Syngas to aromatics(STA)over bifunctional catalysts has attracted much attention in recent years,but the mechanism underlying the formation of aromatics remains controversial.The critical reaction intermediates,carbox...Syngas to aromatics(STA)over bifunctional catalysts has attracted much attention in recent years,but the mechanism underlying the formation of aromatics remains controversial.The critical reaction intermediates,carboxylates,were first identified and then confirmed to essentially promote aromatization in the syngas conversion over a ZnCrAlO_(x)&H-ZSM-5 composite catalyst.This study provides evidence that the carboxylates can be formed during the reactions of formate species and olefins.In addition,it is shown that the carboxylates favor the formation of aromatics over H-ZSM-5 even in the presence of H2.A novel mechanism for the formation of aromatics via the generation and transformation of carboxylate intermediates is proposed,and the transformation of carboxylates to aromatics via methyl-2-cyclopenten-1-one(MCPO)intermediates is indeed likely.A better understanding of the formation mechanism of aromatics would help optimize the composite catalyst.展开更多
Toluene methylation with methanol on H‐ZSM‐5(Z5)zeolite for the directional transformation of toluene to xylene has been industrialized.However,great challenges remain because of the high energy barrier of methanol ...Toluene methylation with methanol on H‐ZSM‐5(Z5)zeolite for the directional transformation of toluene to xylene has been industrialized.However,great challenges remain because of the high energy barrier of methanol deprotonation to the methoxy group,the side reaction of methanol to olefins,coke formation,and the deactivation of zeolites.Herein,we report the toluene methylation coupled with CO hydrogenation to showcase an enhancement in para‐xylene(PX)selectivity by employing a bifunctional catalyst composed of ZnZrO_(x)(ZZO)and modified Z5.The results showed that a PX selectivity of up to 81.8%in xylene and xylene selectivity of 64.8%in hydrocarbons at 10.3%toluene conversion can be realized over the bifunctional catalyst on a fixed‐bed reactor.The selectivity of gaseous hydrocarbons decreased to 10.9%,and approximately half of that was observed in methanol reagent route where the PX selectivity in xylene was 38.8%.We observed that the acid strength,the quantity ratio of Brönsted and Lewis acid sites,and the pore size of zeolites were essential for the PX selectivity.The investigation of the H_(2)/D_(2) kinetic isotope effect revealed that the newborn methyl group in xylene resulted from the hydrogenation of CO rather than toluene disproportionation.Furthermore,the catalyst showed no evident deactivation within the 100 h stability test.The findings offer a promising route for the production of value‐added PX with high selectivity via toluene methylation coupled with syngas conversion.展开更多
Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on s...Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on source treatment is limited.This paper proposes a new coal combustion strategy that significantly reduces NO_(x) emissions during coal combustion.This strategy has two important advantages in reducing NO_(x) emissions.First,by introducing iron-based catalyst at the source,which will catalyze the conversion of coke nitrogen to volatile nitrogen during the pyrolysis process,thereby greatly reducing the coke nitrogen content.The second is de-NO_(x) process by a redox reaction between NO_(x) and reducing agents(coke,HCN,NH_(3),etc.)that occurred during coke combustion.Compared to direct combustion of coal,coke prepared by adding iron-based catalyst has 46.1% reduction in NO_(x) emissions.To determine the effect of iron-based additives on de-NO_(x) performance,demineralized coal(de-coal)was prepared to eliminate the effect of iron-based minerals in coal ash.The effects of iron compounds,additive dosages,and combustion temperatures on de-NO_(x) efficiency are systematically studied.The results revealed that the NO_(x) emission of the coke generated by pyrolysis of de-coal loaded with 3%(mass)Fe_(2)O_(3) decreases to 27.3% at combustion temperature of 900℃.Two main reasons for lower NO_(x) emissions were deduced:(1)During the catalytic coal pyrolysis stage,the nitrogen content in the coke decreases with the release of volatile nitrogen.(2)Part of the NO_(x) emitted during the coke combustion was converted into N_(2) for the catalytic effect of the Fe-based catalysts.It is of great practical value and scientific significance to the comprehensive treatment and the clean utilization process of coal.展开更多
The various surface species[H_XRu_3(CO)_9(CCO)]^(2-X)(X=0-2)prepared from impregnation of[PPN]_2[Ru_3(CO)_9(CCO)]on SiO_2-Al_2O_3,SiO_2 and MgO show quite different activities and selectivities for oxygenates and etha...The various surface species[H_XRu_3(CO)_9(CCO)]^(2-X)(X=0-2)prepared from impregnation of[PPN]_2[Ru_3(CO)_9(CCO)]on SiO_2-Al_2O_3,SiO_2 and MgO show quite different activities and selectivities for oxygenates and ethane in ethylene hydroformylation.展开更多
Excessive emissions of nitrogen oxides from flue gas have imposed various detrimental impacts on environment,and the development of deNO_(x) catalysts with low-cost and high performance is an urgent requirement.Iron o...Excessive emissions of nitrogen oxides from flue gas have imposed various detrimental impacts on environment,and the development of deNO_(x) catalysts with low-cost and high performance is an urgent requirement.Iron oxide-based material has been explored for promising deNO_(x) catalysts.However,the unsatisfactory low-temperature activity limits their practical applications.In this study,a series of excellent low-temperature denitrification catalysts(Ha-FeO_(x)/yZS)were prepared by acid treatment of zinc slag,and the mass ratios of Fe to impure ions was regulated by adjusting the acid concentrations.Ha-FeO_(x)/yZS showed high denitrification performance(>90%)in the range of 180–300℃,and the optimal NO conversion and N2 selectivity were higher than 95%at 250℃.Among them,the Ha-FeO_(x)/2ZS synthesized with 2 mol/L HNO3 exhibited the widest temperature window(175–350℃).The excellent denitrification performance of Ha-FeO_(x)/yZS was mainly attributed to the strong interaction between Fe and impurity ions to inhibit the growth of crystals,making Ha-FeO_(x)/yZS with amorphous structure,nice fine particles,large specific surface area,more surface acid sites and high chemisorbed oxygen.The in-situ DRIFT experiments confirmed that the SCR reaction on the Ha-FeO_(x)/yZS followed both Langmuir-Hinshelwood(L-H)mechanism and Eley-Rideal(E-R)mechanism.The present work proposed a high value-added method for the preparation of cost-effective catalysts from zinc slag,which showed a promising application prospect in NO_(x) removal by selective catalytic reduction with ammonia.展开更多
High-efficiency seawater electrolysis is impeded by the low activity and low durability of oxygen evolution catalysts due to the complex composition and competitive side reactions in seawater.Herein,a heterogeneousstr...High-efficiency seawater electrolysis is impeded by the low activity and low durability of oxygen evolution catalysts due to the complex composition and competitive side reactions in seawater.Herein,a heterogeneousstructured catalyst is constructed by depositing NiFe-layered double hydroxides(NiFe-LDH)on the substrate of MXene(V_(2)CT_(x))modified Ni foam(NF),and abbreviated as NiFe-LDH/V_(2)CT_(x)/NF.As demonstrated,owing to the intrinsic negative charge characteristic of V_(2)CT_(x),chlorine ions are denied entry to the interface between NiFeLDH and V_(2)CT_(x)/NF substrate,thus endowing NiFe-LDH/V_(2)CT_(x)/NF catalyst with high corrosion resistance and durable stability for 110 h at 500 mA cm^(-2).Meanwhile,the two-dimensional structure and high electrical conductivity of V_(2)CT_(x) can respectively enlarge the electrochemical active surface area and guarantee fast charge transfer,thereby synergistically promoting the catalytic performance of NiFe-LDH/V_(2)CT_(x)/NF in both deionized water electrolyte(261 m V at 100 m A cm^(-2))and simulated seawater electrolyte(241 mV at 100 mA cm^(-2)).This work can guide the preparation of oxygen evolution catalysts and accelerate the industrialization of seawater electrolysis.展开更多
文摘Syngas to aromatics(STA)over bifunctional catalysts has attracted much attention in recent years,but the mechanism underlying the formation of aromatics remains controversial.The critical reaction intermediates,carboxylates,were first identified and then confirmed to essentially promote aromatization in the syngas conversion over a ZnCrAlO_(x)&H-ZSM-5 composite catalyst.This study provides evidence that the carboxylates can be formed during the reactions of formate species and olefins.In addition,it is shown that the carboxylates favor the formation of aromatics over H-ZSM-5 even in the presence of H2.A novel mechanism for the formation of aromatics via the generation and transformation of carboxylate intermediates is proposed,and the transformation of carboxylates to aromatics via methyl-2-cyclopenten-1-one(MCPO)intermediates is indeed likely.A better understanding of the formation mechanism of aromatics would help optimize the composite catalyst.
文摘Toluene methylation with methanol on H‐ZSM‐5(Z5)zeolite for the directional transformation of toluene to xylene has been industrialized.However,great challenges remain because of the high energy barrier of methanol deprotonation to the methoxy group,the side reaction of methanol to olefins,coke formation,and the deactivation of zeolites.Herein,we report the toluene methylation coupled with CO hydrogenation to showcase an enhancement in para‐xylene(PX)selectivity by employing a bifunctional catalyst composed of ZnZrO_(x)(ZZO)and modified Z5.The results showed that a PX selectivity of up to 81.8%in xylene and xylene selectivity of 64.8%in hydrocarbons at 10.3%toluene conversion can be realized over the bifunctional catalyst on a fixed‐bed reactor.The selectivity of gaseous hydrocarbons decreased to 10.9%,and approximately half of that was observed in methanol reagent route where the PX selectivity in xylene was 38.8%.We observed that the acid strength,the quantity ratio of Brönsted and Lewis acid sites,and the pore size of zeolites were essential for the PX selectivity.The investigation of the H_(2)/D_(2) kinetic isotope effect revealed that the newborn methyl group in xylene resulted from the hydrogenation of CO rather than toluene disproportionation.Furthermore,the catalyst showed no evident deactivation within the 100 h stability test.The findings offer a promising route for the production of value‐added PX with high selectivity via toluene methylation coupled with syngas conversion.
基金supported by National Natural Science Foundation of China(21878210)Shanxi Provincial Science and Technology Achievement Transformation Guidance Special Program of China(202104021301052)Shanxi Province Patent Transformation Special Program Project(202202054).
文摘Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on source treatment is limited.This paper proposes a new coal combustion strategy that significantly reduces NO_(x) emissions during coal combustion.This strategy has two important advantages in reducing NO_(x) emissions.First,by introducing iron-based catalyst at the source,which will catalyze the conversion of coke nitrogen to volatile nitrogen during the pyrolysis process,thereby greatly reducing the coke nitrogen content.The second is de-NO_(x) process by a redox reaction between NO_(x) and reducing agents(coke,HCN,NH_(3),etc.)that occurred during coke combustion.Compared to direct combustion of coal,coke prepared by adding iron-based catalyst has 46.1% reduction in NO_(x) emissions.To determine the effect of iron-based additives on de-NO_(x) performance,demineralized coal(de-coal)was prepared to eliminate the effect of iron-based minerals in coal ash.The effects of iron compounds,additive dosages,and combustion temperatures on de-NO_(x) efficiency are systematically studied.The results revealed that the NO_(x) emission of the coke generated by pyrolysis of de-coal loaded with 3%(mass)Fe_(2)O_(3) decreases to 27.3% at combustion temperature of 900℃.Two main reasons for lower NO_(x) emissions were deduced:(1)During the catalytic coal pyrolysis stage,the nitrogen content in the coke decreases with the release of volatile nitrogen.(2)Part of the NO_(x) emitted during the coke combustion was converted into N_(2) for the catalytic effect of the Fe-based catalysts.It is of great practical value and scientific significance to the comprehensive treatment and the clean utilization process of coal.
文摘The various surface species[H_XRu_3(CO)_9(CCO)]^(2-X)(X=0-2)prepared from impregnation of[PPN]_2[Ru_3(CO)_9(CCO)]on SiO_2-Al_2O_3,SiO_2 and MgO show quite different activities and selectivities for oxygenates and ethane in ethylene hydroformylation.
基金National Natural Science Foundation of China(21676209)Natural Science Basic Research Program of Shaanxi(2022JQ-328)Postdoctoral Research Foundation of the Xi’an University of Architecture and Technology(19603210120).
文摘Excessive emissions of nitrogen oxides from flue gas have imposed various detrimental impacts on environment,and the development of deNO_(x) catalysts with low-cost and high performance is an urgent requirement.Iron oxide-based material has been explored for promising deNO_(x) catalysts.However,the unsatisfactory low-temperature activity limits their practical applications.In this study,a series of excellent low-temperature denitrification catalysts(Ha-FeO_(x)/yZS)were prepared by acid treatment of zinc slag,and the mass ratios of Fe to impure ions was regulated by adjusting the acid concentrations.Ha-FeO_(x)/yZS showed high denitrification performance(>90%)in the range of 180–300℃,and the optimal NO conversion and N2 selectivity were higher than 95%at 250℃.Among them,the Ha-FeO_(x)/2ZS synthesized with 2 mol/L HNO3 exhibited the widest temperature window(175–350℃).The excellent denitrification performance of Ha-FeO_(x)/yZS was mainly attributed to the strong interaction between Fe and impurity ions to inhibit the growth of crystals,making Ha-FeO_(x)/yZS with amorphous structure,nice fine particles,large specific surface area,more surface acid sites and high chemisorbed oxygen.The in-situ DRIFT experiments confirmed that the SCR reaction on the Ha-FeO_(x)/yZS followed both Langmuir-Hinshelwood(L-H)mechanism and Eley-Rideal(E-R)mechanism.The present work proposed a high value-added method for the preparation of cost-effective catalysts from zinc slag,which showed a promising application prospect in NO_(x) removal by selective catalytic reduction with ammonia.
基金the financial support of the National Natural Science Foundation of China(52162027,52274297 and 52164028)the Hainan Province Science and Technology Special Fund(ZDYF2023SHFZ091)+4 种基金the Hainan Provincial Natural Science Foundation of China(project Nos.221RC540)Hainan Provincial Postdoctoral Science Foundation(project Nos.2022-BH-25)the Collaborative Innovation Center of Marine Science and Technology(Hainan University)the Start-up Research Foundation of Hainan University(KYQD(ZR)2008,23069,23073 and 23067)the specific research fund of The Innovation Platform for Academicians of Hainan Province(YSPTZX202315)。
文摘High-efficiency seawater electrolysis is impeded by the low activity and low durability of oxygen evolution catalysts due to the complex composition and competitive side reactions in seawater.Herein,a heterogeneousstructured catalyst is constructed by depositing NiFe-layered double hydroxides(NiFe-LDH)on the substrate of MXene(V_(2)CT_(x))modified Ni foam(NF),and abbreviated as NiFe-LDH/V_(2)CT_(x)/NF.As demonstrated,owing to the intrinsic negative charge characteristic of V_(2)CT_(x),chlorine ions are denied entry to the interface between NiFeLDH and V_(2)CT_(x)/NF substrate,thus endowing NiFe-LDH/V_(2)CT_(x)/NF catalyst with high corrosion resistance and durable stability for 110 h at 500 mA cm^(-2).Meanwhile,the two-dimensional structure and high electrical conductivity of V_(2)CT_(x) can respectively enlarge the electrochemical active surface area and guarantee fast charge transfer,thereby synergistically promoting the catalytic performance of NiFe-LDH/V_(2)CT_(x)/NF in both deionized water electrolyte(261 m V at 100 m A cm^(-2))and simulated seawater electrolyte(241 mV at 100 mA cm^(-2)).This work can guide the preparation of oxygen evolution catalysts and accelerate the industrialization of seawater electrolysis.
