Heavy-metal-free ternary Cu–In–Se quantum dots(CISe QDs)are promising for solar fuel production because of their low toxicity,tunable band gap,and high light absorption coefficient.Although defects significantly aff...Heavy-metal-free ternary Cu–In–Se quantum dots(CISe QDs)are promising for solar fuel production because of their low toxicity,tunable band gap,and high light absorption coefficient.Although defects significantly affect the photophysical properties of QDs,the influence on photoelectrochemical hydrogen production is not well understood.Herein,we present the defect engineering of CISe QDs for efficient solar-energy conversion.Lewis acid–base reactions between metal halide–oleylamine complexes and oleylammonium selenocarbamate are modulated to achieve CISe QDs with the controlled amount of Cu vacancies without changing their morphology.Among them,CISe QDs with In/Cu=1.55 show the most outstanding photoelectrochemical hydrogen generation with excellent photocurrent density of up to 10.7 mA cm-2(at 0.6 VRHE),attributed to the suitable electronic band structures and enhanced carrier concentrations/lifetimes of the QDs.The proposed method,which can effectively control the defects in heavy-metal-free ternary QDs,offers a deeper understanding of the effects of the defects and provides a practical approach to enhance photoelectrochemical hydrogen generation.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
Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for...Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for assisting in building conductive,hyperelastic,and ultralight Ti_(3)C_(2)T_(x)MXene hybrid aerogels with oriented tracheid-like texture.The biomimetic hybrid aerogels are constructed by a facile bidirectional freezing strategy with CNF,carbon nanotube(CNT),and MXene based on synergistic electrostatic interaction and hydrogen bonding.Entangled CNF and CNT“mortars”bonded with MXene“bricks”of the tracheid structure produce good interfacial binding,and superior mechanical strength(up to 80%compressibility and extraordinary fatigue resistance of 1000 cycles at 50%strain).Benefiting from the biomimetic texture,CNF/CNT/MXene aerogel shows ultralow density of 7.48 mg cm^(-3)and excellent electrical conductivity(~2400 S m^(-1)).Used as pressure sensors,such aerogels exhibit appealing sensitivity performance with the linear sensitivity up to 817.3 kPa^(-1),which affords their application in monitoring body surface information and detecting human motion.Furthermore,the aerogels can also act as electrode materials of compressive solid-state supercapacitors that reveal satisfactory electrochemical performance(849.2 mF cm^(-2)at 0.8 mA cm^(-2))and superior long cycle compression performance(88%after 10,000 cycles at a compressive strain of 30%).展开更多
Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF d...Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF drags down its practical capacity and potential plateau.Herein,FeHCF with high Fe^(LS)(C)electrochemical activity(C-FeHCF)is synthesized via a facile citric acid-assisted solvothermal method.As the cathode of SIBs,C-FeHCF shows superior cycling stability(ca.87.3%capacity retention for 1000 cycles at 10 C)and outstanding rate performance(ca.68.5%capacity retention at 50 C).Importantly,the contribution of Fe^(LS)(C)to the whole capacity was quantitatively analyzed via combining dQ/dV and discharge curve for the first time,and the index reaches 44.53%for C-FeHCF,close to the theoretical value.In-situ X-ray diffraction proves the structure stability of C-FeHCF during charge-discharge process,ensuring its superior cycling performance.Furthermore,the application feasibility of the C-FeHCF cathode in quasi-solid SIBs is also evaluated.The quasi-solid SIBs with the C-FeHCF cathode exhibit excellent electrochemical performance,delivering an initial discharge capacity of 106.5 mAh g^(−1) at 5 C and high capacity retention of 89.8%over 1200 cycles.This work opens new insights into the design and development of advanced cathode materials for SIBs and the beyond.展开更多
Rechargeable lithium-ion batteries(LIBs)afford a profound impact on our modern daily life.However,LIBs are approaching the theoretical energy density,due to the inherent limitations of intercalation chemistry;thus,the...Rechargeable lithium-ion batteries(LIBs)afford a profound impact on our modern daily life.However,LIBs are approaching the theoretical energy density,due to the inherent limitations of intercalation chemistry;thus,they cannot further satisfy the increasing demands of portable electronics,electric vehicles,and grids.Therefore,battery chemistries beyond LIBs are being widely investigated.Next-generation lithium(Li)batteries,which employ Li metal as the anode and intercalation or conversion materials as the cathode,receive the most intensive interest due to their high energy density and excellent potential for commercialization.Moreover,significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions,as well as to technological improvement.This review starts by summarizing the electrolytes for next-generation Li batteries.Key challenges and recent progress in lithium-ion,lithium–sulfur,and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science.Finally,possible directions for further development in Li batteries are presented.Next-generation Li batteries are expected to promote the sustainable development of human civilization.展开更多
The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storag...The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storage and conversion application.The NiCCZ was then oxygen functionalized,facilitating the next step of stoichiometric sulfur anion diffusion during hydrothermal sulfurization,generating a flower-like metal hydroxysulfide structure(NiCCZOS)with strong partial implantation inside CC.Thus obtained NiCCZOS shows an excellent capacity when tested as a supercapacitor electrode in a three-electrode configuration.Moreover,when paired with the biomass-derived nitrogen-rich activated carbon,the asymmetric supercapacitor device shows almost 100%capacity retention even after 45,000 charge–discharge cycles with remarkable energy density(59.4 Wh kg^(-1)/263.8μWh cm^(–2))owing to a uniquely designed cathode.Furthermore,the same electrode performed as an excellent bifunctional water-splitting electrocatalyst with an overpotential of 271 mV for oxygen evolution reaction(OER)and 168.4 mV for hydrogen evolution reaction(HER)at 10 mA cm−2 current density along with 30 h of unhinged chronopotentiometric stability performance for both HER and OER.Hence,a unique metal chalcogenide composite electrode/substrate configuration has been proposed as a highly stable electrode material for flexible energy storage and conversion applications.展开更多
The concept of“green-ammonia-zero-carbon emission”is an emerging research topic in the global community and many countries driving toward decarbonizing a diversity of applications dependent on fossil fuels.In light ...The concept of“green-ammonia-zero-carbon emission”is an emerging research topic in the global community and many countries driving toward decarbonizing a diversity of applications dependent on fossil fuels.In light of this,electrochemical nitrogen reduction reaction(ENRR)received great attention at ambient conditions.The low efficiency(%)and ammonia(NH_(3))production rates are two major challenges in making a sustainable future.Besides,hydrogen evolution reaction is another crucial factor for realizing this NH_(3)synthesis to meet the large-scale commercial demand.Herein,the(i)importance of NH_(3)as an energy carrier for the next future,(ii)discussion with ENRR theory and the fundamental mechanism,(iii)device configuration and types of electrolytic systems for NH_(3)synthesis including key metrics,(iv)then moving into rising electrocatalysts for ENRR such as single-atom catalysts(SACs),MXenes,and metal–organic frameworks that were scientifically summarized,and(v)finally,the current technical contests and future perceptions are discussed.Hence,this review aims to give insightful direction and a fresh motivation toward ENRR and the development of advanced electrocatalysts in terms of cost,efficiency,and technologically large scale for the synthesis of green NH_(3).展开更多
Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utiliza...Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.展开更多
Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to i...Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.展开更多
N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to...N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to characterize.Limited understanding of doping-derived EDL structure hinders insight into the structure-performance relations and the rational design of high-performance materials.Thus,we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance,in-situ X-ray photoelectron spectroscopy,and time-offlight secondary ion mass spectrometry.We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane(IHP),which prevents ion rearrangement and enhances the migration of cations.However,this specific adsorption accelerated solvent decomposition,rendering rapid performance degradation in practical devices.This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure,which complements the classical EDL theory and provide guidance for practical applications.展开更多
1.Introduction Achieving carbon neutrality and sustainable development demands an extensive and profound systemic reform of China’s energy,industry,and economy structures.According to statistics[1,2],almost 90%of CO_...1.Introduction Achieving carbon neutrality and sustainable development demands an extensive and profound systemic reform of China’s energy,industry,and economy structures.According to statistics[1,2],almost 90%of CO_(2) emissions in China come from the energy sector,with the leading emission sources being power(48%),industry(36%),transport(8%),and buildings(5%)[1].展开更多
Activated carbon nanofibers(ACNFs)with small diameter can significantly increase the accessibility of intra pores and accelerate adsorption of molecules from water.In this study,ACNFs were made by blending K_(2)CO_(3)...Activated carbon nanofibers(ACNFs)with small diameter can significantly increase the accessibility of intra pores and accelerate adsorption of molecules from water.In this study,ACNFs were made by blending K_(2)CO_(3)or ZnCl_(2)as the activating agent into the polyacrylonitrile(PAN)in dimethylformamide solution for electrospinning prior to pyrolysis.Bisphenol-A(BPA),an endocrine disruption pollutant,is widely applied in the production of polycarbonate plastics and epoxy resins.Accordingly,BPA is often used as a model contaminant commonly removed via adsorption.Batch adsorption studies were used to evaluate the kinetics and adsorption capacity of the ACNFs.Redlich-Peterson(R-P)and Langmuir models were found to fit the isotherm of BPA adsorption better than Freundlich model,showing the homogeneous nature of the PAN originated ACNFs.The adsorption kinetics was better described by the pseudo second-order model than that by the pseudo first-order model.The fitting by intraparticle diffusion model indicates the adsorption of BPA onto ACNFs is mainly controlled by pore diffusion.High pH value and ionic strength reduced BPA adsorption from aqueous solution.The breakthrough curves studied in two different fixed bed systems(cross flow bed system and packed flow bed system)confirmed the scalability of BPA removal by ACNFs in dynamic adsorption processes.The modified dose-response model predicted well the fixed-bed outlet concentration profiles.展开更多
The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PG...The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PGO)with a P/O ratio of 8.5%was quickly synthesised by one-step electrochemical exfoliation based on a three-dimensiaonal(3D)printed reactor and natural graphite flakes.Compared with the GO prepared by the two-step electrochemical exfoliation method,the PGO synthesized by the one-step electrochemical exfoliation can better improve the performance of the membrane-electrode-assembly(MEA)based on the polybenzimidazole(PBI)membrane in the HTPEMFC.The doping of 1.5 wt%GO synthesised by electrochemical exfoliation with the 2-step method or reactor method in PBI increased the peak power density by 17.4%or 35.4%compared to MEA based on pure PBI membrane at 150℃,respectively.In addition,the doping of PGO in PBI improves its durability under accelerated stress test(AST).展开更多
The aim of this study is to generate operational data that can be used to improve the production capacity in the Fluid Catalytic Cracking Unit (FCCU) in a Refinery and Petrochemical Company. This will aid in tackling ...The aim of this study is to generate operational data that can be used to improve the production capacity in the Fluid Catalytic Cracking Unit (FCCU) in a Refinery and Petrochemical Company. This will aid in tackling the daunting challenge of unavailability of operational data that can be used to better understand and improve production capacity and ensure maximizing catalyst utilization. In addition, it addresses the challenges of analysis and control of the FCCU process due to its very complicated and little-known hydrodynamics, complex kinetics of both reactions of cracking and coke burning, strong interaction between the reactor and regenerator, and numerous operating constraints. Aspen HYSYS version 8.0 was used in modeling the cracking process using parameters extracted from the operating manual of the FCCU in the refinery. The operational data was used to compare the simulated effect of stepwise input in feed and reactor plenum temperatures as well as stepwise increase in reactor length on yield, catalyst-to-oil-ratio and catalyst regeneration. An optimum flow in naphtha was obtained by the interaction of the inlet crude flow rate, riser height, and temperature this optimum was supported by the study of the interaction of these parameters when, catalyst to oil ratio was set as the dependent parameter. The inferences drawn from the results are that the reactor plenum temperature of 560℃and a riser length of 27 m are recommended for optimum performance that ensures lasting effect of an efficient catalyst activity.展开更多
This study presents a comprehensive physicochemical analysis of neem plant leaf extracts with a focus on their potential applications in pharmaceutical and biomedical contexts. Utilizing the soxhlet extraction method ...This study presents a comprehensive physicochemical analysis of neem plant leaf extracts with a focus on their potential applications in pharmaceutical and biomedical contexts. Utilizing the soxhlet extraction method with n-hexane as the solvent, the study investigated the quantitative and qualitative composition of neem leaf extracts in reference to concentrations. The results revealed a diverse array of compounds, including cyanogenic glycoside, cardiac glycoside, tannin, steroids, phytate, flavone, oxalate, rutin, lunamarin, catechin, spatein, naringin, resveratrol, kaempferol, flavonones, epicatechin, and epihedrine, with notable concentrations. Further analyses indicated shared physicochemical properties, such as carboxyl and hydroxyl groups. Qualitative assessments affirmed the presence of flavonoid and phenolic compounds, while FTIR analysis confirmed the existence of carboxyl and hydroxyl groups. These findings emphasize the potential use of neem leaves as pharmaceutical raw materials due to their antioxidant-rich content. Additionally, the study explored the density, viscosity, saponification value, and foaming power of neem leaf extracts, providing insights into their industrial applicability. GC-MS analyses highlighted the presence of significant chemical compounds, with potential therapeutic implications. Mineral analysis demonstrated essential elements for human and animal nutrition. This study underscores neem plant leaves’ multifaceted potential across pharmaceutical, herbal medicine, cosmetic, and functional food sectors. It lays a solid foundation for further research into the specific health benefits, offering valuable insights for harnessing neem leaves’ potential in innovative products and treatments.展开更多
Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-...Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-products.However,the chemical inertness of nitrogen and poor activated capacity on catalyst surface usually produce low ammonia yield and faradic efficiency.Herein,the microfluidic technology is proposed to efficiently fabricate enriched iridium nanodots/carbon architecture.Owing to in-situ co-precipitation reaction and microfluidic manipulation,the iridium nanodots/carbon nanomaterials possess small average size,uniform dispersion,high conductivity and abundant active sites,producing good proton activation and rapid electrons transmission and moderate adsorption/desorption capacity.As a result,the as-prepared iridium nanodots/carbon nanomaterials realize large ammonia yield of 28.73 μg h^(-1) cm^(-2) and faradic efficiency of 9.14%in KOH solution.Moreover,the high ammonia yield of 11.21 μg h^(-1) cm^(-2) and faradic efficiency of 24.30%are also achieved in H_(2)SO_(4) solution.The microfluidic method provides a reference for large-scale fabrication of nano-sized catalyst materials,which may accelerate the progress of electrocatalytic NRR in industrialization field.展开更多
Foam stability tests were performed using sodium dodecyl sulfate(SDS)surfactant and SiO2 nanoparticles as foaming system at different asphaltene concentrations,and the half-life of CO_(2) foam was measured.The mechani...Foam stability tests were performed using sodium dodecyl sulfate(SDS)surfactant and SiO2 nanoparticles as foaming system at different asphaltene concentrations,and the half-life of CO_(2) foam was measured.The mechanism of foam stability reduction in the presence of asphaltene was analyzed by scanning electron microscope(SEM),UV adsorption spectrophotometric concentration measurement and Zeta potential measurement.When the mass ratio of synthetic oil to foam-formation suspension was 1:9 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 751 s to 239 s,and the half-life of SDS/silica-stabilized foams decreased from 912 s to 298 s.When the mass ratio of synthetic oil to foam-formation suspension was 2:8 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 526 s to 171 s,and the half-life of SDS/silica-stabilized foams decreased from 660 s to 205 s.In addition,due to asphaltene-SDS/silica interaction in the aqueous phase,the absolute value of Zeta potential decreases,and the surface charges of particles reduce,leading to the reduction of repulsive forces between two interfaces of thin liquid film,which in turn,damages the foam stability.展开更多
Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of ...Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.展开更多
Elliptical tanks were used as an alternative to circular tanks in order to improve mixing efficiency and reduce mixing time in unbaffled stirred tanks(USTs). Five different aspect ratios of elliptical vessels were des...Elliptical tanks were used as an alternative to circular tanks in order to improve mixing efficiency and reduce mixing time in unbaffled stirred tanks(USTs). Five different aspect ratios of elliptical vessels were designed to compare their mixing time and flow field. Computational fluid dynamics(CFD) simulations were performed using the k–ε model to calculate the mixing time and simulate turbulent flow field features, such as streamline shape, velocity distribution, vortex core region distribution, and turbulent kinetic energy(TKE) transfer. Visualization was also carried out to track the tinctorial evolution of the liquid phase. Results reveal that elliptical stirred tanks can significantly improve mixing performance in USTs. Specifically, the mixing time at an aspect ratio of 2.00 is only 45.3% of the one of a circular stirred tank. Furthermore, the secondary flow is strengthened and the vortex core region increases with the increase of aspect ratio. The axial velocity is more sensitive to the aspect ratio than the circumferential and radial velocity. Additionally, the TKE transfer in elliptical vessels is altered. These findings suggest that elliptical vessels offer a promising alternative to circular vessels for enhancing mixing performance in USTs.展开更多
基金the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(grant nos.2021R1C1C1007844,2021M3I3A1085039,2020R1F1A1061505,and 2020R1C1C1012014).
文摘Heavy-metal-free ternary Cu–In–Se quantum dots(CISe QDs)are promising for solar fuel production because of their low toxicity,tunable band gap,and high light absorption coefficient.Although defects significantly affect the photophysical properties of QDs,the influence on photoelectrochemical hydrogen production is not well understood.Herein,we present the defect engineering of CISe QDs for efficient solar-energy conversion.Lewis acid–base reactions between metal halide–oleylamine complexes and oleylammonium selenocarbamate are modulated to achieve CISe QDs with the controlled amount of Cu vacancies without changing their morphology.Among them,CISe QDs with In/Cu=1.55 show the most outstanding photoelectrochemical hydrogen generation with excellent photocurrent density of up to 10.7 mA cm-2(at 0.6 VRHE),attributed to the suitable electronic band structures and enhanced carrier concentrations/lifetimes of the QDs.The proposed method,which can effectively control the defects in heavy-metal-free ternary QDs,offers a deeper understanding of the effects of the defects and provides a practical approach to enhance photoelectrochemical hydrogen generation.
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supported by the Project of Jinan City(202228044)National Natural Science Foundation of China(32071720,32271814)+1 种基金the China Postdoctoral Science Foundation(2021M702456)China Scholarship Council for supporting their PhD program。
文摘Multifunctional architecture with intriguing structural design is highly desired for realizing the promising performances in wearable sensors and flexible energy storage devices.Cellulose nanofiber(CNF)is employed for assisting in building conductive,hyperelastic,and ultralight Ti_(3)C_(2)T_(x)MXene hybrid aerogels with oriented tracheid-like texture.The biomimetic hybrid aerogels are constructed by a facile bidirectional freezing strategy with CNF,carbon nanotube(CNT),and MXene based on synergistic electrostatic interaction and hydrogen bonding.Entangled CNF and CNT“mortars”bonded with MXene“bricks”of the tracheid structure produce good interfacial binding,and superior mechanical strength(up to 80%compressibility and extraordinary fatigue resistance of 1000 cycles at 50%strain).Benefiting from the biomimetic texture,CNF/CNT/MXene aerogel shows ultralow density of 7.48 mg cm^(-3)and excellent electrical conductivity(~2400 S m^(-1)).Used as pressure sensors,such aerogels exhibit appealing sensitivity performance with the linear sensitivity up to 817.3 kPa^(-1),which affords their application in monitoring body surface information and detecting human motion.Furthermore,the aerogels can also act as electrode materials of compressive solid-state supercapacitors that reveal satisfactory electrochemical performance(849.2 mF cm^(-2)at 0.8 mA cm^(-2))and superior long cycle compression performance(88%after 10,000 cycles at a compressive strain of 30%).
基金supported by the Natural Science Foundation of Jiangsu Province (No.BK20210474)the National Natural Science Foundation of China (No.21938005)the Fundamental Research Funds for the Central Universities (No.JUSRP122013).
文摘Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF drags down its practical capacity and potential plateau.Herein,FeHCF with high Fe^(LS)(C)electrochemical activity(C-FeHCF)is synthesized via a facile citric acid-assisted solvothermal method.As the cathode of SIBs,C-FeHCF shows superior cycling stability(ca.87.3%capacity retention for 1000 cycles at 10 C)and outstanding rate performance(ca.68.5%capacity retention at 50 C).Importantly,the contribution of Fe^(LS)(C)to the whole capacity was quantitatively analyzed via combining dQ/dV and discharge curve for the first time,and the index reaches 44.53%for C-FeHCF,close to the theoretical value.In-situ X-ray diffraction proves the structure stability of C-FeHCF during charge-discharge process,ensuring its superior cycling performance.Furthermore,the application feasibility of the C-FeHCF cathode in quasi-solid SIBs is also evaluated.The quasi-solid SIBs with the C-FeHCF cathode exhibit excellent electrochemical performance,delivering an initial discharge capacity of 106.5 mAh g^(−1) at 5 C and high capacity retention of 89.8%over 1200 cycles.This work opens new insights into the design and development of advanced cathode materials for SIBs and the beyond.
基金the National Key Research and Development Program(2016YFA0202500 and 2016YFA0200102)the National Natural Science Foundation of China(21676160,21776019,and 21825501)the Tsinghua University Initiative Scientific Research Program.
文摘Rechargeable lithium-ion batteries(LIBs)afford a profound impact on our modern daily life.However,LIBs are approaching the theoretical energy density,due to the inherent limitations of intercalation chemistry;thus,they cannot further satisfy the increasing demands of portable electronics,electric vehicles,and grids.Therefore,battery chemistries beyond LIBs are being widely investigated.Next-generation lithium(Li)batteries,which employ Li metal as the anode and intercalation or conversion materials as the cathode,receive the most intensive interest due to their high energy density and excellent potential for commercialization.Moreover,significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions,as well as to technological improvement.This review starts by summarizing the electrolytes for next-generation Li batteries.Key challenges and recent progress in lithium-ion,lithium–sulfur,and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science.Finally,possible directions for further development in Li batteries are presented.Next-generation Li batteries are expected to promote the sustainable development of human civilization.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(2021R1A4A2000934).
文摘The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storage and conversion application.The NiCCZ was then oxygen functionalized,facilitating the next step of stoichiometric sulfur anion diffusion during hydrothermal sulfurization,generating a flower-like metal hydroxysulfide structure(NiCCZOS)with strong partial implantation inside CC.Thus obtained NiCCZOS shows an excellent capacity when tested as a supercapacitor electrode in a three-electrode configuration.Moreover,when paired with the biomass-derived nitrogen-rich activated carbon,the asymmetric supercapacitor device shows almost 100%capacity retention even after 45,000 charge–discharge cycles with remarkable energy density(59.4 Wh kg^(-1)/263.8μWh cm^(–2))owing to a uniquely designed cathode.Furthermore,the same electrode performed as an excellent bifunctional water-splitting electrocatalyst with an overpotential of 271 mV for oxygen evolution reaction(OER)and 168.4 mV for hydrogen evolution reaction(HER)at 10 mA cm−2 current density along with 30 h of unhinged chronopotentiometric stability performance for both HER and OER.Hence,a unique metal chalcogenide composite electrode/substrate configuration has been proposed as a highly stable electrode material for flexible energy storage and conversion applications.
基金Ministry of Science and ICT,South Korea,Grant/Award Numbers:2019R1A2C2088174,2021R1A5A1084921。
文摘The concept of“green-ammonia-zero-carbon emission”is an emerging research topic in the global community and many countries driving toward decarbonizing a diversity of applications dependent on fossil fuels.In light of this,electrochemical nitrogen reduction reaction(ENRR)received great attention at ambient conditions.The low efficiency(%)and ammonia(NH_(3))production rates are two major challenges in making a sustainable future.Besides,hydrogen evolution reaction is another crucial factor for realizing this NH_(3)synthesis to meet the large-scale commercial demand.Herein,the(i)importance of NH_(3)as an energy carrier for the next future,(ii)discussion with ENRR theory and the fundamental mechanism,(iii)device configuration and types of electrolytic systems for NH_(3)synthesis including key metrics,(iv)then moving into rising electrocatalysts for ENRR such as single-atom catalysts(SACs),MXenes,and metal–organic frameworks that were scientifically summarized,and(v)finally,the current technical contests and future perceptions are discussed.Hence,this review aims to give insightful direction and a fresh motivation toward ENRR and the development of advanced electrocatalysts in terms of cost,efficiency,and technologically large scale for the synthesis of green NH_(3).
基金financially supported by the National Key Research and Development Program of China (2018YFA0702002)the Beijing Natural Science Foundation (Z210016)the National Natural Science Foundation of China (21935001)。
文摘Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.
基金supported by the Climate Change Response Project (NRF-2019M1A2A2065612)the Brainlink Project (NRF2022H1D3A3A01081140)+3 种基金the NRF-2021R1A4A3027878 and the No. RS-2023-00212273 funded by the Ministry of Science and ICT of Korea via National Research Foundationresearch funds from Hanhwa Solutions Chemicals (1.220029.01)UNIST (1.190013.01)supported by the Institute for Basic Science (IBS-R019-D1)。
文摘Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.
基金the National Science Foundation for Excellent Young Scholars of China(21922815)the National Natural Science Foundation of China(22179139)+2 种基金the National Key Research and Development Program of China(2020YFB1505800)the Youth Innovation Promotion Association of CAS(2019178)the“Transformational Technologies for Clean Energy and Demonstration”Strategic Priority Research Program of the CAS(XDA21000000)。
文摘N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to characterize.Limited understanding of doping-derived EDL structure hinders insight into the structure-performance relations and the rational design of high-performance materials.Thus,we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance,in-situ X-ray photoelectron spectroscopy,and time-offlight secondary ion mass spectrometry.We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane(IHP),which prevents ion rearrangement and enhances the migration of cations.However,this specific adsorption accelerated solvent decomposition,rendering rapid performance degradation in practical devices.This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure,which complements the classical EDL theory and provide guidance for practical applications.
基金supported by the National Natural Science Foundation of China(21825501)the Ordos–Tsinghua Innovative and Collaborative Research Program in Carbon Neutrality。
文摘1.Introduction Achieving carbon neutrality and sustainable development demands an extensive and profound systemic reform of China’s energy,industry,and economy structures.According to statistics[1,2],almost 90%of CO_(2) emissions in China come from the energy sector,with the leading emission sources being power(48%),industry(36%),transport(8%),and buildings(5%)[1].
基金financially supported by the National Science Foundation(1438518)。
文摘Activated carbon nanofibers(ACNFs)with small diameter can significantly increase the accessibility of intra pores and accelerate adsorption of molecules from water.In this study,ACNFs were made by blending K_(2)CO_(3)or ZnCl_(2)as the activating agent into the polyacrylonitrile(PAN)in dimethylformamide solution for electrospinning prior to pyrolysis.Bisphenol-A(BPA),an endocrine disruption pollutant,is widely applied in the production of polycarbonate plastics and epoxy resins.Accordingly,BPA is often used as a model contaminant commonly removed via adsorption.Batch adsorption studies were used to evaluate the kinetics and adsorption capacity of the ACNFs.Redlich-Peterson(R-P)and Langmuir models were found to fit the isotherm of BPA adsorption better than Freundlich model,showing the homogeneous nature of the PAN originated ACNFs.The adsorption kinetics was better described by the pseudo second-order model than that by the pseudo first-order model.The fitting by intraparticle diffusion model indicates the adsorption of BPA onto ACNFs is mainly controlled by pore diffusion.High pH value and ionic strength reduced BPA adsorption from aqueous solution.The breakthrough curves studied in two different fixed bed systems(cross flow bed system and packed flow bed system)confirmed the scalability of BPA removal by ACNFs in dynamic adsorption processes.The modified dose-response model predicted well the fixed-bed outlet concentration profiles.
基金financially supported by the UK Research Council EPSRC EP/009050/1。
文摘The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PGO)with a P/O ratio of 8.5%was quickly synthesised by one-step electrochemical exfoliation based on a three-dimensiaonal(3D)printed reactor and natural graphite flakes.Compared with the GO prepared by the two-step electrochemical exfoliation method,the PGO synthesized by the one-step electrochemical exfoliation can better improve the performance of the membrane-electrode-assembly(MEA)based on the polybenzimidazole(PBI)membrane in the HTPEMFC.The doping of 1.5 wt%GO synthesised by electrochemical exfoliation with the 2-step method or reactor method in PBI increased the peak power density by 17.4%or 35.4%compared to MEA based on pure PBI membrane at 150℃,respectively.In addition,the doping of PGO in PBI improves its durability under accelerated stress test(AST).
文摘The aim of this study is to generate operational data that can be used to improve the production capacity in the Fluid Catalytic Cracking Unit (FCCU) in a Refinery and Petrochemical Company. This will aid in tackling the daunting challenge of unavailability of operational data that can be used to better understand and improve production capacity and ensure maximizing catalyst utilization. In addition, it addresses the challenges of analysis and control of the FCCU process due to its very complicated and little-known hydrodynamics, complex kinetics of both reactions of cracking and coke burning, strong interaction between the reactor and regenerator, and numerous operating constraints. Aspen HYSYS version 8.0 was used in modeling the cracking process using parameters extracted from the operating manual of the FCCU in the refinery. The operational data was used to compare the simulated effect of stepwise input in feed and reactor plenum temperatures as well as stepwise increase in reactor length on yield, catalyst-to-oil-ratio and catalyst regeneration. An optimum flow in naphtha was obtained by the interaction of the inlet crude flow rate, riser height, and temperature this optimum was supported by the study of the interaction of these parameters when, catalyst to oil ratio was set as the dependent parameter. The inferences drawn from the results are that the reactor plenum temperature of 560℃and a riser length of 27 m are recommended for optimum performance that ensures lasting effect of an efficient catalyst activity.
文摘This study presents a comprehensive physicochemical analysis of neem plant leaf extracts with a focus on their potential applications in pharmaceutical and biomedical contexts. Utilizing the soxhlet extraction method with n-hexane as the solvent, the study investigated the quantitative and qualitative composition of neem leaf extracts in reference to concentrations. The results revealed a diverse array of compounds, including cyanogenic glycoside, cardiac glycoside, tannin, steroids, phytate, flavone, oxalate, rutin, lunamarin, catechin, spatein, naringin, resveratrol, kaempferol, flavonones, epicatechin, and epihedrine, with notable concentrations. Further analyses indicated shared physicochemical properties, such as carboxyl and hydroxyl groups. Qualitative assessments affirmed the presence of flavonoid and phenolic compounds, while FTIR analysis confirmed the existence of carboxyl and hydroxyl groups. These findings emphasize the potential use of neem leaves as pharmaceutical raw materials due to their antioxidant-rich content. Additionally, the study explored the density, viscosity, saponification value, and foaming power of neem leaf extracts, providing insights into their industrial applicability. GC-MS analyses highlighted the presence of significant chemical compounds, with potential therapeutic implications. Mineral analysis demonstrated essential elements for human and animal nutrition. This study underscores neem plant leaves’ multifaceted potential across pharmaceutical, herbal medicine, cosmetic, and functional food sectors. It lays a solid foundation for further research into the specific health benefits, offering valuable insights for harnessing neem leaves’ potential in innovative products and treatments.
基金supported by the National Natural Science Foundation of China(22025801)and(22208190)National Postdoctoral Program for Innovative Talents(BX2021146)Shuimu Tsinghua Scholar Program(2021SM055).
文摘Electrocatalytic nitrogen reduction reaction(NRR)is considered as a promising candidate to achieve ammonia synthesis because of clean electric energy,moderate reaction condition,safe operating process and harmless by-products.However,the chemical inertness of nitrogen and poor activated capacity on catalyst surface usually produce low ammonia yield and faradic efficiency.Herein,the microfluidic technology is proposed to efficiently fabricate enriched iridium nanodots/carbon architecture.Owing to in-situ co-precipitation reaction and microfluidic manipulation,the iridium nanodots/carbon nanomaterials possess small average size,uniform dispersion,high conductivity and abundant active sites,producing good proton activation and rapid electrons transmission and moderate adsorption/desorption capacity.As a result,the as-prepared iridium nanodots/carbon nanomaterials realize large ammonia yield of 28.73 μg h^(-1) cm^(-2) and faradic efficiency of 9.14%in KOH solution.Moreover,the high ammonia yield of 11.21 μg h^(-1) cm^(-2) and faradic efficiency of 24.30%are also achieved in H_(2)SO_(4) solution.The microfluidic method provides a reference for large-scale fabrication of nano-sized catalyst materials,which may accelerate the progress of electrocatalytic NRR in industrialization field.
文摘Foam stability tests were performed using sodium dodecyl sulfate(SDS)surfactant and SiO2 nanoparticles as foaming system at different asphaltene concentrations,and the half-life of CO_(2) foam was measured.The mechanism of foam stability reduction in the presence of asphaltene was analyzed by scanning electron microscope(SEM),UV adsorption spectrophotometric concentration measurement and Zeta potential measurement.When the mass ratio of synthetic oil to foam-formation suspension was 1:9 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 751 s to 239 s,and the half-life of SDS/silica-stabilized foams decreased from 912 s to 298 s.When the mass ratio of synthetic oil to foam-formation suspension was 2:8 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 526 s to 171 s,and the half-life of SDS/silica-stabilized foams decreased from 660 s to 205 s.In addition,due to asphaltene-SDS/silica interaction in the aqueous phase,the absolute value of Zeta potential decreases,and the surface charges of particles reduce,leading to the reduction of repulsive forces between two interfaces of thin liquid film,which in turn,damages the foam stability.
基金supported by Thailand Science Research and Innovation Fund Chulalongkorn University,Thailand(IND66210014)。
文摘Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.
基金supported by the National Key Research and Development Project(2022YFB3504305,2019YFC1905802)National Natural Science Foundation of China(22078030)+2 种基金Joint Funds of the National Natural Science Foundation of China(U1802255)Key Project of Independent Research Project of State Key Laboratory of Coal Mine Disaster Dynamics and Control(2011DA105287-zd201902)Three Gorges Laboratory Open Fund of Hubei Province(SK211009,SK215001).
文摘Elliptical tanks were used as an alternative to circular tanks in order to improve mixing efficiency and reduce mixing time in unbaffled stirred tanks(USTs). Five different aspect ratios of elliptical vessels were designed to compare their mixing time and flow field. Computational fluid dynamics(CFD) simulations were performed using the k–ε model to calculate the mixing time and simulate turbulent flow field features, such as streamline shape, velocity distribution, vortex core region distribution, and turbulent kinetic energy(TKE) transfer. Visualization was also carried out to track the tinctorial evolution of the liquid phase. Results reveal that elliptical stirred tanks can significantly improve mixing performance in USTs. Specifically, the mixing time at an aspect ratio of 2.00 is only 45.3% of the one of a circular stirred tank. Furthermore, the secondary flow is strengthened and the vortex core region increases with the increase of aspect ratio. The axial velocity is more sensitive to the aspect ratio than the circumferential and radial velocity. Additionally, the TKE transfer in elliptical vessels is altered. These findings suggest that elliptical vessels offer a promising alternative to circular vessels for enhancing mixing performance in USTs.
