) enhances the growth rate of the inner layer from 0.22 to 0.75μm/min.Adding PTO into the bath showed a fortifying effect on influence of the cathodic pulse and the mentioned change of cathodic pulse parameters,resulting in an increase of the inner layer growth rate from 0.25 to 1.10μm/min.Based on EDS analysis,Si and Ti were incorporated dominantly in the upper parts of the coatings.XRD technique merely detectedγ-Al_(2)O_(3),and there were no detectable peaks related to Ti and Si compounds.However,the EIS results confirmed that the incorporation of Ti^(4+)into alumina changed the electronic properties of the coating.The coatings obtained from the bath containing PTO using the bipolar waveforms with a cathodic duty cycle of 40%and current density values higher than 6 A/dm^(2) showed highly appropriate electrochemical behavior during 240 d of immersion due to an efficient repairing mechanism.Regarding the effects of studied parameters on the coating properties,the roles of cathodic pulse parameters and PTO in the PEO process were highlighted.
基金the financial support from the Science and Technology Plan of Yunnan Province,China(No.2018ZE001)the National Key Research and Development Program of China(No.2018YFE0110200)+1 种基金the Key Research and Development Program of Hunan Province,China(No.2020SK2125)the Science and Technology Plan of Department of Natural Resources of Hunan Province,China(No.2020-21)。
文摘开发了钠焙烧-还原浸出联合工艺从废Pd/Al_(2)O_(3)催化剂中回收Pd和Al_(2)O_(3)。钠化焙烧热力学分析表明,在最佳的Na_(2)O/Al_(2)O_(3)摩尔比和温度下,NaOH、Na_(2)CO_(3)和Na_(2)C2O4均可以与Al_(2)O_(3)完全反应生成Na Al O2。NaOH、Na_(2)CO_(3)和Na_(2)C_(2)O_(4)的焙烧渣经水浸后,Al_(2)O_(3)浸出率分别为99.6%、61.0%和55.3%。机械活化-NaOH无水焙烧工艺避免了焙烧渣的固结且可获得较高的Al_(2)O_(3)浸出率。N_(2)H_(4)·H_(2)O还原浸出避免了水浸过程中Pd的溶解损失且催化剂中99.7%的Al_(2)O_(3)被浸出。最终得到Na Al O2浸出液和富钯渣,其中有价的铝和钯可被进一步回收。
文摘Silane coupling agent KH560 was used to modify the surface of nano-α-Al<sub>2</sub>O<sub>3</sub> in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> was determined by nano-particle size analyzer, and the effects of nano-α-Al<sub>2</sub>O<sub>3</sub> content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al<sub>2</sub>O<sub>3</sub> were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al<sub>2</sub>O<sub>3</sub> dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al<sub>2</sub>O<sub>3</sub> increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al<sub>2</sub>O<sub>3</sub>.
基金financial support from National Natural Science Foundation of China(Nos.52004102 and 22078125)Postdoctoral Science Foundation of China(No.2021M690068)+2 种基金Fundamental Research Funds for the Central Universities(Nos.JUSRP221018 and JUSRP622038)Key Laboratory of Green Cleaning Technology and Detergent of Zhejiang Province(No.Q202204)Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(No.GCP202112)。
文摘In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can reduce silver ions to generate crystalline silver nanoparticles(Ag NPs)of good dispersion and uniformity on the alumina surface,leading to the formation of Ag/γ-Al_(2)O_(3)catalysts in a green manner without traditional chemical reductants.Ag/γ-Al_(2)O_(3)exhibited good catalytic activity and stability in CO oxidation reactions,and the activity increased with increase in the Ag content.For catalysts with more than 2 wt%Ag,100%CO conversion can be achieved at 300°C.The catalytic activity of the Ag/γ-Al_(2)O_(3)catalysts is also closely related to the size of theγ-alumina,where Ag/nano-γ-Al_(2)O_(3)catalysts demonstrate better performance than Ag/micro-γ-Al_(2)O_(3)catalysts with the same Ag content.In addition,the catalytic properties of plasma-generated Ag/nano-γ-Al_(2)O_(3)(Ag/γ-Al_(2)O_(3)-P)catalysts were compared with those of Ag/nano-γ-Al_(2)O_(3)catalysts prepared by the traditional calcination approach(Ag/γ-Al_(2)O_(3)-C),with the plasma-generated samples demonstrating better overall performance.This simple,rapid and green plasma process is considered to be applicable for the synthesis of diverse noble metal-based catalysts.
基金supported by the National Natural Science Foundation of China (21273221)the National High Technology Research and Development Program of China (863 Program, 2011AA03A406)
文摘Galvanic deposition method was used to prepare the Pd/Ni-Al2O3-GD catalyst for the combustion of methane under lean conditions. The new catalyst and compared catalysts （Pd/Al2O3-IW, Pd-Ni/Al2O3-IW, Pd/Ni-Al2O3-IW） prepared by incipient wetness impregnation were characterized by N2-physisorption, XRD and TEM to clarify particle size and size distribution of palladium species. Combined O2-TPD and XPS results with the catalytic data, it shows that the surface palladium species with low valence exhibits better combustion performance due to their stronger interaction with support. The results indicate that the galvanic deposition method is an effective route to prepare efficient catalyst for methane combustion, and it also provides useful information for improving the present commercial catalyst.
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.
文摘Alkali-promoted Pd/Al2O3 catalysts exhibit much higher activities in NO decomposition than Pd/Al2O3. FTIR study shows that on the alkali promoted catalyst.nitric oxide exists on the surface mainly in negatively charged form(NO-)at high temperatures.which is consistent with the activity improvement.
