The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,...The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,Pd and Ru) modified Cu/alkalized sepiolite(CuX/SEPA) catalysts were prepared and used for the DOMM in a gas-phase system at low temperatures.The CuRu/SEPA exhibited the highest methanol production of 53 μmol·g^(-1)·h^(-1) and methanol selectivity of 90% under the optimal reaction conditions.Various characterizations demonstrated that the addition of Ru promoted the formation of Cu^(2+)and the contraction of Cu—Si/Al bonds to reduce the distance between framework Al atoms of SEPA to further generate more Al pairs,which facilitated the formation of reactive dicopper species([Cu_(2)O]^(2+)or [Cu_(2)O_(2)]^(2+)).Investigation of the reaction mechanism revealed that [Cu_(2)O]^(2+) or [Cu_(2)O_(2)]^(2+) species could adsorb and activate methane to form CH_(3)O^(*) species and ultimately generated methanol with the assistance of water.展开更多
Glycerol steam reforming(GSR)is one of the promising technologies that can realize renewable hydrogen production and efficient utilization of crude glycerol.To illuminate the functions of Ca content(3%,6%,9%,and 12%,b...Glycerol steam reforming(GSR)is one of the promising technologies that can realize renewable hydrogen production and efficient utilization of crude glycerol.To illuminate the functions of Ca content(3%,6%,9%,and 12%,by mass)and preparation method for Ni/ATP catalyst structure and its catalytic behaviors,the Ni-xCa/ATP(x=3%,6%,9%,and 12%,by mass)catalysts are prepared by co-impregnation(ci)and hydrothermal synthesis(hs)method and then tested in GSR.Characterization results of XRD,N_(2) adsorption–desorption,H_(2)-TPR,HRTEM,XPS,and NH_(3)/CO_(2)-TPD demonstrate that the combined effect between appropriate Ca additive(6%,by mass)and hs enhance catalyst reducibility,uniform distribution of Ca additive and nickel species over ATP,and adsorption for CO_(2).This attributes to hs method protects the ATP framework through suppressing the interaction of Ca with ATP and promotes the formation of NiCaOx interface sites.Therefore,Ni-6Ca/ATP-hs exhibits the highest conversion(86.77%)of glycerol to gas product and H_(2) yield(76.17%)and selectivity(58.56%)during GSR.Furthermore,XRD,HRTEM,TGDTG and Raman analyses confirm that Ni-6Ca/ATP-hs also reveals outstanding anti-sintering and coke resistance.In addition,the structural evolution process of Ni/ATP catalyst with Ca introduction and hs method is presented.Considering the high performance,simple preparation process and low cost,the as-prepared catalyst providing new opportunities for utilization of glycerol derived from biodiesel industry.展开更多
基金financial assistance from the Anhui Provincial Major Science and Technology Project(202003a05020022)the Institute of Energy,Hefei Comprehensive National Science Center(21KZS219)。
文摘The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,Pd and Ru) modified Cu/alkalized sepiolite(CuX/SEPA) catalysts were prepared and used for the DOMM in a gas-phase system at low temperatures.The CuRu/SEPA exhibited the highest methanol production of 53 μmol·g^(-1)·h^(-1) and methanol selectivity of 90% under the optimal reaction conditions.Various characterizations demonstrated that the addition of Ru promoted the formation of Cu^(2+)and the contraction of Cu—Si/Al bonds to reduce the distance between framework Al atoms of SEPA to further generate more Al pairs,which facilitated the formation of reactive dicopper species([Cu_(2)O]^(2+)or [Cu_(2)O_(2)]^(2+)).Investigation of the reaction mechanism revealed that [Cu_(2)O]^(2+) or [Cu_(2)O_(2)]^(2+) species could adsorb and activate methane to form CH_(3)O^(*) species and ultimately generated methanol with the assistance of water.
基金the financial assistance from the National Natural Science Foundation of China (51906001 and 51876001)University Natural Science Research Project of Anhui Province (KJ2020ZD31)+1 种基金Key Research and Development Projects of Anhui Province (202004a06020053)Doctoral Fund project of Anhui University of Science and Technology
文摘Glycerol steam reforming(GSR)is one of the promising technologies that can realize renewable hydrogen production and efficient utilization of crude glycerol.To illuminate the functions of Ca content(3%,6%,9%,and 12%,by mass)and preparation method for Ni/ATP catalyst structure and its catalytic behaviors,the Ni-xCa/ATP(x=3%,6%,9%,and 12%,by mass)catalysts are prepared by co-impregnation(ci)and hydrothermal synthesis(hs)method and then tested in GSR.Characterization results of XRD,N_(2) adsorption–desorption,H_(2)-TPR,HRTEM,XPS,and NH_(3)/CO_(2)-TPD demonstrate that the combined effect between appropriate Ca additive(6%,by mass)and hs enhance catalyst reducibility,uniform distribution of Ca additive and nickel species over ATP,and adsorption for CO_(2).This attributes to hs method protects the ATP framework through suppressing the interaction of Ca with ATP and promotes the formation of NiCaOx interface sites.Therefore,Ni-6Ca/ATP-hs exhibits the highest conversion(86.77%)of glycerol to gas product and H_(2) yield(76.17%)and selectivity(58.56%)during GSR.Furthermore,XRD,HRTEM,TGDTG and Raman analyses confirm that Ni-6Ca/ATP-hs also reveals outstanding anti-sintering and coke resistance.In addition,the structural evolution process of Ni/ATP catalyst with Ca introduction and hs method is presented.Considering the high performance,simple preparation process and low cost,the as-prepared catalyst providing new opportunities for utilization of glycerol derived from biodiesel industry.
