Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified...Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified MCM-22 zeolite combined with ZnCeZrOx solid solution is reported to catalyze the tandem CO_(2)hydrogenation and toluene methylation reaction at a relatively low temperature(<603 K),showing xylene selectivity of 92.4%and PX selectivity of 62%(PX/X,67%)in total aromatics at a CO_(2)conversion of 7.7%,toluene conversion of 23.6%and low CO selectivity of 11.6%,as well as giving high STY of xylene(302.0 mg·h^(–1)·gcat^(–1))and PX(201.6 mg·h^(–1)·gcat^(–1)).The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22,which promoted zeolite shape-selectivity and suppressed secondary reactions.展开更多
Nanoscale confinement environments often affect the transport mechanisms of nanofluids.Understanding the dynamic behavior of molecules in two-dimensional(2D)confined channels is of great importance in the areas of sen...Nanoscale confinement environments often affect the transport mechanisms of nanofluids.Understanding the dynamic behavior of molecules in two-dimensional(2D)confined channels is of great importance in the areas of sensing,catalysis and energy storage.As a popular candidate for a new type of gas sensing material,MXenes have the problem of nonselectivity towards polar gases with slow responses,which severely limits their applications.Here,we report a study on regulating the confinement effect of 2D channels between MXene layers through annealing treatment and ion(Na^(+))intercalation for high-performance ammonia(NH_(3))sensing.Firstly,the annealing treatment accurately modulates the size of the 2D channels to effectively block the entry of large-size gas molecules and improve the selectivity for NH_(3).Ab initio molecular dynamics(AIMD)also confirms that the modulated channel size has a special"nano-pumping effect",which can accelerate the dynamic behavior of NH_(3) molecules in the 2D confined space.Moreover,the intercalation of Na+ions increases the adsorption capacity of NH_(3).Therefore,the"nano-pumping effect"and theintercalation of Na+ions effectively enhance the response speed and sensitivity of MXene to NH_(3),respectively.The experimental results show that the modified Ti_(3)C_(2) exhibits high sensitivity(0.17),rapid response(181 s),excellent selectivity and stability towards NH_(3).展开更多
Nanofiltration(NF)membranes with exceptional ion selectivity and permeability are needed for the recovery of lithium from waste lithium-ion batteries.Herein,inspired by the homogeneous microchannels in the skeletal st...Nanofiltration(NF)membranes with exceptional ion selectivity and permeability are needed for the recovery of lithium from waste lithium-ion batteries.Herein,inspired by the homogeneous microchannels in the skeletal structure of glass sponges,an innovative biomimetic sponge-like sub-nanostructured NF membrane was designed using an alkali-induced MXene(AMXene)-ethyl formate(EF)-induced bulk/interfacial diffusion decoupling strategy to simultaneously improve Li^(+)/Co^(2+)selectivity and membrane permeability.The Li^(+)/Co^(2+)separation factor(SLi,co=24)of the engineered membrane was improved by an order of magnitude compared to that of an NF270 membrane(SLi,Co=2).The selectivity of Mg^(2+)/Na+(B_(NaCl)/B_(MgCl_(2))=286)and SO_(4)^(2-)/Cl^(-)(BNaCl/BNaSO_(4)=941)increased by 3~12 times,and the permeability(25.8 L m-2 h-1 bar-1)remained at a desirable level,beyond the current upper bound of the other cutting-edge membranes.The superior performance was attributed to the limited release of amine in bulk phase and the boosted interfacial diffusion by reducing interfacial energy barrier during the interfacial polymerization reaction,which were realized via the synergetic effects of AMXene and EF.This approach yielded a biomimetic sponge-like sub-nanostructured NF membrane with controlled homogeneous pore radii(0.202 nm)and a thickness as small as 16.08 nm,which led to high ion selectivity and permeability.The engineered membrane was capable of efficient separation and recovery of Li^(+)/metal ions.展开更多
CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport e...CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport efficiency of photogenerated carriers.To address the above issues,a cost-effective ternary Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode was designed.Firstly,a thin Cu:NiO_(X)film was inserted between CuBi_(2)O_(4)and FTO conducting substrate as a hole-selective layer,which promotes the transmission of photogenerated holes to the FTO substrate effectively.Furthermore,the modification of CuO film on the CuBi_(2)O_(4)electrode not only increases the absorption of sunlight and generates more photogenerated carriers,but also constitutes a heterojunction with CuBi_(2)O_(4),creating a built-in electric field,which facilitates the separation of electrons and holes,and accelerates the electrons transfer to electrode–electrolyte interface.The fabricated Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode exhibits a surprisingly high photocurrent density of−1.51 mA·cm^(−2)at 0.4 V versus RHE,which is 2.6 times that of the pristine CuBi_(2)O_(4)photocathode.The improved PEC performance is attributed to the synergy effect of the Cu:NiO_(X)hole-selective layer and the CuBi_(2)O_(4)/CuO heterojunction.Moreover,the combination with the BiVO_(4)/CoS,an unbiased overall water splitting was achieved,which has a photocurrent of 0.193 mA·cm^(−2).展开更多
Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost target...Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost targets for CO2 capture. This study attempts to develop membranes with multiple permselective mechanisms in order to enhance CO2 separation performance of fixed carder membrane. In this study, a novel membrane with multiplepermselective mechanisms of solubility selectivity and reaction selectivity was developed by incorporating CO2-selective adsorptive silica nanoparticles in situ into the tertiary amine containing polyamide membrane formed by interfacial polymerization （IP）. Various techniques were employed to characterize the polyamide and polyam-ide-silica composite membranes. The TGA result shows that nanocomposite membranes exhlbit superior-thermal stability than pure polyamide membranes. In addition, gas permeation experiments show that both nanocomposite membranes have larger CO2 permeance than pure polyamide membranes. The enhanced CO2/N2 separation performance for nanocomposite membranes is mainly due to the thin film thickness, and multiple permselective mechanisms of solubility selectivity and reaction selectivity.展开更多
文摘Selective synthesis of value-added xylenes and para-xylene(PX)by CO_(2)hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO_(2).Herein,modified MCM-22 zeolite combined with ZnCeZrOx solid solution is reported to catalyze the tandem CO_(2)hydrogenation and toluene methylation reaction at a relatively low temperature(<603 K),showing xylene selectivity of 92.4%and PX selectivity of 62%(PX/X,67%)in total aromatics at a CO_(2)conversion of 7.7%,toluene conversion of 23.6%and low CO selectivity of 11.6%,as well as giving high STY of xylene(302.0 mg·h^(–1)·gcat^(–1))and PX(201.6 mg·h^(–1)·gcat^(–1)).The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22,which promoted zeolite shape-selectivity and suppressed secondary reactions.
基金supported by the National Natural Science Foundation of China(Nos.52422505 and 12274124)the Innovative Research Group Project of the National Natural Science Foundation of China(No.52321002).
文摘Nanoscale confinement environments often affect the transport mechanisms of nanofluids.Understanding the dynamic behavior of molecules in two-dimensional(2D)confined channels is of great importance in the areas of sensing,catalysis and energy storage.As a popular candidate for a new type of gas sensing material,MXenes have the problem of nonselectivity towards polar gases with slow responses,which severely limits their applications.Here,we report a study on regulating the confinement effect of 2D channels between MXene layers through annealing treatment and ion(Na^(+))intercalation for high-performance ammonia(NH_(3))sensing.Firstly,the annealing treatment accurately modulates the size of the 2D channels to effectively block the entry of large-size gas molecules and improve the selectivity for NH_(3).Ab initio molecular dynamics(AIMD)also confirms that the modulated channel size has a special"nano-pumping effect",which can accelerate the dynamic behavior of NH_(3) molecules in the 2D confined space.Moreover,the intercalation of Na+ions increases the adsorption capacity of NH_(3).Therefore,the"nano-pumping effect"and theintercalation of Na+ions effectively enhance the response speed and sensitivity of MXene to NH_(3),respectively.The experimental results show that the modified Ti_(3)C_(2) exhibits high sensitivity(0.17),rapid response(181 s),excellent selectivity and stability towards NH_(3).
基金financial support from the National Key Research and Development Program of China(2023YFC3208002)National Natural Science Foundation of China(NSFC)(52370007)+2 种基金the Natural Science Foundation of Heilongjiang Province(YQ2022E034)Project funded by China Postdoctoral Science Foundation(2019 M651290,2019 M651290)State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2021TS27)。
文摘Nanofiltration(NF)membranes with exceptional ion selectivity and permeability are needed for the recovery of lithium from waste lithium-ion batteries.Herein,inspired by the homogeneous microchannels in the skeletal structure of glass sponges,an innovative biomimetic sponge-like sub-nanostructured NF membrane was designed using an alkali-induced MXene(AMXene)-ethyl formate(EF)-induced bulk/interfacial diffusion decoupling strategy to simultaneously improve Li^(+)/Co^(2+)selectivity and membrane permeability.The Li^(+)/Co^(2+)separation factor(SLi,co=24)of the engineered membrane was improved by an order of magnitude compared to that of an NF270 membrane(SLi,Co=2).The selectivity of Mg^(2+)/Na+(B_(NaCl)/B_(MgCl_(2))=286)and SO_(4)^(2-)/Cl^(-)(BNaCl/BNaSO_(4)=941)increased by 3~12 times,and the permeability(25.8 L m-2 h-1 bar-1)remained at a desirable level,beyond the current upper bound of the other cutting-edge membranes.The superior performance was attributed to the limited release of amine in bulk phase and the boosted interfacial diffusion by reducing interfacial energy barrier during the interfacial polymerization reaction,which were realized via the synergetic effects of AMXene and EF.This approach yielded a biomimetic sponge-like sub-nanostructured NF membrane with controlled homogeneous pore radii(0.202 nm)and a thickness as small as 16.08 nm,which led to high ion selectivity and permeability.The engineered membrane was capable of efficient separation and recovery of Li^(+)/metal ions.
基金supported by the National Natural Science Foundation of China(No.61804039)the University Natural Sciences Research Project of Anhui Province(No.2022AH010096)+1 种基金the Talent Research Fund of Hefei University(No.20RC35)the Natural Science Foundation of Anhui Higher Education Institution of China(No.2023AH040160).
文摘CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport efficiency of photogenerated carriers.To address the above issues,a cost-effective ternary Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode was designed.Firstly,a thin Cu:NiO_(X)film was inserted between CuBi_(2)O_(4)and FTO conducting substrate as a hole-selective layer,which promotes the transmission of photogenerated holes to the FTO substrate effectively.Furthermore,the modification of CuO film on the CuBi_(2)O_(4)electrode not only increases the absorption of sunlight and generates more photogenerated carriers,but also constitutes a heterojunction with CuBi_(2)O_(4),creating a built-in electric field,which facilitates the separation of electrons and holes,and accelerates the electrons transfer to electrode–electrolyte interface.The fabricated Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode exhibits a surprisingly high photocurrent density of−1.51 mA·cm^(−2)at 0.4 V versus RHE,which is 2.6 times that of the pristine CuBi_(2)O_(4)photocathode.The improved PEC performance is attributed to the synergy effect of the Cu:NiO_(X)hole-selective layer and the CuBi_(2)O_(4)/CuO heterojunction.Moreover,the combination with the BiVO_(4)/CoS,an unbiased overall water splitting was achieved,which has a photocurrent of 0.193 mA·cm^(−2).
基金Supported by the National Natural Science Foundation of China （20836006）, the National Basic Research Program （2009CB623405）, the Science ＆ Technology Pillar Program of Tianjin （10ZCKFSH01700）, the Programme of Introducing Talents of Discipline to Universities （B06006）, and the Cheung Kong Scholar Program for Innovative Teams of the Ministry of Education （IRT0641）.
文摘Fixed carrier membrane exhibits attractive CO2 permeance and selectivity due to its transport mechanism of reaction selectivity （facilitated transport）. However, its performance needs improvement to meet cost targets for CO2 capture. This study attempts to develop membranes with multiple permselective mechanisms in order to enhance CO2 separation performance of fixed carder membrane. In this study, a novel membrane with multiplepermselective mechanisms of solubility selectivity and reaction selectivity was developed by incorporating CO2-selective adsorptive silica nanoparticles in situ into the tertiary amine containing polyamide membrane formed by interfacial polymerization （IP）. Various techniques were employed to characterize the polyamide and polyam-ide-silica composite membranes. The TGA result shows that nanocomposite membranes exhlbit superior-thermal stability than pure polyamide membranes. In addition, gas permeation experiments show that both nanocomposite membranes have larger CO2 permeance than pure polyamide membranes. The enhanced CO2/N2 separation performance for nanocomposite membranes is mainly due to the thin film thickness, and multiple permselective mechanisms of solubility selectivity and reaction selectivity.
