Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making th...Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making them a highly promising technology for low-grade heat recovery and utilization.However,the low output power density and energy conversion efficiency resulted by the slow diffusion kinetics of Zn2+hinder their development.Herein,we present a highperformance thermal charging cell design using Zn2+/NH4+hybrid ion electrolyte,which not only maintains the high output voltage of the Zn-based thermoelectric system,but also significantly enhances the output power density due to the fast diffusion kinetics of NH4+.Based on this strategy,the thermal charging cell displays a high thermopower of 12.5 mV K-1and an excellent normalized power density of 19.6 mW m-2K-2at a temperature difference of 35 K.The Carnot-relative efficiency is as high as 12.74%.Moreover,it can operate continuously for over 72 h when the temperature difference persists,achieving a balance between thermoelectric conversion and output.This work provides a simple and effective strategy for the design of high-performance thermal charging cells for low-grade heat conversion and utilization.展开更多
二噁英会降低人类的免疫力,影响人体和神经发育;氮氧化物则会对人体的各项脏器和血液组织有严重危害,还会破坏臭氧层,加速酸雨的形成.商业钒钛催化剂既能脱除氮氧化物又能催化分解二噁英(邻二氯苯作为模拟物),二噁英活性温度区为200~300...二噁英会降低人类的免疫力,影响人体和神经发育;氮氧化物则会对人体的各项脏器和血液组织有严重危害,还会破坏臭氧层,加速酸雨的形成.商业钒钛催化剂既能脱除氮氧化物又能催化分解二噁英(邻二氯苯作为模拟物),二噁英活性温度区为200~300℃,而脱硝活性温度为300~400℃.研究了VOx/TiO2、MnOx/TiO2以及VOx-MnOx/TiO2等催化剂在200~300℃脱硝、脱除二噁英的情况.结果表明,在VOx/TiO2催化剂中掺入MnOx促进脱硝活性温度区间由300~400℃往200~300℃偏移,当MnOx和VOx摩尔比为3∶1时,催化剂在250℃脱硝和脱除二噁英的效果最好,催化NO和邻二氯苯效率分别为92.0%和89.0%.原位红外漫反射光谱研究表明,1V3M/T催化剂表面的脱硝反应在250℃遵循L-H机理,—NH2、Nx Hy Oz、单齿亚硝酸盐和二齿硝酸盐是主要的反应中间体.展开更多
V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for N...V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for NOx conversion using NH3 as the reductant. Hydrothermal ageing decreased the NOx conversion of V2O5/WO3‐TiO2 catalyst severely over the entire measured tem‐perature range. Interestingly, the NH3‐SCR activity of the silica‐modified catalyst at 220–480℃ is enhanced after ageing. The catalysts were characterized by X‐ray diffraction, nitrogen adsorption, X‐ray fluorescence, Raman spectroscopy, H2 temperature‐programmed reduction, and NH3 temper‐ature‐programmed desorption. The addition of silica inhibited the phase transition from anatase to rutile titania, growth of TiO2 crystallite size and shrinkage of catalyst surface area. Consequently, the vanadia species remained highly dispersed and the hydrothermal stability of the V2O5/WO3‐TiO2 catalyst was significantly improved.展开更多
A series of V2O5‐WO3/TiO2‐ZrO2,V2O5‐WO3/TiO2‐CeO2,and V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalysts were synthesized to improve the selective catalytic reduction(SCR)performance and the K‐poisoning resistance of a V2O5‐W...A series of V2O5‐WO3/TiO2‐ZrO2,V2O5‐WO3/TiO2‐CeO2,and V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalysts were synthesized to improve the selective catalytic reduction(SCR)performance and the K‐poisoning resistance of a V2O5‐WO3/TiO2 catalyst.The physicochemical properties were investigated by using XRD,BET,NH3‐TPD,H2‐TPR,and XPS,and the catalytic performance and K‐poisoning resistance were evaluated via a NH3‐SCR model reaction.Ce^4+and Zr^4+co‐doping were found to enhance the conversion of NOx,and exhibit the best K‐poisoning resistance owing to the largest BET‐specific surface area,pore volume,and total acid site concentration,as well as the minimal effects on the surface acidity and redox ability from K poisoning.The V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst also presents outstanding H2O+SO2 tolerance.Finally,the in situ DRIFTS reveals that the NH3‐SCR reaction over the V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst follows an L‐H mechanism,and that K poisoning does not change the reaction mechanism.展开更多
In this work, the effectiveness of V2O5-WO3/TiO2 catalysts modified with different CeO2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied compara...In this work, the effectiveness of V2O5-WO3/TiO2 catalysts modified with different CeO2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V2O5-WO3/CeO2-TiO2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%(All Ce contents are in mass fractions), but the NO conversion of V2O5-WO3/CeO2/TiO2 catalysts modified by impregnation methods was lower than V2O5-WO3/CeO2-TiO2 catalysts especially beyond 2.5% Ce doping contents. The V2O5-WO3/CeO2-TiO2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce^(3+)species and more Br?nsted acid sites than that by impregnation. The vacancies caused by more Ce^(3+)species were favorable for more NO oxidation to NO2, and the interaction between Ce species and WOxspecies generated more Br?nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V2O5-WO3/CeO2-TiO2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V2O5-WO3/TiO2 catalysts.展开更多
TiO2 supports doped with different amounts of Si were prepared by a sol-gel method, and 1 wt% vanadia (V2O5) loaded on Si-doped TiO2 was obtained by an impregnation method. The mole ratio of Si/Ti was 0.2, NOx conve...TiO2 supports doped with different amounts of Si were prepared by a sol-gel method, and 1 wt% vanadia (V2O5) loaded on Si-doped TiO2 was obtained by an impregnation method. The mole ratio of Si/Ti was 0.2, NOx conversion exceeds 94% at 300℃ and GHSV of 41,324 hr-1 , which is about 20% higher than pure V2O5/TiO2 . The catalysts were characterized by XRD, BET, TEM, FT-IR, NH3-TPD, XPS, H2-TPR, Raman and in situ DRIFTS. The results of FT-IR and XPS indicated that Si was doped into the TiO2 lattice successfully and a solid solution was obtained. V2O5 active component could be dispersed well on the support with the increasing of surface area of the catalyst, which was confirmed by Raman and XRD results. Above all, the numbers of acid sites (especially the Br nsted-acid) and oxidation properties were enhanced for Si-doped V2O5/TiO2 catalysts, which improved the deNOx catalytic activity.展开更多
A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. ...A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. A special heat treatment was used in the calcination to maintain the large surface area and high dispersion of vanadium species. This catalyst was compared to a common V2O5-TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new catalyst has a surface area of 117.7 m^2/g, which was 38% higher than the traditional V2O5-TiO2 catalyst. The selective catalytic reduction(SCR) performance demonstrated that the new catalyst had a wider temperature window and better N2 selectivity compared to the traditional one. The NO conversion was 80% from 200 to 450 °C. The temperature window was 100 °C wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V-O-V linkages on the catalyst prepared by the traditional method. The amount of V-O-Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X-ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.展开更多
The selective catalytic reduction of NOV with NH3 (NH3-SCR) is a very effective technology to control the emission of NOA, and the thermal stability of NH3-SCR catalyst is very important for removal of NOV from diesel...The selective catalytic reduction of NOV with NH3 (NH3-SCR) is a very effective technology to control the emission of NOA, and the thermal stability of NH3-SCR catalyst is very important for removal of NOV from diesel engines. In this work, V2O5/WO3-TiO2 (VWT) and SiO2- doped V2O5/WO3-TiO2 (VWTSi10)) catalysts were prepared by impregnation method and characterized by Brunauer- Emmett-Teller (BET), X-ray diffraction (XRD), Raman, temperature programmed reduction by hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption by ammonia (NH3- TPD). The doping of SiO2 promotes the thermal stability of V2O5/WO3-TiO? for NH3-SCR significantly. After calcination at 650 °C for 50 h, the operation window of 10% SiO2-doped V2O5/WO3-TiO2 is 220-480 °C, while the maximum NOV conversion on V2O5/WO3-TiO2 is about 77%. The presenee of SiO2 obviously blocks the transformation of TiO2 from anatase to rutile and stabilizes the dispersion of VOv and WO3 on the surface. It is available for the existence of V44 and the amount of surface acid sites increases, which inhabits the NH3 oxidation at the high temperature range and promotes NH3-SCR activity.展开更多
基金supported by the Leading Edge Technology of Jiangsu Province(BK20222009-X.Z.,BK20202008-X.Z.)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)National Undergraduate Innovation Training Program of NUAA(202410287179Y).
摘要Zn-based thermal charging devices,utilizing the synergistic effect of ion thermoextraction and thermodiffusion,are able to efficiently convert thermal energy into electrical energy and storage in the devices,making them a highly promising technology for low-grade heat recovery and utilization.However,the low output power density and energy conversion efficiency resulted by the slow diffusion kinetics of Zn2+hinder their development.Herein,we present a highperformance thermal charging cell design using Zn2+/NH4+hybrid ion electrolyte,which not only maintains the high output voltage of the Zn-based thermoelectric system,but also significantly enhances the output power density due to the fast diffusion kinetics of NH4+.Based on this strategy,the thermal charging cell displays a high thermopower of 12.5 mV K-1and an excellent normalized power density of 19.6 mW m-2K-2at a temperature difference of 35 K.The Carnot-relative efficiency is as high as 12.74%.Moreover,it can operate continuously for over 72 h when the temperature difference persists,achieving a balance between thermoelectric conversion and output.This work provides a simple and effective strategy for the design of high-performance thermal charging cells for low-grade heat conversion and utilization.
摘要二噁英会降低人类的免疫力,影响人体和神经发育;氮氧化物则会对人体的各项脏器和血液组织有严重危害,还会破坏臭氧层,加速酸雨的形成.商业钒钛催化剂既能脱除氮氧化物又能催化分解二噁英(邻二氯苯作为模拟物),二噁英活性温度区为200~300℃,而脱硝活性温度为300~400℃.研究了VOx/TiO2、MnOx/TiO2以及VOx-MnOx/TiO2等催化剂在200~300℃脱硝、脱除二噁英的情况.结果表明,在VOx/TiO2催化剂中掺入MnOx促进脱硝活性温度区间由300~400℃往200~300℃偏移,当MnOx和VOx摩尔比为3∶1时,催化剂在250℃脱硝和脱除二噁英的效果最好,催化NO和邻二氯苯效率分别为92.0%和89.0%.原位红外漫反射光谱研究表明,1V3M/T催化剂表面的脱硝反应在250℃遵循L-H机理,—NH2、Nx Hy Oz、单齿亚硝酸盐和二齿硝酸盐是主要的反应中间体.
基金supported by the National Natural Science Foundation of China (51372137)the National High Technology Research and Development Program of China (863 Program,2015AA034603)~~
摘要V2O5/WO3‐TiO2 and V2O5/WO3‐TiO2‐SiO2 catalysts were prepared by a wetness impregnation method, and both the catalysts were hydrothermally aged at 750℃ in 10 vol%H2O/air for 24 h. The catalysts were evaluated for NOx conversion using NH3 as the reductant. Hydrothermal ageing decreased the NOx conversion of V2O5/WO3‐TiO2 catalyst severely over the entire measured tem‐perature range. Interestingly, the NH3‐SCR activity of the silica‐modified catalyst at 220–480℃ is enhanced after ageing. The catalysts were characterized by X‐ray diffraction, nitrogen adsorption, X‐ray fluorescence, Raman spectroscopy, H2 temperature‐programmed reduction, and NH3 temper‐ature‐programmed desorption. The addition of silica inhibited the phase transition from anatase to rutile titania, growth of TiO2 crystallite size and shrinkage of catalyst surface area. Consequently, the vanadia species remained highly dispersed and the hydrothermal stability of the V2O5/WO3‐TiO2 catalyst was significantly improved.
基金supported by the National Natural Science Foundation of China(21876168,21507130)the Key Projects for Common Key Technology Innovation in Key Industries in Chongqing(cstc2016zdcy-ztzx0020-01)+2 种基金the Chongqing Science&Technology Commission(cstc2016jcyjA0070,cstckjcxljrc13)the Open Project Program of Chongqing Key Laboratory of Catalysis and Functional Organic Molecules from Chongqing Technology and Business University(1456029)the Graduate Innovation Project of Chongqing Technology and Business University(yjscxx201803-028-22)~~
摘要A series of V2O5‐WO3/TiO2‐ZrO2,V2O5‐WO3/TiO2‐CeO2,and V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalysts were synthesized to improve the selective catalytic reduction(SCR)performance and the K‐poisoning resistance of a V2O5‐WO3/TiO2 catalyst.The physicochemical properties were investigated by using XRD,BET,NH3‐TPD,H2‐TPR,and XPS,and the catalytic performance and K‐poisoning resistance were evaluated via a NH3‐SCR model reaction.Ce^4+and Zr^4+co‐doping were found to enhance the conversion of NOx,and exhibit the best K‐poisoning resistance owing to the largest BET‐specific surface area,pore volume,and total acid site concentration,as well as the minimal effects on the surface acidity and redox ability from K poisoning.The V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst also presents outstanding H2O+SO2 tolerance.Finally,the in situ DRIFTS reveals that the NH3‐SCR reaction over the V2O5‐WO3/TiO2‐CeO2‐ZrO2 catalyst follows an L‐H mechanism,and that K poisoning does not change the reaction mechanism.
基金Project supported by the Guangxi Natural Science Foundation(2014GXNSFAA118057)Guangxi Science and Technology Planning Project(AB16380276)
摘要In this work, the effectiveness of V2O5-WO3/TiO2 catalysts modified with different CeO2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V2O5-WO3/CeO2-TiO2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%(All Ce contents are in mass fractions), but the NO conversion of V2O5-WO3/CeO2/TiO2 catalysts modified by impregnation methods was lower than V2O5-WO3/CeO2-TiO2 catalysts especially beyond 2.5% Ce doping contents. The V2O5-WO3/CeO2-TiO2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce^(3+)species and more Br?nsted acid sites than that by impregnation. The vacancies caused by more Ce^(3+)species were favorable for more NO oxidation to NO2, and the interaction between Ce species and WOxspecies generated more Br?nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V2O5-WO3/CeO2-TiO2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V2O5-WO3/TiO2 catalysts.
基金supported by the National Natural Science Foundation of China (No. 51078185, U1162119)the research fund of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province (No. AE201001)the research fund for the Doctoral Program of Higher Education of China (No.20113219110009)
摘要TiO2 supports doped with different amounts of Si were prepared by a sol-gel method, and 1 wt% vanadia (V2O5) loaded on Si-doped TiO2 was obtained by an impregnation method. The mole ratio of Si/Ti was 0.2, NOx conversion exceeds 94% at 300℃ and GHSV of 41,324 hr-1 , which is about 20% higher than pure V2O5/TiO2 . The catalysts were characterized by XRD, BET, TEM, FT-IR, NH3-TPD, XPS, H2-TPR, Raman and in situ DRIFTS. The results of FT-IR and XPS indicated that Si was doped into the TiO2 lattice successfully and a solid solution was obtained. V2O5 active component could be dispersed well on the support with the increasing of surface area of the catalyst, which was confirmed by Raman and XRD results. Above all, the numbers of acid sites (especially the Br nsted-acid) and oxidation properties were enhanced for Si-doped V2O5/TiO2 catalysts, which improved the deNOx catalytic activity.
基金supported by the National Natural Science Foundation of China(21325731,21221004)the National High Technology Research and Development Program of China(863 Program)the State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex
摘要A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. A special heat treatment was used in the calcination to maintain the large surface area and high dispersion of vanadium species. This catalyst was compared to a common V2O5-TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new catalyst has a surface area of 117.7 m^2/g, which was 38% higher than the traditional V2O5-TiO2 catalyst. The selective catalytic reduction(SCR) performance demonstrated that the new catalyst had a wider temperature window and better N2 selectivity compared to the traditional one. The NO conversion was 80% from 200 to 450 °C. The temperature window was 100 °C wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V-O-V linkages on the catalyst prepared by the traditional method. The amount of V-O-Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X-ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.
基金Supported by Fundamental Research Funds for Central Universities(HEUCF201403002)Advanced Technique Project Funds of the Manufacture and Information Ministry
基金financially supported by the National Key Research and Development Program of China (No. 2016YFC0204300)the National High Technology Research and Development Program of China (No. 2015AA034603)+2 种基金the National Natural Science Foundation of China (Nos. 21333003 and 21571061)the "Shu Guang" Project of the Shanghai Municipal Education Commission (No. 12SG29)the Commission of Science and Technology of Shanghai Municipality (No. 15DZ1205305)
摘要The selective catalytic reduction of NOV with NH3 (NH3-SCR) is a very effective technology to control the emission of NOA, and the thermal stability of NH3-SCR catalyst is very important for removal of NOV from diesel engines. In this work, V2O5/WO3-TiO2 (VWT) and SiO2- doped V2O5/WO3-TiO2 (VWTSi10)) catalysts were prepared by impregnation method and characterized by Brunauer- Emmett-Teller (BET), X-ray diffraction (XRD), Raman, temperature programmed reduction by hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption by ammonia (NH3- TPD). The doping of SiO2 promotes the thermal stability of V2O5/WO3-TiO? for NH3-SCR significantly. After calcination at 650 °C for 50 h, the operation window of 10% SiO2-doped V2O5/WO3-TiO2 is 220-480 °C, while the maximum NOV conversion on V2O5/WO3-TiO2 is about 77%. The presenee of SiO2 obviously blocks the transformation of TiO2 from anatase to rutile and stabilizes the dispersion of VOv and WO3 on the surface. It is available for the existence of V44 and the amount of surface acid sites increases, which inhabits the NH3 oxidation at the high temperature range and promotes NH3-SCR activity.