This review paper aims at analysing the state of the art for partial oxidation and oxidative dehydrogenation（ODH） reactions of lower alkanes C–Cinto olefins and oxygenated products（aldehydes, anhydrides,carboxylic...This review paper aims at analysing the state of the art for partial oxidation and oxidative dehydrogenation（ODH） reactions of lower alkanes C–Cinto olefins and oxygenated products（aldehydes, anhydrides,carboxylic acids） on metal oxide catalysts with cations of variable oxidation state, such as Mo and V in particular. Key parameters to be met by the catalysts, such as their redox properties, their structural aspects, active sites composed of ensembles of atoms isolated one from the others, mechanisms of reactions, are discussed. Main features of the different reactions of C–Calkanes and catalysts are analysed and their generalisation for determining more active and more selective catalysts is attempted. Prospective views for the future of the domain are proposed.展开更多
The utilization of lighter alkanes into useful chemical products is essential for modern chemistry and reducing the CO_(2)emission.Particularly,n-butane has gained special attention across the globe due to the abundan...The utilization of lighter alkanes into useful chemical products is essential for modern chemistry and reducing the CO_(2)emission.Particularly,n-butane has gained special attention across the globe due to the abundant production of maleic anhydride(MA).Vanadium phosphorous oxide(VPO)is the most effective catalyst for selective oxidation of n-butane to MA so far.Interestingly,the VPO complex exists in more or less fifteen different structures,each one having distinct phase composition and exclusive surface morphology and physiochemical properties such as valence state,lattice oxygen,acidity etc.,which relies on precursor preparation method and the activation conditions of catalysts.The catalytic performance of VPO catalyst is improved by adding different promoters or co-catalyst such as various metals dopants,or either introducing template or structural-directing agents.Meanwhile,new preparation strategies such as electrospinning,ball milling,hydrothermal,barothermal,ultrasound,microwave irradiation,calcination,sol-gel method and solvothermal synthesis are also employed for introducing improvement in catalytic performance.Research in above-mentioned different aspects will be ascribed in current review in addition to summarizing overall catalysis activity and final yield.To analyze the performance of the catalytic precursor,the reaction mechanism and reaction kinetics both are discussed in this review to help clarify the key issues such as strong exothermic reaction,phosphorus supplement,water supplement,deactivation,and air/n-butane pretreatment etc.related to the various industrial applications of VPO.展开更多
Selective catalysis,particularly when differentiating substrates with similar reactivities in a mixture,is a significant challenge.In this study,anomaly detection algorithms—tools traditionally used for identifying o...Selective catalysis,particularly when differentiating substrates with similar reactivities in a mixture,is a significant challenge.In this study,anomaly detection algorithms—tools traditionally used for identifying outliers in data cleaning—are applied to catalyst screening.We focus on developing catalytic methods to selectively oxidize cyclic alkanes over linear alkanes in mixtures such as naphtha.By inserting cyclohexane oxidation data one by one into a database of n-hexane oxidization,we used several anomaly detection algorithms to evaluate whether the inserted cyclohexane oxidation data could be considered anomalous.Conditions identified as anomalies imply that they are likely not suitable for n-hexane oxidization.As these anomalies come from conditions for cyclohexane oxidation,they are promising conditions for selective oxidation of cyclohexane while leaving n-hexane unaltered.These anomalies were thus further investigated,leading to the discovery of a specific catalytic approach that selectively oxidizes cyclohexane.This application of anomaly detection offers a novel method to search for selective catalyst for chemical reactions involving mixed substrates.展开更多
文摘This review paper aims at analysing the state of the art for partial oxidation and oxidative dehydrogenation（ODH） reactions of lower alkanes C–Cinto olefins and oxygenated products（aldehydes, anhydrides,carboxylic acids） on metal oxide catalysts with cations of variable oxidation state, such as Mo and V in particular. Key parameters to be met by the catalysts, such as their redox properties, their structural aspects, active sites composed of ensembles of atoms isolated one from the others, mechanisms of reactions, are discussed. Main features of the different reactions of C–Calkanes and catalysts are analysed and their generalisation for determining more active and more selective catalysts is attempted. Prospective views for the future of the domain are proposed.
基金supported by the National Key Research and Development Program of China(2017YFA0206803)the innovation Academy for Green Manufacture of Chinese Academy of Science(IAGM2020C17)+3 种基金the Key Programs of the Chinese Academy of Sciences(KFZD-SW-413)the National Nature Science Foundation of China(21808223)the Key Programs of Fujian Institute of Innovation,CAS(FJCXY18020203)Chinese Academy of Sciences,the One Hundred Talent Program of CAS。
文摘The utilization of lighter alkanes into useful chemical products is essential for modern chemistry and reducing the CO_(2)emission.Particularly,n-butane has gained special attention across the globe due to the abundant production of maleic anhydride(MA).Vanadium phosphorous oxide(VPO)is the most effective catalyst for selective oxidation of n-butane to MA so far.Interestingly,the VPO complex exists in more or less fifteen different structures,each one having distinct phase composition and exclusive surface morphology and physiochemical properties such as valence state,lattice oxygen,acidity etc.,which relies on precursor preparation method and the activation conditions of catalysts.The catalytic performance of VPO catalyst is improved by adding different promoters or co-catalyst such as various metals dopants,or either introducing template or structural-directing agents.Meanwhile,new preparation strategies such as electrospinning,ball milling,hydrothermal,barothermal,ultrasound,microwave irradiation,calcination,sol-gel method and solvothermal synthesis are also employed for introducing improvement in catalytic performance.Research in above-mentioned different aspects will be ascribed in current review in addition to summarizing overall catalysis activity and final yield.To analyze the performance of the catalytic precursor,the reaction mechanism and reaction kinetics both are discussed in this review to help clarify the key issues such as strong exothermic reaction,phosphorus supplement,water supplement,deactivation,and air/n-butane pretreatment etc.related to the various industrial applications of VPO.
基金funding support from the National Key R&D Program of China(2021YFA1502500)the National Natural Science Foundation of China(22125502,22071207,22121001)the Fundamental Research Funds for the Central Universities(20720220011,20720240151)。
文摘Selective catalysis,particularly when differentiating substrates with similar reactivities in a mixture,is a significant challenge.In this study,anomaly detection algorithms—tools traditionally used for identifying outliers in data cleaning—are applied to catalyst screening.We focus on developing catalytic methods to selectively oxidize cyclic alkanes over linear alkanes in mixtures such as naphtha.By inserting cyclohexane oxidation data one by one into a database of n-hexane oxidization,we used several anomaly detection algorithms to evaluate whether the inserted cyclohexane oxidation data could be considered anomalous.Conditions identified as anomalies imply that they are likely not suitable for n-hexane oxidization.As these anomalies come from conditions for cyclohexane oxidation,they are promising conditions for selective oxidation of cyclohexane while leaving n-hexane unaltered.These anomalies were thus further investigated,leading to the discovery of a specific catalytic approach that selectively oxidizes cyclohexane.This application of anomaly detection offers a novel method to search for selective catalyst for chemical reactions involving mixed substrates.
