An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant s...An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt.Notably,electron-enriched Coδ-species participated in efficient chemisorption and activation of CO_(2)to generate monodentate carbonate.Simultaneously,plentiful available Ni0sites facilitated H2dissociation,thus CO_(2)and H2were smoothly activated at zones of Coδ-species and Ni0,respectively.Detailed in situ DRIFTS,quasi situ XPS,TPSR,and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ-species and Ni0.The zonal activation of CO_(2)and H2by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.展开更多
Phosphate ions promoted Cu-SAPO-34(P-Cu-SAPO-34)were prepared using bulk CuO particles as Cu^(2+)precursor by a solid-state ion exchange technique for the selective catalytic reduction of NO_(x) with NH_3(NH_3-SCR).Th...Phosphate ions promoted Cu-SAPO-34(P-Cu-SAPO-34)were prepared using bulk CuO particles as Cu^(2+)precursor by a solid-state ion exchange technique for the selective catalytic reduction of NO_(x) with NH_3(NH_3-SCR).The effects of high temperature(H-T)hydrothermal aging on the NO_(x) removal(de-NO_(x))performance of Cu-SAPO-34 with and without phosphate ions were systematically investigated at atomic level.The results displayed that both Cu-SAPO-34 and P-Cu-SAPO-34 presented relatively poor NO_(x) removal activity with a low conversion(<30%)at 250-500℃.However,after H-T hydrothermal treatment(800℃ for 10 hr at 10%H_2O),these two samples showed significantly satisfied NO_(x) elimination performance with a quite high conversion(70%-90%)at 250-500℃.Additionally,phosphate ions decoration can further enhance the catalytic performance of Cu-SAPO-34 after hydrothermal treatment(Cu-SAPO-34H).The textural properties,morphologies,structural feature,acidity,redox characteristic,and surface-active species of the fresh and hydrothermally aged samples were analyzed using various characterization methods.The systematical characterization results revealed that increases of 28%of the isolated Cu^(2+)active species(Cu^(2+)-2Z,Cu(OH)^(+)-Z)mainly from bulk CuO and 50%of the Bronsted acid sites,the high dispersion of isolated Cu^(2+)active component as well as the Bronsted acid sites were mainly responsible for the accepted catalytic activity of these two hydrothermally aged samples,especially for P-Cu-SAPO-34H.展开更多
A series of CeO2–ZrO2–WO3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH3 over a wide temperature of 150–550℃....A series of CeO2–ZrO2–WO3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH3 over a wide temperature of 150–550℃.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H2O.The fresh catalyst showed above 90% NOx conversion at 201–459℃,which is applicable to diesel exhaust NOx purification(200–440℃).The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures(below 300℃),while the activity was notably enhanced at high temperature(above 450℃).The aged CZW catalyst(hydrothermal aging at 700℃ for 8 hr)showed almost 80% NOx conversion at 229–550℃,while the V2O5–WO3/TiO2 catalyst presented above 80% NOx conversion at 308–370℃.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO2–ZrO2 solid solution,amorphous WO3 phase and optimal acidity.In addition,the formation of WO3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.展开更多
基金funded by the Science and Technology Project of Southwest United Graduate School of Yunnan Province(No.202302AQ370002)the National Natural Science Foundation of China(No.22206066)。
文摘An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt.Notably,electron-enriched Coδ-species participated in efficient chemisorption and activation of CO_(2)to generate monodentate carbonate.Simultaneously,plentiful available Ni0sites facilitated H2dissociation,thus CO_(2)and H2were smoothly activated at zones of Coδ-species and Ni0,respectively.Detailed in situ DRIFTS,quasi situ XPS,TPSR,and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ-species and Ni0.The zonal activation of CO_(2)and H2by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.
基金supported by the National Natural Science Foundation of China (No.NSFC22166020)。
文摘Phosphate ions promoted Cu-SAPO-34(P-Cu-SAPO-34)were prepared using bulk CuO particles as Cu^(2+)precursor by a solid-state ion exchange technique for the selective catalytic reduction of NO_(x) with NH_3(NH_3-SCR).The effects of high temperature(H-T)hydrothermal aging on the NO_(x) removal(de-NO_(x))performance of Cu-SAPO-34 with and without phosphate ions were systematically investigated at atomic level.The results displayed that both Cu-SAPO-34 and P-Cu-SAPO-34 presented relatively poor NO_(x) removal activity with a low conversion(<30%)at 250-500℃.However,after H-T hydrothermal treatment(800℃ for 10 hr at 10%H_2O),these two samples showed significantly satisfied NO_(x) elimination performance with a quite high conversion(70%-90%)at 250-500℃.Additionally,phosphate ions decoration can further enhance the catalytic performance of Cu-SAPO-34 after hydrothermal treatment(Cu-SAPO-34H).The textural properties,morphologies,structural feature,acidity,redox characteristic,and surface-active species of the fresh and hydrothermally aged samples were analyzed using various characterization methods.The systematical characterization results revealed that increases of 28%of the isolated Cu^(2+)active species(Cu^(2+)-2Z,Cu(OH)^(+)-Z)mainly from bulk CuO and 50%of the Bronsted acid sites,the high dispersion of isolated Cu^(2+)active component as well as the Bronsted acid sites were mainly responsible for the accepted catalytic activity of these two hydrothermally aged samples,especially for P-Cu-SAPO-34H.
基金supported by the National Natural Science Foundation of China(Nos.U1137603,21307047)the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education(No.LYJ1309)
文摘A series of CeO2–ZrO2–WO3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH3 over a wide temperature of 150–550℃.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H2O.The fresh catalyst showed above 90% NOx conversion at 201–459℃,which is applicable to diesel exhaust NOx purification(200–440℃).The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures(below 300℃),while the activity was notably enhanced at high temperature(above 450℃).The aged CZW catalyst(hydrothermal aging at 700℃ for 8 hr)showed almost 80% NOx conversion at 229–550℃,while the V2O5–WO3/TiO2 catalyst presented above 80% NOx conversion at 308–370℃.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO2–ZrO2 solid solution,amorphous WO3 phase and optimal acidity.In addition,the formation of WO3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.