Inspired by molecular catalysts,researchers developed atomically precise nitrogen-coordinated single or dual metal sites imbedded in graphitized carbon(M-N-C)to fully utilize metallic sites for 02activation.These cata...Inspired by molecular catalysts,researchers developed atomically precise nitrogen-coordinated single or dual metal sites imbedded in graphitized carbon(M-N-C)to fully utilize metallic sites for 02activation.These catalysts performed remarkably well in the electrocatalytic oxygen reduction reaction(ORR)due to their distinct coordination and electrical structures,Nonetheless,their maximum efficacy in practical applications has yet to be achieved.This agenda identifies tailoring the coordination environment,spin states,intersite distance,and metal-metal interaction as innovative approaches to regulate the ORR performance of these catalysts.However,it is necessary to undertake a precise assessment of these methodologies and the knowledge obtained to be implemented in the design of future M-N-C catalysts for ORR.Therefore,this review aims to analyze recent progress in M-N-C ORR catalysts,emphasizing their innovative engineering with aspects such as alteration in intersite distance,metal-metal interaction,coordination environment,and spin states.Additionally,we critically discuss how to logically monitor the atomic structure,local coordination,spin,and electronic states of M-N-C catalysts to modulate their ORR activity.We have also highlighted the challenges associated with M-N-C catalysts and proposed suggestions for their future design and fabrication.展开更多
Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient cat...Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.展开更多
With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy stor...With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.展开更多
CO_(2)-based carbon-neutral organics production processes could potentially reshape the chemical industry.However,their feasibility and net carbon footprint rely strongly on the sources of H_(2).Herein,we present a co...CO_(2)-based carbon-neutral organics production processes could potentially reshape the chemical industry.However,their feasibility and net carbon footprint rely strongly on the sources of H_(2).Herein,we present a comprehensive comparative techno-economic analysis of CO_(2)-based methanol(CO_(2)TM)and aolefins(CO_(2)TO)manufacturing using various feedstock supply modes:(1)the standalone mode with external CO_(2)but H_(2)from on-site water electrolysis,(2)the integrated mode with both CO_(2)and H_(2)recovered from coal-chemical plants,and(3)the integrated mode with recycled CO_(2)but H_(2)from on-site water electrolysis.The integration of CO_(2)TM and CO_(2)TO into coal-to-olefins(CTO)and coal-to-methanol(CTM)facilities is currently cost-effective and can reduce net CO_(2)emissions by 65.7%and 68.5%,resulting in a three-fold and two-fold increase in carbon efficiency,respectively.As carbon tax policies and electrolysis technologies continue to evolve,standalone CO_(2)TM and CO_(2)TO are projected to become more economically competitive than CTO and CTM by 2035-2045.展开更多
The concept of“carbon neutrality”poses a huge challenge for chemical engineering and brings great opportunities for boosting the development of novel technologies to realize carbon offsetting and reduce carbon emiss...The concept of“carbon neutrality”poses a huge challenge for chemical engineering and brings great opportunities for boosting the development of novel technologies to realize carbon offsetting and reduce carbon emissions.Developing high-efficient,low-cost,energy-efficient and eco-friendly microfluidicbased microchemical engineering is of great significance.Such kind of“green microfluidics”can reduce carbon emissions from the source of raw materials and facilitate controllable and intensified microchemical engineering processes,which represents the new power for the transformation and upgrading of chemical engineering industry.Here,a brief review of green microfluidics for achieving carbon neutral microchemical engineering is presented,with specific discussions about the characteristics and feasibility of applying green microfluidics in realizing carbon neutrality.Development of green microfluidic systems are categorized and reviewed,including the construction of microfluidic devices by bio-based substrate materials and by low carbon fabrication methods,and the use of more biocompatible and nondestructive fluidic systems such as aqueous two-phase systems(ATPSs).Moreover,low carbon applications benefit from green microfluidics are summarized,ranging from separation and purification of biomolecules,high-throughput screening of chemicals and drugs,rapid and cost-effective detections,to synthesis of fine chemicals and novel materials.Finally,challenges and perspectives for further advancing green microfluidics in microchemical engineering for carbon neutrality are proposed and discussed.展开更多
Gas-phase polyethylene(PE)processes are among the most important methods for PE production.A deeper understanding of the process characteristics and dynamic behavior,such as properties of PE and reactor stability,hold...Gas-phase polyethylene(PE)processes are among the most important methods for PE production.A deeper understanding of the process characteristics and dynamic behavior,such as properties of PE and reactor stability,holds substantial interest for both academic researchers and industries.In this study,both steady-state and dynamic models for a gas-phase polyethylene process are established as a simulation platform,which can be used to study a variety of operation tasks for commercial solution polyethylene processes,such as new product development,process control and real-time optimization.The copolymerization kinetic parameters are fitted by industrial data.Additionally,a multi-reactor series model is developed to characterize the temperature distribution within the fluidized bed reactor.The accuracy in predicting melt index and density of the polymer,and the dynamic behavior of the developed models are verified by real plant data.Moreover,the dynamic simulation platform is applied to compare four practical control schemes for reactor temperature by a series of simulation experiments,since temperature control is important in industrial production.The results reveal that all four schemes effectively track the setpoint temperature.However,only the demineralized water temperature cascade control demonstrates excellent performance in handling disturbances from both the recycle gas subsystem and the heat exchange subsystem.展开更多
Carbon nitride(CN)-based heterojunction photocatalysts hold promise for efficient carbon dioxide(CO_(2))reduction.However,suboptimal production yields and limited selectivity in CO_(2)conversion pose significant barri...Carbon nitride(CN)-based heterojunction photocatalysts hold promise for efficient carbon dioxide(CO_(2))reduction.However,suboptimal production yields and limited selectivity in CO_(2)conversion pose significant barriers to achieving efficient CO_(2)conversion.Here,we present the construction of a p-n heterojunction between ultrasmall Te NPs and CN nanosheet using a novel tandem hydrothermal-calcination synthesis strategy.Through ammonia-assisted calcination,ultrasmall Te NPs are grown in-situ on the CN nanosheets’surface,resulting in the generation of a robust p-n heterojunction.The synthesized heterojunction exhibits increased specific surface area,reinforced visible light absorption,intensive CO_(2)adsorption capacity,and efficient charge transfer.The optimum Te/CN-NH_(3)demonstrates superior photocatalytic CO_(2)reduction activity and durability,with nearly 100%selectivity for CO and a yield as high as 92.0μmol g^(-1)h^(-1),a fourfold increase compared to pure CN.Experimental and theoretical calculations unravel that the strong built-in electric field of the Te/CN-NH_(3)p-n heterojunction accelerates the migration of photogenerated electrons from Te NPs to the N site on CN nanosheets,thereby promoting CO_(2)reduction.This study provides a promising material design approach for the construction of highperformance p-n heterojunction photocatalysts.展开更多
With the development of manufacturing technology on the nanoscale, the precision of nano-devices is rapidly increasing with lower cost. Different from macroscale or microscale fluids, many specific phenomena and advan...With the development of manufacturing technology on the nanoscale, the precision of nano-devices is rapidly increasing with lower cost. Different from macroscale or microscale fluids, many specific phenomena and advantages are observed in nanofluidics. Devices and process involving and utilizing these phenomena play an important role in many fields in chemical engineering including separation, chemical analysis and transmission.In this article, we summarize the state-of-the-art progress in theoretical studies and manufacturing technologies on nanofluidics. Then we discuss practical applications of nanofluidics in many chemical engineering fields,especially in separation and encountering problems. Finally, we are looking forward to the future of nanofluidics and believe it will be more important in the separation process and the modern chemical industry.展开更多
1 Introduction Magnesium salts are very important by-product of salt lake industry in West China.Nearly 200 million cubic meters of waste brine are released to the environment
Electrochemical methods are environmentally friendly and have unique advantages in the synthesis of organic chemicals.However,their implementation is limited due to the complex transport problems posed by traditional ...Electrochemical methods are environmentally friendly and have unique advantages in the synthesis of organic chemicals.However,their implementation is limited due to the complex transport problems posed by traditional electrochemical reactors.Recently,the application of microreaction technology in electrosynthesis studies has reduced the transport distance of ions and increased the specific surface area of electrodes,leading to efficient,successive,and easily scaled-up electrosynthesis technologies.In this review article,engineering advantages of using microchannels in electrosynthesis are discussed from process enhancement perspective.Flow patterns and mass transfer behaviors in recently reported electrochemical microreactors are analyzed,and prototypes for the reactor scale-up are reviewed.As a relatively new research area,many scientific rules and engineering features of electrosynthesis in microreactors require elucidation.Potential research foci,considered crucial for the development of novel electrosynthesis technology,are therefore proposed.展开更多
Membrane technology holds significant potential for augmenting or partially substituting conventional separation techniques,such as heatdriven distillation,thereby reducing energy consumption.Organic solvent nanofiltr...Membrane technology holds significant potential for augmenting or partially substituting conventional separation techniques,such as heatdriven distillation,thereby reducing energy consumption.Organic solvent nanofiltration represents an advanced membrane separation technology capable of discerning molecules within a molecular weight range of approximately 100-1000 Da in organic solvents,offering low energy requirements and minimal carbon footprints.Molecular separation in non-polar solvent system,such as toluene,n-hexane,and n-heptane,has gained paramount importance due to their extensive use in the pharmaceutical,biochemical,and petrochemical industries.In this review,we presented recent advancements in membrane materials,membrane fabrication techniques and their promising applications for separation in nonpolar solvent system,encompassing hydrocarbon separation,bioactive molecule purification and organic solvent recovery.Furthermore,this review highlighted the challenges and opportunities associated with membrane scale-up strategies and the direct translation of this promising technology into industrial applications.展开更多
Essentially clearing the structure-activity relationship between iron carbide catalysts involving multiple active centers to understand the reaction mechanism of CO hydrogenation conversion process is still a great ch...Essentially clearing the structure-activity relationship between iron carbide catalysts involving multiple active centers to understand the reaction mechanism of CO hydrogenation conversion process is still a great challenge.Here,two main micro-environment factors,namely electronic properties and geometrical effects were found to have an integrated effect on the mechanism of CO hydrogenation conversion,involving active sites on multiple crystal phases.The Bader charge of the surface Fe atoms on the active sites had a guiding effect on the CO activation pathway,while the spatial configuration of the active sites greatly affected the energy barriers of CO activation.Although the defective surfaces were more conducive to CO activation,the defective sites were not the only sites to dissociate CO,as CO always tended to dissociate in a wider area.This synergistic effect of the micro-environment also occurred during the CO conversion process.Surface C atoms on relatively flat configurations were more likely to form methane,while the electronic properties of the active sites could effectively describe the C-C coupling process,as well as distinguish the coupling mechanisms.展开更多
Current ever-accumulating plastic waste can be considered a significant carbon resource for energy conversion and chemical production.The development of new approaches for upcycling plastic waste through chemical degr...Current ever-accumulating plastic waste can be considered a significant carbon resource for energy conversion and chemical production.The development of new approaches for upcycling plastic waste through chemical degradation may enable circularity and promote closed-loop recycling of carbon sources compared to traditional recycling methods.Zeolite,a widely used solid acid catalyst with high industrial potential in petroleum and biomass refining,has been extensively studied for its role in transforming plastics.In this review,we present an overview of zeolite-based catalytic systems for the chemical recycling of plastic waste and discuss how zeolites could potentially contribute to the future development of a circular economy.To provide a comprehensive understanding,we begin with a brief introduction to zeolites,analyzing their key features and exploring their opportunities as well as challenges in processing plastic waste.Subsequently,we delve into the chemistry of catalytic cracking and tandem catalysis using zeolite-based catalysts on plastics.Overall,we emphasize the importance of intelligent catalyst design and lower-energy pathways to incentivize plastic upcycling while alleviating the burden caused by waste plastics.展开更多
The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a ...The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.展开更多
Microreaction technology is one of the most innovative and rapid developing fields in chemical engineering, synthesis and process technology. Many expectations toward enhanced product selectivity, yield and purity, im...Microreaction technology is one of the most innovative and rapid developing fields in chemical engineering, synthesis and process technology. Many expectations toward enhanced product selectivity, yield and purity, improved safety, and access to new products and processes are directed to the microreaction technology. Microfluidic mixer is the most important component in microfluidic devices. Based on various principles, active and passive micromixers have been designed and investigated. This review is focused on the recent developments in microfluidic mixers. An overview of the flow phenomena and mixing characteristics in active and passive micromixers is presented, including the types of physical phenomena and their utilization in micromixers. Due to the simple fabrication technology and the easy implementation in a complex microfluidic system, T-micromixer is highlighted as an example to illustrate the effect of design and operating parameters on mixing efficiency and fuid flow inside microfluidic mixers.展开更多
Microwave has been widely used in many fields,including communication,medical treatment and military industry;however,the corresponding generated radiations have been novel hazardous sources of pollution threating hu...Microwave has been widely used in many fields,including communication,medical treatment and military industry;however,the corresponding generated radiations have been novel hazardous sources of pollution threating human’s daily life.Therefore,designing high-performance microwave absorption materials(MAMs)has become an indispensable requirement.Recently,metal-organic frameworks(MOFs)have been considered as one of the most ideal precursor candidates of MAMs because of their tunable structure,high porosity and large specific surface area.Usually,MOF-derived MAMs exhibit excellent electrical conductivity,good magnetism and sufficient defects and interfaces,providing obvious merits in both impedance matching and microwave loss.In this review,the recent research progresses on MOF-derived MAMs were profoundly reviewed,including the categories of MOFs and MOF composites precursors,design principles,preparation methods and the relationship between mechanisms of microwave absorption and microstructures of MAMs.Finally,the current challenges and prospects for future opportunities of MOF-derived MAMs are also discussed.展开更多
The enhancement of chemical absorption of CO2 by K2CO3/H2O absorbents in the presence of activated carbon （AC） particles was investigated. The results show that the gas absorption rates can be enhanced significantly...The enhancement of chemical absorption of CO2 by K2CO3/H2O absorbents in the presence of activated carbon （AC） particles was investigated. The results show that the gas absorption rates can be enhanced significantly in the presence of AC particles, and the maximum enhancement factor 3.7 was observed at low stirring intensities. The enhancement factor increased rapidly with the solid loading during the initial period of absorption and then be- came mild gradually to a maximum value. Both the liquid-solid contact area and the probability of solid particles residing at the gas-liquid interface decreased with the increase of the particle size, leading to a negative effect on the enhancement of mass transfer. The influence of the particles on gas absorption decreased with the reaction rate. The stirring speed changed the interfacial coverage and mass transfer rate on the liquid side and consequently affected the mass transfer between the gas and liquid phases; the enhancement factor decreased with the stirring intensity. A heterogeneous two-zone model was proposed for predicting the enhancement factor and the calculated results agreed well with the experimental data.展开更多
Understanding carbon-supported Pt-catalyzed oxygen reduction reaction(ORR)from the perspective of the active sites is of fundamental and practical importance.In this study,three differently sized carbon nanotube-suppo...Understanding carbon-supported Pt-catalyzed oxygen reduction reaction(ORR)from the perspective of the active sites is of fundamental and practical importance.In this study,three differently sized carbon nanotube-supported Pt nanoparticles(Pt/CNT)are prepared by both atomic layer deposition(ALD)and impregnation methods.The performances of the catalysts toward the ORR in acidic media are comparatively studied to probe the effects of the sizes of the Pt nanoparticles together with their distributions,electronic properties,and local environments.The ALD-Pt/CNT catalysts show much higher ORR activity and selectivity than the impregnation-Pt/CNT catalysts.This outstanding ORR performance is ascribed to the well-controlled Pt particle sizes and distributions,desirable Pt^04f binding energy,and the Cl-free Pt surfaces based on the electrocatalytic measurements,catalyst characterizations,and model calculations.The insights reported here could guide the rational design and fine-tuning of carbon-supported Pt catalysts for the ORR.展开更多
An equation of state （EOS） for square-well chain fluids with variable range （SWCF-VR） developed based on statistical mechanics for chemical association was employed for the calculations of pressure-volume-temperat...An equation of state （EOS） for square-well chain fluids with variable range （SWCF-VR） developed based on statistical mechanics for chemical association was employed for the calculations of pressure-volume-temperature （pVT） and phase equilibrium of pure ionic liquids （ILs） and their mixtures. The new molecular parameters for 23 ILs were obtained by fitting their experimental density data over a wide temperature and pressure ranges. The mo- lecular parameters of ILs composed of homologous organic cation and an identical anion such as [Cxmim][NTf2] are good linear with respect to their molecular weight, indicating that the molecular parameters of homologous substances, subsequently p VT and vapor-liquid equilibria vapor-liquid equilibria （VLE） can be predicted using the generalized parameter when no experimental data were available. The new set of parameters were satisfactorily used for calculations of the property of solvent and ILs mixture and the solubility of gas in various ILs at low pressure only using one temperature-independent binary interaction parameter.展开更多
Coordination tuning electronic structure of host materials is a quite effective strategy for activating and improving the intrinsic properties.Herein,halogen anion(X-)-incorporated β-FeOOH(β-FeOOH(X),X=F-,Cl-,and Br...Coordination tuning electronic structure of host materials is a quite effective strategy for activating and improving the intrinsic properties.Herein,halogen anion(X-)-incorporated β-FeOOH(β-FeOOH(X),X=F-,Cl-,and Br-) was investigated with a spontaneous adsorption process,which realized a great improvement of supercapacitor performances by adjusting the coordination geometry.Experiments coupled with theoretical calculations demonstrated that the change of Fe-O bond length and structural distortion of β-FeOOH,which is rooted in halogen ions embedment,led to the relatively narrow band gap.Because of the strong electronegativity of X-,the Fe element in β-FeOOH(X)s presented the unexpected high valence state(3+δ),which is facilitating to adsorb S032-species.Consequently,the designed β-FeOOH(X)s exhibited the good electric conductivity and enhanced the contact between electrode and electrolyte.When used as a negative electrode,the β-FeOOH(F) showed the excellent specific capacity of 391.9 F g-1 at 1 A g-1 current density,almost tenfold improvement compared with initial β-FeOOH,with the superior rate capacity and cyclic stability.This combinational design principle of electronic structure and electrochemical performances provides a promising way to develop advanced electrode materials for supercapacitor.展开更多
基金supported by the Research Fund for International Scientists(RFIS-Grant numbers:52150410410)National Natural Science Foundation of Chinathe Deanship of Scientific Research and Graduate Studies at King Khalid University for funding this research work through Large Research Project under the grant number RGP2/121/1445.
文摘Inspired by molecular catalysts,researchers developed atomically precise nitrogen-coordinated single or dual metal sites imbedded in graphitized carbon(M-N-C)to fully utilize metallic sites for 02activation.These catalysts performed remarkably well in the electrocatalytic oxygen reduction reaction(ORR)due to their distinct coordination and electrical structures,Nonetheless,their maximum efficacy in practical applications has yet to be achieved.This agenda identifies tailoring the coordination environment,spin states,intersite distance,and metal-metal interaction as innovative approaches to regulate the ORR performance of these catalysts.However,it is necessary to undertake a precise assessment of these methodologies and the knowledge obtained to be implemented in the design of future M-N-C catalysts for ORR.Therefore,this review aims to analyze recent progress in M-N-C ORR catalysts,emphasizing their innovative engineering with aspects such as alteration in intersite distance,metal-metal interaction,coordination environment,and spin states.Additionally,we critically discuss how to logically monitor the atomic structure,local coordination,spin,and electronic states of M-N-C catalysts to modulate their ORR activity.We have also highlighted the challenges associated with M-N-C catalysts and proposed suggestions for their future design and fabrication.
基金National Natural Science Foundation of China,Grant/Award Number:22179029Fundamental Research Funds for the Central Universities,Grant/Award Number:buctrc202324+2 种基金Young Elite Scientists Sponsorship Program by BAST,Grant/Award Number:BYESS2023093Ministero dell'Istruzione,dell'Universitàe della Ricerca,Grant/Award Number:2022FNL89YKempestiftelserna。
文摘Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.
基金financially supported by the National Natural Science Foundation of China(51872090,51772097,22304055)the Hebei Natural Science Fund for Distinguished Young Scholar(E2019209433)+4 种基金the Youth Talent Program of Hebei Provincial Education Department(BJ2018020)the Natural Science Foundation of Hebei Province(E2020209151,E2022209158,B2022209026,D2023209012)the Central Guiding Local Science and Technology Development Fund Project(236Z4409G)the Science and Technology Project of Hebei Education Department(SLRC2019028)the Science and Technology Planning Project of Tangshan City(22130227H)。
文摘With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.
基金supported by National Key Research&Development Program-Intergovernmental International Science and Technology Innovation Cooperation Project(2021YFE0112800)National Natural Science Foundation of China(Key Program:62136003)+1 种基金National Natural Science Foundation of China(62273149)the Programme of Introducing Talents of Discipline to Universities(the 111 Project)under Grant B17017 and the Fundamental Research Funds for the Central Universities.
文摘CO_(2)-based carbon-neutral organics production processes could potentially reshape the chemical industry.However,their feasibility and net carbon footprint rely strongly on the sources of H_(2).Herein,we present a comprehensive comparative techno-economic analysis of CO_(2)-based methanol(CO_(2)TM)and aolefins(CO_(2)TO)manufacturing using various feedstock supply modes:(1)the standalone mode with external CO_(2)but H_(2)from on-site water electrolysis,(2)the integrated mode with both CO_(2)and H_(2)recovered from coal-chemical plants,and(3)the integrated mode with recycled CO_(2)but H_(2)from on-site water electrolysis.The integration of CO_(2)TM and CO_(2)TO into coal-to-olefins(CTO)and coal-to-methanol(CTM)facilities is currently cost-effective and can reduce net CO_(2)emissions by 65.7%and 68.5%,resulting in a three-fold and two-fold increase in carbon efficiency,respectively.As carbon tax policies and electrolysis technologies continue to evolve,standalone CO_(2)TM and CO_(2)TO are projected to become more economically competitive than CTO and CTM by 2035-2045.
基金the supports of the National Science Foundation of China (22008130, 22025801)the China Postdoctoral Science Foundation (2020M682124)+1 种基金the Qingdao Postdoctoral Researchers Applied Research Project Foundation (RZ2000001426)the Scientific Research Foundation for Youth Scholars from Qingdao University (DC1900014265) for this work
文摘The concept of“carbon neutrality”poses a huge challenge for chemical engineering and brings great opportunities for boosting the development of novel technologies to realize carbon offsetting and reduce carbon emissions.Developing high-efficient,low-cost,energy-efficient and eco-friendly microfluidicbased microchemical engineering is of great significance.Such kind of“green microfluidics”can reduce carbon emissions from the source of raw materials and facilitate controllable and intensified microchemical engineering processes,which represents the new power for the transformation and upgrading of chemical engineering industry.Here,a brief review of green microfluidics for achieving carbon neutral microchemical engineering is presented,with specific discussions about the characteristics and feasibility of applying green microfluidics in realizing carbon neutrality.Development of green microfluidic systems are categorized and reviewed,including the construction of microfluidic devices by bio-based substrate materials and by low carbon fabrication methods,and the use of more biocompatible and nondestructive fluidic systems such as aqueous two-phase systems(ATPSs).Moreover,low carbon applications benefit from green microfluidics are summarized,ranging from separation and purification of biomolecules,high-throughput screening of chemicals and drugs,rapid and cost-effective detections,to synthesis of fine chemicals and novel materials.Finally,challenges and perspectives for further advancing green microfluidics in microchemical engineering for carbon neutrality are proposed and discussed.
基金financial support provided by the Project of the National Key Research and Development Program of China(2018YFA0704601)the National Natural Science Foundation of China(U22A20415,22308314)+1 种基金the Natural Science Foundation of Zhejiang Province,China(LQ24B060001)the“Pioneer”and“Leading Goose”Research and Development Program of Zhejiang,China(2022C01SA442617)are gratefully acknowledged.
文摘Gas-phase polyethylene(PE)processes are among the most important methods for PE production.A deeper understanding of the process characteristics and dynamic behavior,such as properties of PE and reactor stability,holds substantial interest for both academic researchers and industries.In this study,both steady-state and dynamic models for a gas-phase polyethylene process are established as a simulation platform,which can be used to study a variety of operation tasks for commercial solution polyethylene processes,such as new product development,process control and real-time optimization.The copolymerization kinetic parameters are fitted by industrial data.Additionally,a multi-reactor series model is developed to characterize the temperature distribution within the fluidized bed reactor.The accuracy in predicting melt index and density of the polymer,and the dynamic behavior of the developed models are verified by real plant data.Moreover,the dynamic simulation platform is applied to compare four practical control schemes for reactor temperature by a series of simulation experiments,since temperature control is important in industrial production.The results reveal that all four schemes effectively track the setpoint temperature.However,only the demineralized water temperature cascade control demonstrates excellent performance in handling disturbances from both the recycle gas subsystem and the heat exchange subsystem.
基金funded by China Postdoctoral Science Foundation(2023T160406)Shanghai Pujiang Program(21PJD022)+1 种基金This project was also supported by Singapore Ministry of Education AcRF Tier 2(MOE-MOET2EP10121-0006)and AcRF Tier 1(RG7/21)This work is Supported by Shanghai Technical Service Center of Science and Engineering Computing,Shanghai University.
文摘Carbon nitride(CN)-based heterojunction photocatalysts hold promise for efficient carbon dioxide(CO_(2))reduction.However,suboptimal production yields and limited selectivity in CO_(2)conversion pose significant barriers to achieving efficient CO_(2)conversion.Here,we present the construction of a p-n heterojunction between ultrasmall Te NPs and CN nanosheet using a novel tandem hydrothermal-calcination synthesis strategy.Through ammonia-assisted calcination,ultrasmall Te NPs are grown in-situ on the CN nanosheets’surface,resulting in the generation of a robust p-n heterojunction.The synthesized heterojunction exhibits increased specific surface area,reinforced visible light absorption,intensive CO_(2)adsorption capacity,and efficient charge transfer.The optimum Te/CN-NH_(3)demonstrates superior photocatalytic CO_(2)reduction activity and durability,with nearly 100%selectivity for CO and a yield as high as 92.0μmol g^(-1)h^(-1),a fourfold increase compared to pure CN.Experimental and theoretical calculations unravel that the strong built-in electric field of the Te/CN-NH_(3)p-n heterojunction accelerates the migration of photogenerated electrons from Te NPs to the N site on CN nanosheets,thereby promoting CO_(2)reduction.This study provides a promising material design approach for the construction of highperformance p-n heterojunction photocatalysts.
基金Supported by the National Natural Science Foundation of China(No.21476125)Tsinghua University Foundation,(No.2013108930)performed at the “Exploration 100” platform supported by Tsinghua National Laboratory for Information Science and Technology
文摘With the development of manufacturing technology on the nanoscale, the precision of nano-devices is rapidly increasing with lower cost. Different from macroscale or microscale fluids, many specific phenomena and advantages are observed in nanofluidics. Devices and process involving and utilizing these phenomena play an important role in many fields in chemical engineering including separation, chemical analysis and transmission.In this article, we summarize the state-of-the-art progress in theoretical studies and manufacturing technologies on nanofluidics. Then we discuss practical applications of nanofluidics in many chemical engineering fields,especially in separation and encountering problems. Finally, we are looking forward to the future of nanofluidics and believe it will be more important in the separation process and the modern chemical industry.
基金supported by the National Natural Science Foundationthe National Key Technologies R&D Program (2011BAE28B01)the 863 Program (2013AA032501)
文摘1 Introduction Magnesium salts are very important by-product of salt lake industry in West China.Nearly 200 million cubic meters of waste brine are released to the environment
基金We would like to acknowledge the supports from the National Natural Science Foundation of China(21776150)and the State Key Laboratory of Chemical Engineering(SKL-ChE-20Z01).
文摘Electrochemical methods are environmentally friendly and have unique advantages in the synthesis of organic chemicals.However,their implementation is limited due to the complex transport problems posed by traditional electrochemical reactors.Recently,the application of microreaction technology in electrosynthesis studies has reduced the transport distance of ions and increased the specific surface area of electrodes,leading to efficient,successive,and easily scaled-up electrosynthesis technologies.In this review article,engineering advantages of using microchannels in electrosynthesis are discussed from process enhancement perspective.Flow patterns and mass transfer behaviors in recently reported electrochemical microreactors are analyzed,and prototypes for the reactor scale-up are reviewed.As a relatively new research area,many scientific rules and engineering features of electrosynthesis in microreactors require elucidation.Potential research foci,considered crucial for the development of novel electrosynthesis technology,are therefore proposed.
基金supported by the National Natural Science Foundation of China(Grant No.2230081973)Shanghai Pilot Program for Basic Research(22TQ1400100-4).
文摘Membrane technology holds significant potential for augmenting or partially substituting conventional separation techniques,such as heatdriven distillation,thereby reducing energy consumption.Organic solvent nanofiltration represents an advanced membrane separation technology capable of discerning molecules within a molecular weight range of approximately 100-1000 Da in organic solvents,offering low energy requirements and minimal carbon footprints.Molecular separation in non-polar solvent system,such as toluene,n-hexane,and n-heptane,has gained paramount importance due to their extensive use in the pharmaceutical,biochemical,and petrochemical industries.In this review,we presented recent advancements in membrane materials,membrane fabrication techniques and their promising applications for separation in nonpolar solvent system,encompassing hydrocarbon separation,bioactive molecule purification and organic solvent recovery.Furthermore,this review highlighted the challenges and opportunities associated with membrane scale-up strategies and the direct translation of this promising technology into industrial applications.
基金supported by the Research Fund for National Key Research and Development Program of China(2022YFA1503804,2021YFA1501403)the Natural Science Foundation of China(22208094,21922803,92034301,22008066 and 21776077)+2 种基金the China Postdoctoral Science Foundation(BX20190116)the Innovation Program of Shanghai Municipal Education Commission(17ZR1407300)the Program of Shanghai Academic/Technology Research Leader(21XD1421000).
文摘Essentially clearing the structure-activity relationship between iron carbide catalysts involving multiple active centers to understand the reaction mechanism of CO hydrogenation conversion process is still a great challenge.Here,two main micro-environment factors,namely electronic properties and geometrical effects were found to have an integrated effect on the mechanism of CO hydrogenation conversion,involving active sites on multiple crystal phases.The Bader charge of the surface Fe atoms on the active sites had a guiding effect on the CO activation pathway,while the spatial configuration of the active sites greatly affected the energy barriers of CO activation.Although the defective surfaces were more conducive to CO activation,the defective sites were not the only sites to dissociate CO,as CO always tended to dissociate in a wider area.This synergistic effect of the micro-environment also occurred during the CO conversion process.Surface C atoms on relatively flat configurations were more likely to form methane,while the electronic properties of the active sites could effectively describe the C-C coupling process,as well as distinguish the coupling mechanisms.
文摘Current ever-accumulating plastic waste can be considered a significant carbon resource for energy conversion and chemical production.The development of new approaches for upcycling plastic waste through chemical degradation may enable circularity and promote closed-loop recycling of carbon sources compared to traditional recycling methods.Zeolite,a widely used solid acid catalyst with high industrial potential in petroleum and biomass refining,has been extensively studied for its role in transforming plastics.In this review,we present an overview of zeolite-based catalytic systems for the chemical recycling of plastic waste and discuss how zeolites could potentially contribute to the future development of a circular economy.To provide a comprehensive understanding,we begin with a brief introduction to zeolites,analyzing their key features and exploring their opportunities as well as challenges in processing plastic waste.Subsequently,we delve into the chemistry of catalytic cracking and tandem catalysis using zeolite-based catalysts on plastics.Overall,we emphasize the importance of intelligent catalyst design and lower-energy pathways to incentivize plastic upcycling while alleviating the burden caused by waste plastics.
基金Natural Science Foundation of Xinjiang Uygur Autonomous Region,Grant/Award Number:2023D01C11National Natural Science Foundation of China,Grant/Award Numbers:22369019,U2003216+2 种基金Special Projects on Regional Collaborative Innovation-SCO Science and Technology Partnership Program,International Science and Technology Cooperation Program,Grant/Award Number:2022E01020Tianshan Talent Training Program,Grant/Award Number:2023TSYCLJ0019National Key Research and Development Program of China,Grant/Award Numbers:2022YFB4101600,2022YFB4101601。
文摘The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.
基金the National High Technology Research and Development Program of China(2006AA030202,2006AA05Z316)
文摘Microreaction technology is one of the most innovative and rapid developing fields in chemical engineering, synthesis and process technology. Many expectations toward enhanced product selectivity, yield and purity, improved safety, and access to new products and processes are directed to the microreaction technology. Microfluidic mixer is the most important component in microfluidic devices. Based on various principles, active and passive micromixers have been designed and investigated. This review is focused on the recent developments in microfluidic mixers. An overview of the flow phenomena and mixing characteristics in active and passive micromixers is presented, including the types of physical phenomena and their utilization in micromixers. Due to the simple fabrication technology and the easy implementation in a complex microfluidic system, T-micromixer is highlighted as an example to illustrate the effect of design and operating parameters on mixing efficiency and fuid flow inside microfluidic mixers.
基金Open access funding provided by Shanghai Jiao Tong University.
文摘Microwave has been widely used in many fields,including communication,medical treatment and military industry;however,the corresponding generated radiations have been novel hazardous sources of pollution threating human’s daily life.Therefore,designing high-performance microwave absorption materials(MAMs)has become an indispensable requirement.Recently,metal-organic frameworks(MOFs)have been considered as one of the most ideal precursor candidates of MAMs because of their tunable structure,high porosity and large specific surface area.Usually,MOF-derived MAMs exhibit excellent electrical conductivity,good magnetism and sufficient defects and interfaces,providing obvious merits in both impedance matching and microwave loss.In this review,the recent research progresses on MOF-derived MAMs were profoundly reviewed,including the categories of MOFs and MOF composites precursors,design principles,preparation methods and the relationship between mechanisms of microwave absorption and microstructures of MAMs.Finally,the current challenges and prospects for future opportunities of MOF-derived MAMs are also discussed.
基金Supported by the National Natural Science Foundation of China （No.20176036）.
文摘The enhancement of chemical absorption of CO2 by K2CO3/H2O absorbents in the presence of activated carbon （AC） particles was investigated. The results show that the gas absorption rates can be enhanced significantly in the presence of AC particles, and the maximum enhancement factor 3.7 was observed at low stirring intensities. The enhancement factor increased rapidly with the solid loading during the initial period of absorption and then be- came mild gradually to a maximum value. Both the liquid-solid contact area and the probability of solid particles residing at the gas-liquid interface decreased with the increase of the particle size, leading to a negative effect on the enhancement of mass transfer. The influence of the particles on gas absorption decreased with the reaction rate. The stirring speed changed the interfacial coverage and mass transfer rate on the liquid side and consequently affected the mass transfer between the gas and liquid phases; the enhancement factor decreased with the stirring intensity. A heterogeneous two-zone model was proposed for predicting the enhancement factor and the calculated results agreed well with the experimental data.
基金financially supported by the Natural Science Foundation of China(21922803 and 21776077)the Shanghai Natural Science Foundation(17ZR1407300 and 17ZR1407500)+3 种基金the Program for the Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learningthe Shanghai Rising-Star Program(17QA1401200)the State Key Laboratory of Organic-Inorganic Composites(oic-201801007)the Open Project of State Key Laboratory of Chemical Engineering(SKLChe-15C03)。
文摘Understanding carbon-supported Pt-catalyzed oxygen reduction reaction(ORR)from the perspective of the active sites is of fundamental and practical importance.In this study,three differently sized carbon nanotube-supported Pt nanoparticles(Pt/CNT)are prepared by both atomic layer deposition(ALD)and impregnation methods.The performances of the catalysts toward the ORR in acidic media are comparatively studied to probe the effects of the sizes of the Pt nanoparticles together with their distributions,electronic properties,and local environments.The ALD-Pt/CNT catalysts show much higher ORR activity and selectivity than the impregnation-Pt/CNT catalysts.This outstanding ORR performance is ascribed to the well-controlled Pt particle sizes and distributions,desirable Pt^04f binding energy,and the Cl-free Pt surfaces based on the electrocatalytic measurements,catalyst characterizations,and model calculations.The insights reported here could guide the rational design and fine-tuning of carbon-supported Pt catalysts for the ORR.
基金Supported by the National Natural Science Foundation of China （20876041, 20736002）, the National Basic Research Program of China （2009CB219902）, Program for Changjiang Scholars and Innovative Research Team in University of China （IRT0721） and the 111 Project of China （B08021）.
文摘An equation of state （EOS） for square-well chain fluids with variable range （SWCF-VR） developed based on statistical mechanics for chemical association was employed for the calculations of pressure-volume-temperature （pVT） and phase equilibrium of pure ionic liquids （ILs） and their mixtures. The new molecular parameters for 23 ILs were obtained by fitting their experimental density data over a wide temperature and pressure ranges. The mo- lecular parameters of ILs composed of homologous organic cation and an identical anion such as [Cxmim][NTf2] are good linear with respect to their molecular weight, indicating that the molecular parameters of homologous substances, subsequently p VT and vapor-liquid equilibria vapor-liquid equilibria （VLE） can be predicted using the generalized parameter when no experimental data were available. The new set of parameters were satisfactorily used for calculations of the property of solvent and ILs mixture and the solubility of gas in various ILs at low pressure only using one temperature-independent binary interaction parameter.
基金supported by the National Natural Science Foundation of China(Nos.2177060378,21627813,and 21521005)the Program for Changjiang Scholars,Innovative Research Teams in Universities(No.IRT1205)the Fundamental Research Funds for the Central Universities(Nos.12060093063 and XK1803-05).
文摘Coordination tuning electronic structure of host materials is a quite effective strategy for activating and improving the intrinsic properties.Herein,halogen anion(X-)-incorporated β-FeOOH(β-FeOOH(X),X=F-,Cl-,and Br-) was investigated with a spontaneous adsorption process,which realized a great improvement of supercapacitor performances by adjusting the coordination geometry.Experiments coupled with theoretical calculations demonstrated that the change of Fe-O bond length and structural distortion of β-FeOOH,which is rooted in halogen ions embedment,led to the relatively narrow band gap.Because of the strong electronegativity of X-,the Fe element in β-FeOOH(X)s presented the unexpected high valence state(3+δ),which is facilitating to adsorb S032-species.Consequently,the designed β-FeOOH(X)s exhibited the good electric conductivity and enhanced the contact between electrode and electrolyte.When used as a negative electrode,the β-FeOOH(F) showed the excellent specific capacity of 391.9 F g-1 at 1 A g-1 current density,almost tenfold improvement compared with initial β-FeOOH,with the superior rate capacity and cyclic stability.This combinational design principle of electronic structure and electrochemical performances provides a promising way to develop advanced electrode materials for supercapacitor.
