Perovskite oxides has been attracted much attention as high-performance oxygen carriers for chemical looping reforming of methane,but they are easily inactivated by the presence of trace H_(2)S.Here,we propose to modu...Perovskite oxides has been attracted much attention as high-performance oxygen carriers for chemical looping reforming of methane,but they are easily inactivated by the presence of trace H_(2)S.Here,we propose to modulate both the activity and resistance to sulfur poisoning by dual substitution of Mo and Ni ions with the Fe-sites of LaFeO_(3)perovskite.It is found that partial substitution of Ni for Fe substantially improves the activity of LaFeO_(3)perovskite,while Ni particles prefer to grow and react with H_(2)S during the long-term successive redox process,resulting in the deactivation of oxygen carriers.With the presence of Mo in LaNi_(0.05)Fe_(0.95)O_(3−σ)perovskite,H_(2)S preferentially reacts with Mo to generate MoS_(2),and then the CO_(2)oxidation can regenerate Mo via removing sulfur.In addition,Mo can inhibit the accumulation and growth of Ni,which helps to improve the redox stability of oxygen carriers.The LaNi_(0.05)Mo_(0.07)Fe_(0.88)O_(3−σ)oxygen carrier exhibits stable and excellent performance,with the CH_(4)conversion higher than 90%during the 50 redox cycles in the presence of 50 ppm H_(2)S at 800℃.This work highlights a synergistic effect in the perovskite oxides induced by dual substitution of different cations for the development of high-performance oxygen carriers with excellent sulfur tolerance.展开更多
The challenges posed by energy and environmental issues have forced mankind to explore and utilize unconventional energy sources.It is imperative to convert the abundant coalbed gas(CBG)into high value-added products,...The challenges posed by energy and environmental issues have forced mankind to explore and utilize unconventional energy sources.It is imperative to convert the abundant coalbed gas(CBG)into high value-added products,i.e.,selective and efficient conversion of methane from CBG.Methane activation,known as the“holy grail”,poses a challenge to the design and development of catalysts.The structural complexity of the active metal on the carrier is of particular concern.In this work,we have studied the nucleation growth of small Co clusters(up to Co_(6))on the surface of CeO_(2)(110)using density functional theory,from which a stable loaded Co/CeO_(2)(110)structure was selected to investigate the methane activation mechanism.Despite the relatively small size of the selected Co clusters,the obtained Co_(x)/CeO_(2)(110)exhibits interesting properties.The optimized Co_(5)/CeO_(2)(110)structure was selected as the optimal structure to study the activation mechanism of methane due to its competitive electronic structure,adsorption energy and binding energy.The energy barriers for the stepwise dissociation of methane to form CH3^(*),CH2^(*),CH^(*),and C^(*)radical fragments are 0.44,0.55,0.31,and 1.20 eV,respectively,indicating that CH^(*)dissociative dehydrogenation is the rate-determining step for the system under investigation here.This fundamental study of metal-support interactions based on Co growth on the CeO_(2)(110)surface contributes to the understanding of the essence of Co/CeO_(2) catalysts with promising catalytic behavior.It provides theoretical guidance for better designing the optimal Co/CeO_(2) catalyst for tailored catalytic reactions.展开更多
An appropriate optimal number of market segments(ONS)estimation is essential for an enterprise to achieve successful market segmentation,but at present,there is a serious lack of attention to this issue in market segm...An appropriate optimal number of market segments(ONS)estimation is essential for an enterprise to achieve successful market segmentation,but at present,there is a serious lack of attention to this issue in market segmentation.In our study,an independent adaptive ONS estimation method BWCON-NSDK-means++is proposed by integrating a newinternal validity index(IVI)Between-Within-Connectivity(BWCON)and a newstable clustering algorithmNatural-SDK-means++(NSDK-means++)in a novel way.First,to complete the evaluation dimensions of the existing IVIs,we designed a connectivity formula based on the neighbor relationship and proposed the BWCON by integrating the connectivity with other two commonly considered measures of compactness and separation.Then,considering the stability,number of parameters and clustering performance,we proposed the NSDK-means++to participate in the integrationwhere the natural neighbor was used to optimize the initial cluster centers(ICCs)determination strategy in the SDK-means++.At last,to ensure the objectivity of the estimatedONS,we designed a BWCON-based ONS estimation framework that does not require the user to set any parameters in advance and integrated the NSDK-means++into this framework forming a practical ONS estimation tool BWCON-NSDK-means++.The final experimental results showthat the proposed BWCONand NSDK-means++are significantlymore suitable than their respective existing models to participate in the integration for determining theONS,and the proposed BWCON-NSDK-means++is demonstrably superior to the BWCON-KMA,BWCONMBK,BWCON-KM++,BWCON-RKM++,BWCON-SDKM++,BWCON-Single linkage,BWCON-Complete linkage,BWCON-Average linkage and BWCON-Ward linkage in terms of the ONS estimation.Moreover,as an independentmarket segmentation tool,the BWCON-NSDK-means++also outperforms the existing models with respect to the inter-market differentiation and sub-market size.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 52174279, U2202251, and 52266008)Applied Basic Research Program of Yunnan Province for Distinguished Young Scholars (No. 202201AV070004)+1 种基金Central Guiding Local Science and Technology Development Fund (No. 202207AA110001)the Yunnan Fundamental Research Projects (No. 202301AU070027, 202401AT070388)
文摘Perovskite oxides has been attracted much attention as high-performance oxygen carriers for chemical looping reforming of methane,but they are easily inactivated by the presence of trace H_(2)S.Here,we propose to modulate both the activity and resistance to sulfur poisoning by dual substitution of Mo and Ni ions with the Fe-sites of LaFeO_(3)perovskite.It is found that partial substitution of Ni for Fe substantially improves the activity of LaFeO_(3)perovskite,while Ni particles prefer to grow and react with H_(2)S during the long-term successive redox process,resulting in the deactivation of oxygen carriers.With the presence of Mo in LaNi_(0.05)Fe_(0.95)O_(3−σ)perovskite,H_(2)S preferentially reacts with Mo to generate MoS_(2),and then the CO_(2)oxidation can regenerate Mo via removing sulfur.In addition,Mo can inhibit the accumulation and growth of Ni,which helps to improve the redox stability of oxygen carriers.The LaNi_(0.05)Mo_(0.07)Fe_(0.88)O_(3−σ)oxygen carrier exhibits stable and excellent performance,with the CH_(4)conversion higher than 90%during the 50 redox cycles in the presence of 50 ppm H_(2)S at 800℃.This work highlights a synergistic effect in the perovskite oxides induced by dual substitution of different cations for the development of high-performance oxygen carriers with excellent sulfur tolerance.
基金National Natural Science Foundation of China(52174279)Analysis and Testing Foundation of Kunming University of Science and Technology(2022M20202202138)Yunnan Fundamental Research Projects(202301AU070027).
文摘The challenges posed by energy and environmental issues have forced mankind to explore and utilize unconventional energy sources.It is imperative to convert the abundant coalbed gas(CBG)into high value-added products,i.e.,selective and efficient conversion of methane from CBG.Methane activation,known as the“holy grail”,poses a challenge to the design and development of catalysts.The structural complexity of the active metal on the carrier is of particular concern.In this work,we have studied the nucleation growth of small Co clusters(up to Co_(6))on the surface of CeO_(2)(110)using density functional theory,from which a stable loaded Co/CeO_(2)(110)structure was selected to investigate the methane activation mechanism.Despite the relatively small size of the selected Co clusters,the obtained Co_(x)/CeO_(2)(110)exhibits interesting properties.The optimized Co_(5)/CeO_(2)(110)structure was selected as the optimal structure to study the activation mechanism of methane due to its competitive electronic structure,adsorption energy and binding energy.The energy barriers for the stepwise dissociation of methane to form CH3^(*),CH2^(*),CH^(*),and C^(*)radical fragments are 0.44,0.55,0.31,and 1.20 eV,respectively,indicating that CH^(*)dissociative dehydrogenation is the rate-determining step for the system under investigation here.This fundamental study of metal-support interactions based on Co growth on the CeO_(2)(110)surface contributes to the understanding of the essence of Co/CeO_(2) catalysts with promising catalytic behavior.It provides theoretical guidance for better designing the optimal Co/CeO_(2) catalyst for tailored catalytic reactions.
基金supported by the earmarked fund for CARS-29 and the open funds of the Key Laboratory of Viticulture and Enology,Ministry of Agriculture,China.
文摘An appropriate optimal number of market segments(ONS)estimation is essential for an enterprise to achieve successful market segmentation,but at present,there is a serious lack of attention to this issue in market segmentation.In our study,an independent adaptive ONS estimation method BWCON-NSDK-means++is proposed by integrating a newinternal validity index(IVI)Between-Within-Connectivity(BWCON)and a newstable clustering algorithmNatural-SDK-means++(NSDK-means++)in a novel way.First,to complete the evaluation dimensions of the existing IVIs,we designed a connectivity formula based on the neighbor relationship and proposed the BWCON by integrating the connectivity with other two commonly considered measures of compactness and separation.Then,considering the stability,number of parameters and clustering performance,we proposed the NSDK-means++to participate in the integrationwhere the natural neighbor was used to optimize the initial cluster centers(ICCs)determination strategy in the SDK-means++.At last,to ensure the objectivity of the estimatedONS,we designed a BWCON-based ONS estimation framework that does not require the user to set any parameters in advance and integrated the NSDK-means++into this framework forming a practical ONS estimation tool BWCON-NSDK-means++.The final experimental results showthat the proposed BWCONand NSDK-means++are significantlymore suitable than their respective existing models to participate in the integration for determining theONS,and the proposed BWCON-NSDK-means++is demonstrably superior to the BWCON-KMA,BWCONMBK,BWCON-KM++,BWCON-RKM++,BWCON-SDKM++,BWCON-Single linkage,BWCON-Complete linkage,BWCON-Average linkage and BWCON-Ward linkage in terms of the ONS estimation.Moreover,as an independentmarket segmentation tool,the BWCON-NSDK-means++also outperforms the existing models with respect to the inter-market differentiation and sub-market size.
