A series CeO2(ZrO2)/TiO2 catalysts were modified with Er using a sol-gel method.The catalytic activity of the obtained catalysts in the selective catalytic reduction(SCR) of NO with NH3 was investigated to determi...A series CeO2(ZrO2)/TiO2 catalysts were modified with Er using a sol-gel method.The catalytic activity of the obtained catalysts in the selective catalytic reduction(SCR) of NO with NH3 was investigated to determine the appropriate Er dosage.The catalysts were characterized using X-ray diffraction,N2 adsorption,NH3 temperature-programmed desorption,H2 temperature-programmed reduction,photoluminescence spectroscopy,electron paramagnetic resonance spectroscopy,and X-ray photoelectron spectroscopy.The results showed that the optimum Er/Ce molar ratio was 0.10;this catalyst had excellent resistance to catalyst poisoning caused by vapor and sulfur and gave more than 90% NO conversion at 220–395 ℃ and a gas hourly space velocity of 71 400 h^-1.Er incorporation increased the Ti^3+ concentrations,oxygen storage capacities,and oxygen vacancy concentrations of the catalysts,resulting in excellent catalytic performance.Er incorporation also decreased the acid strength and inhibited growth of TiO2 and CeO2 crystal particles,which increased the catalytic activity.The results show that high oxygen vacancy concentrations and oxygen storage capacities,large amounts of Ti^3+,and low acid strengths give excellent SCR activity.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
Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg3Al1-xFex,containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective ...Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg3Al1-xFex,containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde(CAL).When x was changed from 0(Ir/Mg3Al)to 1(Ir/Mg3Fe),the rate of CAL hydrogenation reached a maximum at approximately x=0.25,while the selectivity to unsaturated alcohol,i.e.,cinnamyl alcohol,monotonously increased from 44.9%to 80.3%.Meanwhile,the size of the supported Ir particles did not change significantly with x,remaining at 1.7-0.2 nm,as determined by transmission electron microscopy.The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy.The surface of the supported Ir particles was also examined through the in‐situ diffuse reflectance infrared Fourier‐transform of a probe molecule of CO.On the basis of these characterization results,the effects of Fe doping to Mg3Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed.The significant factors are the electron transfer from Fe2+in the Mg3Al1–xFex support to the dispersed Ir particles and the surface geometry.展开更多
Sm-doped Fe_(2)O_(3)catalysts,with a homogeneous distribution of Sm in Fe_(2)O_(3)nanoparticles,were synthesized using a citric acid-assisted sol-gel method.Kinetic studies show that the reaction rate for NO_(x)reduct...Sm-doped Fe_(2)O_(3)catalysts,with a homogeneous distribution of Sm in Fe_(2)O_(3)nanoparticles,were synthesized using a citric acid-assisted sol-gel method.Kinetic studies show that the reaction rate for NO_(x)reduction using the optimal catalyst(0.06 mol%doping of Sm in Fe_(2)O_(3))was nearly 11 times higher than that for pure Fe_(2)O_(3),when calculated based on specific surface area.Furthermore,the Fe_(0.94)Sm_(0.06)O_(x)catalyst maintains>83%NO_(x)conversion for 168 h at a high space velocity in the presence of SO_(2)and H_(2)O at 250℃.A substantial amount of surface-adsorbed oxygen was generated on the surface of Fe_(0.94)Sm_(0.06)O_(x),which promoted NO oxidation and the subsequent fast reaction between NO_(x)and NH_(3).The adsorption and activation of NH_(3)was also enhanced by Sm doping.In addition,Sm doping facilitated the decomposition of NH_(4)HSO_(4)on the surface of Fe_(0.94)Sm_(0.06)O_(x),resulting in its high activity and stability in the presence of SO_(2)+H_(2)O.展开更多
Here,we report cobalt nanoparticles encapsulated in nitrogen‐doped carbon(Co@NC)that exhibit excellent catalytic activity and chemoselectivity for room‐temperature hydrogenation of nitroarenes.Co@NC was synthesized ...Here,we report cobalt nanoparticles encapsulated in nitrogen‐doped carbon(Co@NC)that exhibit excellent catalytic activity and chemoselectivity for room‐temperature hydrogenation of nitroarenes.Co@NC was synthesized by pyrolyzing a mixture of a cobalt salt,an inexpensive organic molecule,and carbon nitride.Using the Co@NC catalyst,a turnover frequency of^12.3 h?1 and selectivity for 4‐aminophenol of>99.9%were achieved for hydrogenation of 4‐nitrophenol at room temperature and 10 bar H2 pressure.The excellent catalytic performance can be attributed to the cooperative effect of hydrogen activation by electron‐deficient Co nanoparticles and energetically preferred adsorption of the nitro group of nitroarenes to electron‐rich N‐doped carbon.In addition,there is electron transfer from the Co nanoparticles to N‐doped carbon,which further enhances the functionality of the metal center and carbon support.The catalyst also exhibits stable recycling performance and high activity for nitroaromatics with various substituents.展开更多
Amidst the development of photoelectrochemical(PEC)CO_(2) conversion toward practical application,the production of high-value chemicals beyond C1 compounds under mild conditions is greatly desired yet challenging.Her...Amidst the development of photoelectrochemical(PEC)CO_(2) conversion toward practical application,the production of high-value chemicals beyond C1 compounds under mild conditions is greatly desired yet challenging.Here,through rational PEC device design by combining Au-loaded and N-doped TiO_(2) plate nanoarray photoanode with Zn-doped Cu_(2)O dark cathode,efficient conversion of CO_(2) to CH3COOH has been achieved with an outstanding Faradaic efficiency up to 58.1%(91.5%carbon selectivity)at 0.5 V vs.Ag/AgCl.Temperature programmed desorption and in situ Raman spectra reveal that the Zn-dopant in Cu_(2)O plays multiple roles in selective catalytic CO_(2) conversion,including local electronic structure manipulation and active site modification,which together promote the formation of intermediate*CH2/*CH3 for C-C coupling.Apart from that,it is also unveiled that the sufficient electron density provided by the Au-loaded and N-doped TiO_(2) plate nanoarray photoanode plays an equally important role by initiating multi-electron CO_(2) reduction.This work provides fresh insights into the PEC system design to reach the multi-electron reduction reaction and facilitate the C-C coupling reaction toward high-value multicarbon(C2+)chemical production via CO_(2) conversion.展开更多
基金supported by the National Natural Science Foundation of China(51272105)Jiangsu Provincial Science and Technology Supporting Program(BE2013718)+1 种基金Research Subject of Environmental Protection Department of Jiangsu Province of China(2013006)Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)~~
文摘A series CeO2(ZrO2)/TiO2 catalysts were modified with Er using a sol-gel method.The catalytic activity of the obtained catalysts in the selective catalytic reduction(SCR) of NO with NH3 was investigated to determine the appropriate Er dosage.The catalysts were characterized using X-ray diffraction,N2 adsorption,NH3 temperature-programmed desorption,H2 temperature-programmed reduction,photoluminescence spectroscopy,electron paramagnetic resonance spectroscopy,and X-ray photoelectron spectroscopy.The results showed that the optimum Er/Ce molar ratio was 0.10;this catalyst had excellent resistance to catalyst poisoning caused by vapor and sulfur and gave more than 90% NO conversion at 220–395 ℃ and a gas hourly space velocity of 71 400 h^-1.Er incorporation increased the Ti^3+ concentrations,oxygen storage capacities,and oxygen vacancy concentrations of the catalysts,resulting in excellent catalytic performance.Er incorporation also decreased the acid strength and inhibited growth of TiO2 and CeO2 crystal particles,which increased the catalytic activity.The results show that high oxygen vacancy concentrations and oxygen storage capacities,large amounts of Ti^3+,and low acid strengths give excellent SCR activity.
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)~~
文摘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.
文摘Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg3Al1-xFex,containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde(CAL).When x was changed from 0(Ir/Mg3Al)to 1(Ir/Mg3Fe),the rate of CAL hydrogenation reached a maximum at approximately x=0.25,while the selectivity to unsaturated alcohol,i.e.,cinnamyl alcohol,monotonously increased from 44.9%to 80.3%.Meanwhile,the size of the supported Ir particles did not change significantly with x,remaining at 1.7-0.2 nm,as determined by transmission electron microscopy.The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy.The surface of the supported Ir particles was also examined through the in‐situ diffuse reflectance infrared Fourier‐transform of a probe molecule of CO.On the basis of these characterization results,the effects of Fe doping to Mg3Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed.The significant factors are the electron transfer from Fe2+in the Mg3Al1–xFex support to the dispersed Ir particles and the surface geometry.
文摘Sm-doped Fe_(2)O_(3)catalysts,with a homogeneous distribution of Sm in Fe_(2)O_(3)nanoparticles,were synthesized using a citric acid-assisted sol-gel method.Kinetic studies show that the reaction rate for NO_(x)reduction using the optimal catalyst(0.06 mol%doping of Sm in Fe_(2)O_(3))was nearly 11 times higher than that for pure Fe_(2)O_(3),when calculated based on specific surface area.Furthermore,the Fe_(0.94)Sm_(0.06)O_(x)catalyst maintains>83%NO_(x)conversion for 168 h at a high space velocity in the presence of SO_(2)and H_(2)O at 250℃.A substantial amount of surface-adsorbed oxygen was generated on the surface of Fe_(0.94)Sm_(0.06)O_(x),which promoted NO oxidation and the subsequent fast reaction between NO_(x)and NH_(3).The adsorption and activation of NH_(3)was also enhanced by Sm doping.In addition,Sm doping facilitated the decomposition of NH_(4)HSO_(4)on the surface of Fe_(0.94)Sm_(0.06)O_(x),resulting in its high activity and stability in the presence of SO_(2)+H_(2)O.
文摘Here,we report cobalt nanoparticles encapsulated in nitrogen‐doped carbon(Co@NC)that exhibit excellent catalytic activity and chemoselectivity for room‐temperature hydrogenation of nitroarenes.Co@NC was synthesized by pyrolyzing a mixture of a cobalt salt,an inexpensive organic molecule,and carbon nitride.Using the Co@NC catalyst,a turnover frequency of^12.3 h?1 and selectivity for 4‐aminophenol of>99.9%were achieved for hydrogenation of 4‐nitrophenol at room temperature and 10 bar H2 pressure.The excellent catalytic performance can be attributed to the cooperative effect of hydrogen activation by electron‐deficient Co nanoparticles and energetically preferred adsorption of the nitro group of nitroarenes to electron‐rich N‐doped carbon.In addition,there is electron transfer from the Co nanoparticles to N‐doped carbon,which further enhances the functionality of the metal center and carbon support.The catalyst also exhibits stable recycling performance and high activity for nitroaromatics with various substituents.
基金financially supported in part by the National Key R&D Program of China (2017YFA0207301, and 2017YFA0403402)the National Natural Science Foundation of China (21725102, 91961106, U1832156, 22075267, 21803002, 91963108, 21950410514, and U1732272)+5 种基金CAS Key Research Program of Frontier Sciences (QYZDB-SSW-SLH018)Science and Technological Fund of Anhui Province for Outstanding Youth (2008085 J05)Youth Innovation Promotion Association of CAS (2019444)Young Elite Scientist Sponsorship Program by CAST, China Postdoctoral Science Foundation (2019 M652190, 2020 T130627)Chinese Universities Scientific Fund (WK2060190096), MOST (2018YFA0208603)DNL Cooperation Fund, CAS (DNL201922, DNL180201)
文摘Amidst the development of photoelectrochemical(PEC)CO_(2) conversion toward practical application,the production of high-value chemicals beyond C1 compounds under mild conditions is greatly desired yet challenging.Here,through rational PEC device design by combining Au-loaded and N-doped TiO_(2) plate nanoarray photoanode with Zn-doped Cu_(2)O dark cathode,efficient conversion of CO_(2) to CH3COOH has been achieved with an outstanding Faradaic efficiency up to 58.1%(91.5%carbon selectivity)at 0.5 V vs.Ag/AgCl.Temperature programmed desorption and in situ Raman spectra reveal that the Zn-dopant in Cu_(2)O plays multiple roles in selective catalytic CO_(2) conversion,including local electronic structure manipulation and active site modification,which together promote the formation of intermediate*CH2/*CH3 for C-C coupling.Apart from that,it is also unveiled that the sufficient electron density provided by the Au-loaded and N-doped TiO_(2) plate nanoarray photoanode plays an equally important role by initiating multi-electron CO_(2) reduction.This work provides fresh insights into the PEC system design to reach the multi-electron reduction reaction and facilitate the C-C coupling reaction toward high-value multicarbon(C2+)chemical production via CO_(2) conversion.