It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(...It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.展开更多
A series of heteropoly acid (HPA) based Al2O3 catalysts with three-dimensional ordered (3DOM) structure were synthesized by colloidal crystal template method.Interconnected macropores (250 nm) could be clearly observe...A series of heteropoly acid (HPA) based Al2O3 catalysts with three-dimensional ordered (3DOM) structure were synthesized by colloidal crystal template method.Interconnected macropores (250 nm) could be clearly observed by scanning electron microscope (SEM) and transmission electron microscope (TEM).Mesopores could be detected by N2 adsorption-desorption isotherms which further confirmed the 3DOM structural characteristics of catalyst.Moreover,Keggin-type HPW was highly dispersed in the Al2O3 framework,which suggested by powder X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) results.The oxidation desulfurization (ODS) performance of 3DOM H3PW12O40/Al2O3 of refractory sulphur compounds was evaluated in the presence of hydrogen peroxide.It oxidized 98.5% of dibenzothiophene (DBT) into corresponding sulfone within 3 h,which exhibited superior ODS performance than corresponding mesoporous and microporous H3PW12O40/Al2O3 catalyst.The enhancement of ODS efficiency is related to the improvement of mass transfer of DBT in the pore channel resulting from the interconnected 3DOM structure.Furthermore,the as-prepared catalyst still demonstrates outstanding cycle performance after 6 runs,which could be easily recovered from the model fuel.展开更多
NH_(3)-SCR is an effective mean of NOxremoval in the non-electric industry, however, the high activation temperature and poor H_(2)O resistance of SCR catalysts posed a barrier to its application. In this work, a seri...NH_(3)-SCR is an effective mean of NOxremoval in the non-electric industry, however, the high activation temperature and poor H_(2)O resistance of SCR catalysts posed a barrier to its application. In this work, a series of three-dimensionally ordered macroporous(3DOM) catalysts were synthesized via a colloidal crystal template(CCT) method, and various characterizations were carried out to explore the physicochemical property of catalysts. The experiment results reveal that Ce_(0.2)Mn_(0.2)/3DOM-TiO_(2) catalyst presents the excellent low-temperature catalytic activity of nearly 100% at 100℃. Furthermore, the enhanced H_(2)O resistance is achieved, certified by the unaffected NO remove at 150℃ in the participation of 15 vol% H_(2)O. The characterizations results exhibit that the improved dispersion of the active component and enhanced redox ability are conducive to the low-temperature catalytic activity. N_(2) adsorption and desorption experiments indicate that catalyst with 3DOM support possesses a larger pore diameter and specific surface area, which may weaken the condensation of H_(2)O in the microporosity of catalysts and improved the H_(2)O resistance of the catalyst. In situ DRIFTS results manifest that Ce_(0.2)Mn_(0.2)/3DOM-TiO_(2) catalyst could not only absorb more NH_(3) and generate more surface-active sites, but inhibit the competitive adsorption between H_(2)O and SCR reactants.展开更多
基金supported by the National Key Research and Development Program of China(Nos.2022YFB3504100,2022YFB3506200)the National Natural Science Foundation of China(Nos.22208373,22376217)+1 种基金the Beijing Nova Program(No.20220484215)the Science Foundation of China University of Petroleum,Beijing(No.2462023YJRC030)。
文摘It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.
基金Funded by the National Natural Science Foundation of China(No.21476177)。
文摘A series of heteropoly acid (HPA) based Al2O3 catalysts with three-dimensional ordered (3DOM) structure were synthesized by colloidal crystal template method.Interconnected macropores (250 nm) could be clearly observed by scanning electron microscope (SEM) and transmission electron microscope (TEM).Mesopores could be detected by N2 adsorption-desorption isotherms which further confirmed the 3DOM structural characteristics of catalyst.Moreover,Keggin-type HPW was highly dispersed in the Al2O3 framework,which suggested by powder X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) results.The oxidation desulfurization (ODS) performance of 3DOM H3PW12O40/Al2O3 of refractory sulphur compounds was evaluated in the presence of hydrogen peroxide.It oxidized 98.5% of dibenzothiophene (DBT) into corresponding sulfone within 3 h,which exhibited superior ODS performance than corresponding mesoporous and microporous H3PW12O40/Al2O3 catalyst.The enhancement of ODS efficiency is related to the improvement of mass transfer of DBT in the pore channel resulting from the interconnected 3DOM structure.Furthermore,the as-prepared catalyst still demonstrates outstanding cycle performance after 6 runs,which could be easily recovered from the model fuel.
基金Project supported by National Key Research and Development Program of China(2021YFB3500601)。
文摘NH_(3)-SCR is an effective mean of NOxremoval in the non-electric industry, however, the high activation temperature and poor H_(2)O resistance of SCR catalysts posed a barrier to its application. In this work, a series of three-dimensionally ordered macroporous(3DOM) catalysts were synthesized via a colloidal crystal template(CCT) method, and various characterizations were carried out to explore the physicochemical property of catalysts. The experiment results reveal that Ce_(0.2)Mn_(0.2)/3DOM-TiO_(2) catalyst presents the excellent low-temperature catalytic activity of nearly 100% at 100℃. Furthermore, the enhanced H_(2)O resistance is achieved, certified by the unaffected NO remove at 150℃ in the participation of 15 vol% H_(2)O. The characterizations results exhibit that the improved dispersion of the active component and enhanced redox ability are conducive to the low-temperature catalytic activity. N_(2) adsorption and desorption experiments indicate that catalyst with 3DOM support possesses a larger pore diameter and specific surface area, which may weaken the condensation of H_(2)O in the microporosity of catalysts and improved the H_(2)O resistance of the catalyst. In situ DRIFTS results manifest that Ce_(0.2)Mn_(0.2)/3DOM-TiO_(2) catalyst could not only absorb more NH_(3) and generate more surface-active sites, but inhibit the competitive adsorption between H_(2)O and SCR reactants.
